WO2008041468A1 - Method of forming pattern - Google Patents

Method of forming pattern Download PDF

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Publication number
WO2008041468A1
WO2008041468A1 PCT/JP2007/067880 JP2007067880W WO2008041468A1 WO 2008041468 A1 WO2008041468 A1 WO 2008041468A1 JP 2007067880 W JP2007067880 W JP 2007067880W WO 2008041468 A1 WO2008041468 A1 WO 2008041468A1
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WIPO (PCT)
Prior art keywords
group
pattern
resist
acid
alkyl group
Prior art date
Application number
PCT/JP2007/067880
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French (fr)
Japanese (ja)
Inventor
Hisanobu Harada
Shinichi Kohno
Jun Iwashita
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
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Publication date
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Publication of WO2008041468A1 publication Critical patent/WO2008041468A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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

Definitions

  • the present invention relates to a pattern forming method for forming a pattern by a double patterning method using a chemically amplified resist composition.
  • the fine pattern is usually made of an organic material, and is formed by a technique such as a lithography method or a nanoimprint method.
  • a lithography method a resist film made of a resist composition containing a base material component such as a resin is formed on a support such as a substrate, and a mask in 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 such as light or an electron beam through (mask pattern) and performing development.
  • a resist composition that changes its characteristics so that the exposed part dissolves in the developer is positive, and a resist composition that changes its characteristics does not dissolve in the developer!
  • a semiconductor element or the like is manufactured through a process of processing the substrate by etching using the resist pattern as a mask.
  • Resist compositions 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 composition containing a base material component 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 usually contains, as a base material component, a resin whose alkali solubility is increased by the action of an acid.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-241385
  • Non-Patent Document 1 Proceeding of SPIE, Volume 5, 256, 985-994 (2003).
  • Non-Patent Document 2 Proceedings of SPIE, Vol. 6 153, 61531K;! To p. 7 (2006).
  • the patterns that can be actually formed on the substrate by the conventional double-battered-lung method including the methods proposed in Non-Patent Documents 1 and 2 are those that have a pattern collapse or high verticality and shape. There were still problems in forming high-definition and high-aspect-ratio patterns.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of forming a high-definition and high aspect ratio pattern on a support. Means for solving the problem In order to achieve the above object, the present invention employs the following configuration.
  • the present invention is a pattern forming method for forming a pattern using a chemically amplified resist composition, the method comprising: forming a lower layer film using a lower layer film forming material on a support; and Forming a hard mask using a silicon-based hard mask forming material on the film; applying a chemically amplified negative resist composition on the hard mask; and forming a first resist film; The first resist film is selectively exposed through a first mask pattern and developed to form a first resist pattern, and the hard mask is etched using the first resist pattern as a mask.
  • a step of forming a first pattern, and a step of forming a second resist film by applying a chemically amplified positive silicon resist composition on the first pattern and the lower layer film.
  • a pattern with high definition and a high aspect ratio can be formed on a support.
  • FIG. IE is a schematic process diagram illustrating a patterning process (1) in a preferred embodiment of a pattern forming method of the present invention.
  • FIG. 2D is a schematic process diagram illustrating a patterning process (2) in a preferred embodiment of the pattern forming method of the present invention.
  • the chemically amplified positive silicon resist composition is not particularly limited, but is usually a component that increases alkali solubility by the action of an acid and an acid generator component that generates an acid upon exposure.
  • the thing containing is used. And what has resistance with respect to the oxygen plasma etching generally used for pattern formation of the lower layer film mentioned later is preferable.
  • a resin component (A) whose alkali solubility is increased by the action of an acid hereinafter referred to as “component (A)”
  • an acid generator component (B) hereinafter referred to as “acid generator” which generates an acid upon exposure
  • the resin component (A) is a structural unit (al) represented by the following general formula (al) and the following general formula (a2):
  • R 1 is an acid-decomposable group represented by the following general formula (I).
  • R 2 to R 3 are each independently a linking group;
  • L is a C 1 -C; linear or branched alkylene group having 10 carbons, and a linear chain having 2 to 20 carbons.
  • the resist composition which is strong, is insoluble in alkali before exposure, and is exposed to the component (B) by exposure.
  • the acid acts on the component (A) to increase its alkali solubility.
  • the exposed portion becomes alkali-soluble.
  • the unexposed area remains insoluble in alkali and does not change, a resist pattern can be formed by performing alkali development.
  • the structural unit (al) contributes to the improvement of the transparency of the resin (A1), in particular, the transparency to light having a wavelength of 200 nm or less, thereby improving the sensitivity and resolution of the resist composition.
  • Resin (A1), the proportion of the structural unit (al), based on the combined total of all the structural units that constitute the resin (A1), 20 to 90 Monore 0/0 Ca Preferably, preferably from 30 to 80 Monore 0/0 Ca , 40-60 Monore 0/0 mosquitoes further preferred.
  • the proportion of the structural unit (al) is 20 mol% or more, transparency to light having a wavelength of 200 nm or less is improved. If it is 90 mol% or less, the balance with other structural units such as the structural unit (a2) is good.
  • the structural unit (a2) has an acid-decomposable group R 1 represented by the above general formula (I).
  • R 1 an acid-decomposable group represented by the above general formula (I).
  • R 2 to R 3 are each independently a linking group.
  • the linking group is not particularly limited.
  • a linear or branched alkylene group having 1 to 5 carbon atoms is preferable, and a methylene group and an ethylene group are more preferable.
  • L represents a linear or branched alkylene group, a linear or branched fluoroalkylene group, an arylene group, a cyclic alkylene group, or an alkali monolene group.
  • the linear or branched alkylene group of L is preferably 1 to 10 carbon atoms, more preferably a linear or branched alkylene group having 1 to 5 carbon atoms, particularly a methylene group.
  • An ethylene group is preferred.
  • the hydrogen atoms of the linear or branched alkyl group having 2 to 20 carbon atoms are fluorine atoms.
  • the arylene group of L may be an unsubstituted arylene group, or a substituted arylene group in which some or all of the hydrogen atoms bonded to the carbon atoms constituting the ring of the unsubstituted arylene group are substituted with a substituent. It may be.
  • the unsubstituted arylene group include groups in which two hydrogen atoms have been removed from benzene, naphthalene, anthracene and the like.
  • the unsubstituted arylene group preferably has 6 to 14 carbon atoms.
  • substituents in the substituted arylene group include an alkyl group, an alkoxy group, and an aryl group. These substituents preferably have 1 to 10 carbon atoms.
  • the cyclic alkylene group of L may be an unsubstituted cyclic alkylene group, or a substituted alkylene in which part or all of the hydrogen atoms bonded to the carbon atoms constituting the ring of the cyclic alkylene group are substituted with a substituent. It may be a group! / As the unsubstituted cyclic alkylene group, a cyclic alkylene group having 4 to 12 carbon atoms is preferable.
  • two hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane; , Norbornenenes, norbornene, methylnorbornane, ethylnorbornane, methylnorbornene, ethylnorbornene, isobornane, tricyclodecane, tetracyclododecane, etc.
  • a monocycloalkane such as cyclopentane or cyclohexane
  • Norbornenenes norbornene, methylnorbornane, ethylnorbornane, methylnorbornene, ethylnorbornene, isobornane, tricyclodecane, tetracyclododecane, etc.
  • substituent in the substituted cyclic alkylene group include the same groups as those described above as the substituent in the substituted arylene group.
  • the alkali monolene group of L is a group formed by bonding two alkylene groups to an aromatic ring such as benzene, naphthalene or anthracene.
  • the aromatic ring preferably has 6 to 14 carbon atoms.
  • Examples of the alkylene group include the same groups as those described above for R 2 to, and the two alkylene groups may be the same or different.
  • Examples of the unsubstituted alkali monolene group include a group represented by the following formula (AL-1).
  • Examples of the substituted alkali monolene group include groups in which part or all of the hydrogen atoms bonded to the carbon atoms constituting the aromatic ring of the unsubstituted alkali monolene group are substituted with a substituent. Examples of the group include the same groups as those described above as the substituent in the substituted arylene group.
  • L is preferably a methylene group, an ethylene group, a cyclic alkylene group, or an alkali monolene group, and an unsubstituted cyclic alkylene group is more preferred. (Norbornene group) is particularly preferred!
  • Z is an acid-dissociable group.
  • the “acid-dissociable group” means a group that is dissociated by the action of an acid generated by (B) component force by exposure.
  • the acid force generated from the component (B) by the exposure is dissociated.
  • the alkali solubility of the resin (A1) increases.
  • the acid dissociable group of Z is not particularly limited as long as it is a group that can be dissociated from the polymer main chain of the resin (A1) by the action of the acid generated from the component (B).
  • those conventionally proposed as acid dissociable, dissolution inhibiting groups for the base component of the positive resist composition can be used.
  • the “acid-dissociable, dissolution-inhibiting group” means an acid-dissociation property that has an alkali-dissolution inhibitory property that renders the entire compound insoluble in alkali before dissociation, and changes the entire compound to alkali-soluble after dissociation. It is a group.
  • the acid dissociable group are not particularly limited.
  • the group represented by the general formula COOR 7 the group represented by the general formula 1 OCOOR 8 ; and the general formula 1 OR 9 Groups and the like.
  • R 7 to R 9 are each an organic group having an action of imparting acid dissociation to the group represented by COOR 7 , the group represented by OCOOR 8 , and the group represented by —OR 9. is there.
  • the organic group means a group having at least a carbon atom and one or more other atoms.
  • R 7 examples include a chain-like tertiary alkyl group; an aliphatic cyclic group containing a tertiary carbon atom on the ring; a 2-trialkylethyl group.
  • the chain-like tertiary alkyl group is preferably 4 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. More specific examples of the chain-like tertiary alkyl group include a tert butyl group and a tert amyl group.
  • the “aliphatic cyclic group” refers to a monocyclic group or polycyclic group having no aromaticity.
  • the aliphatic cyclic group containing a tertiary carbon atom on the ring 4 to 14 carbon atoms are preferable, 5 to 10 carbon atoms are more preferable.
  • aliphatic cyclic group examples include an adamantyl group, a nonolebonorinole group, an isobornyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 2-methyl-2-isobornyl group, 2-butyl-2-adamantyl group, 2-propyl-2-isobornyl group, 2-methyl-2-tetracyclodece 2-nore group, 2-methylolene 2-dihydrodicyclopentageninole cyclohexylene group, 1-methyl-1-cyclopentyl Group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, and the like.
  • Examples of the 2-trialkylethyl group include a 2-trimethinoresilinoreethinole group and a 2-triethinorecyleethyl group.
  • R 8 examples include the same as R 7 described above.
  • R 9 examples include a tetrahydrobiranyl group, a 1-adamantoxymethyl group, a 1-cyclohexylanoloxymethyl group, and a trialkylsilyl group.
  • examples of the trialkylsilyl group include a trimethylsilyl group. .
  • Z is preferably a group represented by the general formula 1 COOR 7 ;
  • R 7 is more preferably a chain-like tertiary alkyl group; and
  • R 7 is tert butyl.
  • the group which is the group, ie the tert butoxycarbonyl group is most preferred!
  • g may be 0 or 1 and is preferably 0.
  • h may be 0, may be 1, and is preferably 0.
  • R 1 is particularly preferably a group represented by the following general formula (1-1).
  • R ′ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z ′ is a chain-like tertiary alkyl group.
  • one type may be used alone, or two or more types may be used in combination.
  • Resin (A1) the proportion of the structural unit (a2), based on the combined total of all the structural units that constitute the resin (A1), 10 to 80 Monore 0/0 Ca
  • the proportion of the structural unit (a2) is 10 mol% or more, a pattern can be obtained when the resist composition is used, and when it is less than the upper limit, the balance with other structural units is good.
  • Mashigu 70 mole 0/0 or more and 50 mol% or more may be more preferable instrument 100 mole 0/0.
  • the resin (A1) may contain other structural units other than the structural units (al) and (a2) as long as the effects of the present invention are not impaired!
  • Examples of the structural unit other than the structural units (al) and (a2) include the structural unit (a3) represented by the following formula (a3).
  • R 15 is an alkyl group having 1 to 20 carbon atoms or an aryl group.
  • the alkyl group for R 15 may be linear, branched, or cyclic. Carbon number;! -6 to 6 linear or branched alkyl group, or 5 to 6 carbon atoms; Specific examples of preferred cyclic alkyl groups include methyl, ethyl, n-propyl, isopropylene, n-butyl, tert-butyl, cyclopentyl, and cyclohexyl groups. I can get lost.
  • Examples of the aryl group of R 15 include a phenyl group and a naphthyl group, and these have an alkyl group or the like as a substituent!
  • the resin (A1) can be produced using a known method for producing a hydrogen silsesquioxane resin.
  • One example is trihalogenation such as trichlorosilane (HSiCl).
  • a hydrogen silsesquioxane resin (hereinafter referred to as precursor resin) containing the structural unit (al) is synthesized.
  • the precursor resin produced in this way contains the structural unit (al).
  • the structural unit (al) usually, in addition to the structural unit (al), (Si (OH) O), (HSi (OH) 0), (SiO
  • polymers having various network structures such as ladder type, random type, and cage type are usually used.
  • a structural unit or the like substituted with is also formed.
  • R 1 is, for example, a compound corresponding to R 1 to be introduced by hydrosilylation reaction in the presence of a catalyst (for example, bicyclo [2, 2, 1] hept-5-ene-2-tert-butylcarboxylate, etc.) Can be introduced by reacting with the precursor resin.
  • a catalyst for example, bicyclo [2, 2, 1] hept-5-ene-2-tert-butylcarboxylate, etc.
  • the proportion of the structural units (al), (a2), etc. in the resin (A1) can be adjusted by adjusting the amount of the compound corresponding to R 1 to be introduced and the reaction conditions.
  • 65 is particularly preferred, and 65: 35-40: 60 is most preferred! /.
  • Mass average molecular weight (Mw) of resin (A1) gel permeation chromatography
  • GPC Polystyrene
  • Mw / Mn is not particularly limited, but is preferably 1.0 to 6.0, and more preferably 1.0 to 2.5.
  • resin (A1) one type may be used alone, or two or more types may be used in combination.
  • the proportion of the resin (A1) in the component ( ⁇ ⁇ ⁇ ) is excellent in forming a high-definition and high aspect ratio pattern on the support, which is the effect of the present invention.
  • % Or more is preferred 70 mass% or more may be 100 mass%.
  • the component ( ⁇ ⁇ ⁇ ) may contain a resin component ( ⁇ 2) other than the resin (A1) (hereinafter referred to as the component ( ⁇ 2)) as long as the effects of the present invention are not impaired. Good. There are no particular restrictions on the strength and strength ( ⁇ 2).
  • any of a number of resins generally proposed as base resins for chemically amplified resist compositions can be used. It can be selected and used.
  • the component (ii) is not particularly limited, and any component that has been proposed as an acid generator for chemically amplified resists can be used.
  • Such ( ⁇ ) components have so far included onium salt-based acid generators such as odonium salts and sulfonium salts, oxime sulfonate-based acid generators, bisalkyl or bis-sulfonylsulfonyl diazomethanes.
  • diazomethane acid generators such as poly (bissulfonino) diazomethanes, nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators.
  • Examples of the onium salt-based acid generator include an acid generator represented by the following general formula (b-0).
  • R 51 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, a halogen atom, a straight Chain or branched alkyl group, linear or branched alkyl halide group
  • R 53 is an aryl group which may have a substituent;
  • u ′′ is an integer of 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 still more preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 6 to 10 carbon atoms, and most preferably 10 to 10 carbon atoms.
  • the fluorinated alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the alkyl fluoride 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%.
  • all hydrogen atoms are substituted with fluorine atoms. This is preferable because the strength of the acid increases.
  • R 51 is most preferably a linear alkyl group or a 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 a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably;!-5, in particular;!-4, and more preferably 1-3.
  • 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.
  • Alkyl group here, "in the R 52 The same thing as an "alkyl group” is mentioned.
  • Examples of the halogen atom to be substituted are the same as those described above for “no, log atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly preferably !! to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 has a substituent! /, May! /, An aryl group, and the structure of the basic ring (matrix ring) is a naphthyl group or a phenyl group. And anthracenyl group. From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
  • substituents examples include a hydroxyl group and a lower alkyl group (straight chain or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
  • lower means 1 to 5 carbon atoms.
  • the aryl group of R 53 has no substituent! /, More preferably! / ,.
  • u is an integer of 1 to 3, 2 or 3 is preferred and 3 is particularly desirable.
  • Preferable examples of the acid generator represented by the general formula (b-0) include the following.
  • Examples of other onium salt acid generators other than the above include compounds represented by the following general formula (b-1) or (b-2).
  • R 5 represents an aryl group or an alkyl group
  • R 4 represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group; Representation;
  • R to R ' represents one group, and at least one of R 5 "to" represents an aryl group.
  • 1 “ ⁇ ! ⁇ ” Each independently represents an aryl group or an alkyl group. ! ⁇ ,, to 3 "out of, representing at least 1 Tsu is Ariru group. 1" ⁇ ! ⁇ 3 "out of, 2 or more preferably be a ⁇ Li Lumpur based tool 1" ⁇ ! ⁇ "Of Most preferably all are aryl.
  • the aryl group of Ri “to” 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. It does not need to be substituted with an atom or the like.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group.
  • the hydrogen atom of the aryl group is substituted! /, May! /,
  • the alkyl group is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert. Most preferred is a butyl group.
  • alkoxy group that may be substituted for the hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having from 5 to 5 carbon atoms being preferred.
  • the halogen atom with which the hydrogen atom of the aryl group may be substituted is preferably a fluorine atom.
  • R1 as alkyl group "to R 3", Nag particularly limited for example, the number of carbon atoms;! A ⁇ 10 linear
  • the number of carbon atoms is preferably 1 to 5.
  • R 4 ′′ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
  • the linear alkyl group preferably has 1 to 10 carbon atoms; preferably 8 to 8 carbon atoms; Most preferably, it is 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as indicated by R 1 ′′ and preferably has 4 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Most preferably, it has 6 to 10 carbon atoms.
  • the fluorinated alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Also.
  • the fluoride The fluorination rate of the alkyl group is preferably 10 to; 100%, more preferably 50 to 100%. Particularly, all the hydrogen atoms were substituted with fluorine atoms. It is preferable because the strength of the acid is increased.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ to R 6 ′′ each independently represents an aryl group or an alkyl group.
  • At least one of R 5 "to R 6 " represents an aryl group. All of R 5 “to R 6 " are preferably aryl groups.
  • R 5 " ⁇ R 6 " arele groups are the same as those for 1 " ⁇ ! ⁇ "
  • R 5 " ⁇ R 6" 1 " ⁇ ! ⁇ "
  • R 5 " ⁇ R 6" is a phenyl group preferable.
  • R 4 in the formula (b-1) Formula (b-2) R 4 in the same groups as those described above for.
  • onion salt acid generators represented by the formulas (b-1) and (b-2) include diphenols.
  • onium salts in which the anion portion of these onium salts is replaced by methanesulfonate, n-propanesulfonate, or n-butanesulfonate Kn-octanesulfonate can also be used.
  • an anion salt system in which an anion is replaced with an anion represented by the following general formula (b-3) or (b-4) Also included are acid generators (the cation moiety is the same as (b-1) or (b-2)).
  • X represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; ⁇ " and ⁇ "are each independently at least one hydrogen atom is fluorine.
  • the number of carbon atoms substituted with an atom represents an alkyl group having! -10.
  • X is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5, most preferably 3 carbon atoms.
  • ⁇ "and ⁇ " are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably Has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the number of carbons in the alkylene group of X ′′ or the number of carbons in the alkyl group of Y ′′ and ⁇ ⁇ ⁇ ′′ is preferably as small as possible because the solubility in a resist solvent is good within the above-mentioned range of carbon numbers.
  • the ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
  • Preferable examples also include an ion salt-based acid generator having an anion moiety represented by the following general formula (b-5) (hereinafter also referred to as component (b-5)).
  • the EL margin is an exposure range that can form a resist pattern with a dimension within which the deviation from the target dimension is within a specified range when exposure is performed with different exposure amounts, that is, an exposure that provides a resist pattern that is faithful to the mask. It is a range of quantity, and the larger the EL margin, the better.
  • the EL margin is improved without deteriorating the resist pattern shape by using an onion salt acid generator having an anion portion represented by the following general formula (b-5). That's the power S.
  • the alkyl group is preferably linear or branched, and the alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the carbon number of the alkyl group of U “, V", and W “ is preferably as small as possible for reasons such as good solubility in a resist solvent within the above carbon number range.
  • the proportion of fluorine atoms in the alkyl group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably 100%. That is, as the alkyl group of U “, V", and W ", a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms is most preferable.
  • the cation part of the component (b-5) is not particularly limited, and examples thereof include those similar to the cation part of acid generators proposed so far.
  • the cation part of the component (b-5) in particular, the cation part of the onium salt acid generator represented by the general formula (b-1) or (b-2), that is, the following general formula ( -The cation moiety represented by 1) or (b '2) is preferred.
  • cation moiety represented by the formula (b′—1) or (b′—2) include diphenylsulfonyl ion, bis (4-tert-butylphenyl) iodonium ion, and triphenylsnorephoni.
  • an onium salt represented by the following general formula (b-5-1) is particularly preferable.
  • R bl to R bd are each independently an alkyl group; a, b and c are integers of 0 to 2. ]
  • R 61 to R 63 are each independently an alkyl group, and the alkyl group may be substituted with a hydrogen atom of the above 1 " ⁇ ! ⁇ " Aryl group.
  • alkyl group mentioned as a preferable alkyl group include methyl and / or tert-butyl group, and tert-butyl group is particularly preferable.
  • a is an integer of 0 to 2, 0 or 1 is preferred, and 1 is particularly preferred.
  • b is an integer of 0, 0 or 1 is preferred, and 1 is particularly preferred.
  • c is an integer of 0, 0 or 1 is preferred, and 1 is particularly preferred.
  • the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and generates 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 R 32 each independently represents an organic group.
  • the organic group of R 31 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 (fluorine atom, chlorine atom, etc.)) Etc.).
  • an atom other than a carbon atom for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.)
  • a linear, branched or cyclic alkyl group or aryl group is preferable.
  • These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 6 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • the alkyl group preferably has 120 carbon atoms. Carbon number 1 to; 10 is more preferable carbon number 18 is more preferable carbon number;! To 6 is particularly preferable carbon number 14 is most preferable.
  • 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 fully halogenated alkyl group means that all the hydrogen atoms are halogen atoms. It means an alkyl group substituted by.
  • Halogen atoms include fluorine, chlorine, odor Elementary atoms, iodine atoms and the like can be mentioned, and fluorine atoms are 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, and more preferably 6 to 1 carbon atoms.
  • aryl group 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 in particular, an alkyl group having 1 to 4 carbon atoms having no substituent, or 1 carbon atom
  • a fluorinated alkyl group of ⁇ 4 is preferred!
  • 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.
  • Examples thereof include compounds represented by B-2) or (B-3).
  • R 33 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group;
  • R 34 is an aryl group;
  • R 35 is not having a substituent. ! /, An alkyl group or a halogenated alkyl group.
  • R db is a cyano group, 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 unsubstituted alkyl group or a halogenated alkyl group
  • the alkyl group or halogenated alkyl group having no substituent for R 33 preferably has 1 to 10 carbon atoms, preferably 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 for R 33 preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. .
  • the aryl group of R 34 includes a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group. And a heteroaryl group in which a 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. 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 is preferably 1 to 4 carbon atoms, more preferably 1 to 8 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 has carbon number;
  • 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 a hydrogen atom of the alkyl group of 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more. This is preferable because the strength of the generated 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 halogenated alkyl group having no R db substituent does not have the above R 33 substituent! /
  • Alkyl group or halogenated Examples are the same as the alkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups obtained by further removing 1 or 2 hydrogen atoms from the aryl group for R 34 .
  • Examples of the alkyl group or halogenated alkyl group having no substituent of R 38 include those similar to the alkyl group or halogenated alkyl group having no substituent of the above 5 .
  • P is preferably 2.
  • oxime sulfonate acid generator examples include ⁇ (p-toluenesulfonyloxyimino) benzyl cyanide, ⁇ ( ⁇ chlorobenzenesulfonyloxyimino) benzylcyanide, ⁇ - (4 Benzenesulfonyloxymino) Benzyl cyanide, ⁇ (4 12 tallow 2 trifluoromethylbenzenesulfonyloxymino) benzyl cyanide, ⁇ (benzenesulfonyloxyimino) -4 clonal benzil cyanide, ⁇ — (Benzenesulfonyloxyimino) -2, 4-dichlorodiphenylcyanide, ⁇ (benzenesulfonyloxyimino) -2,6-dichlorodiethylcyanide, ⁇ (benzenesulfonyloxyimino) -4-Meth
  • JP-A-9 208554 (paragraphs [0012] to [0014] [Chemical 18]-[Chemical 1 9]), an oxime sulfonate acid generator disclosed in WO2004 / 074242A2 (Examples on pages 65 to 85; Examples 40! To 40) is also preferably used. Can do.
  • bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfur) diazomethane, bis (p-toluenenolehoninore) diazomethane, bis (1 , 1-dimethylenoethylethylrephoninole) diazomethane, bis (cyclohexylsulfoninole) diazomethane, bis (2,4 dimethinophenylsulfonyl) 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 (bissulfonyl) diazomethanes include, for example, 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane, 1,4 bis (phenyl) disclosed in JP-A-11 322707.
  • Sulfonyl diazomethylsulfoninole) butane 1 6 bis (pheninosulphonyl diazomethinolesnolephonyl) hexane, 1,10-bis (phenylsulphonyl diazomethylsulfoninole) decane, 1 , 2-bis (cyclohexylsulfonyldiazomethylsulfoninole) ethane, 1,3-bis (cyclohexylsulfonyldiazomethylsulphoninole) propane, 1 6 bis (cyclohexinoresnorephoninoresi) Zomethinolesnorehoninole) Hexane, 1, 10-bis (cyclohexylsulfonyldiazomethylsulfoninole) decane Can do.
  • one type of these acid generators may be used alone, or two or more types may be used in combination.
  • the component (b-5) is particularly preferred because it has excellent lithography properties for the resulting resist composition. It is also preferable to use the component (b-5) in combination with an onium salt acid generator having a fluorinated alkylsulfonic acid ion in the anion part. Inside In particular, it is particularly preferable to use the component (b-5) in combination with the onium salt acid generator represented by the general formula (b-1).
  • the content of the component (B) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A); more preferably 10 to 10 parts by mass. 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 chemically amplified positive silicon resist composition preferably contains the following optional components.
  • the lithography properties of the storage stability (storage stability as a resist solution by particles) JP Juo without t summer
  • mouth can be force S to above.
  • “improving foreign matter aging characteristics” refers to an increase in storage stability when a chemically amplified positive silicon resist is used as a solution. Specifically, it means that generation of fine particulate foreign matters in the solution is suppressed over time. Such foreign matter aging tends to occur particularly when a silsesquioxane resin is used. Further, the occurrence of foreign matter may cause deterioration of lithography characteristics, diffate (surface defect) of a formed resist pattern, and the like.
  • defect means, for example, general defects detected when the resist pattern after development is observed from directly above with a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. It is. Examples of defects include scum, bubbles, dust, bridges (bridge structures between resist patterns), uneven color, and precipitates after development.
  • a method of adjusting the composition of the base material component has been generally used. For example, by increasing the solubility of the base material component in an organic solvent, it is considered that the generation of foreign substances due to precipitation of the dissolved component can be suppressed. However, if the composition of the silicon-containing resin is changed, the lithography properties such as sensitivity and resolution deteriorate, and it is difficult to change the composition immediately.
  • the positive silicon-based resist composition strength contains ⁇ -petit-mouth ratatone as an optional component, so that the lithography can be performed without changing the composition of the silicon-containing resin. It is possible to improve foreign matter aging characteristics without impairing luffy characteristics.
  • the content of ⁇ -butyrolatatane in the positive silicon resist composition is preferably from 3 to 100 parts by mass; 5 to 30 parts by mass is more preferable and 10 to 20 parts by mass is particularly preferable.
  • the above effect is excellent, and by setting it to the upper limit value or less, the film forming property, coating property, etc. when forming the resist film using the resist composition are improved.
  • the compound (C) represented by the following general formula (c 1) as the optional component, it is possible to suppress the occurrence of diffetats when forming a resist pattern. In addition, the shape of the formed resist pattern is improved.
  • the term “diffeta” refers to the force S, as described above, when forming a high-resolution resist pattern, especially after the ArF excimer laser, that is, ArF excimer laser, F excimer.
  • the suppression is important.
  • a method of suppressing the diffetato a method of adjusting the composition of the base material component has been generally used.
  • changing the composition of the silicon-containing resin may affect the lithography properties such as sensitivity and resolution. As mentioned earlier, it is easy to cause deterioration.
  • the positive silicon resist composition contains the compound (C) as an optional component, it is possible to reduce the lithographic characteristics without impairing the lithography characteristics without changing the composition of the silicon-containing resin. Occurrence can be suppressed.
  • R 11 is an acid-dissociable group, and R ′′ to R 14 are each independently a hydrogen atom or a hydroxyl group.
  • R 11 is an acid dissociable group.
  • the acid dissociable group for R 11 is not particularly limited as long as it is a group dissociable by the action of an acid generated from the component (B). For example, it is possible to use what has been proposed as an acid dissociable, dissolution inhibiting group for a base resin for a chemically amplified resist.
  • the acid dissociable, dissolution inhibiting group include a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an alkoxyalkyl group And acetal type acid dissociable, dissolution inhibiting groups such as “(Meth) acrylic acid” means one or both of acrylic acid having a hydrogen atom bonded to the ⁇ -position and methacrylic acid having a methyl group bonded to the ⁇ -position.
  • (Meth) acrylic acid ester means one or both of an acrylic acid ester having a hydrogen atom bonded to the ⁇ -position and a methacrylate ester having a methyl group bonded to the ⁇ -position.
  • (meth) acrylate means one or both of an arylate having a hydrogen atom bonded to the ⁇ -position and a metatalylate having a methyl group bonded to the a-position.
  • the “tertiary alkyl ester” is an ester formed by replacing the hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carboxy group (one C A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the oxygen atom at the terminal of (O) —O—).
  • an acid acts on this tertiary alkyl ester, 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 is referred to as “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
  • Examples of 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” is a relative concept with respect to aromaticity, and is defined to mean a group, compound, or the like that does not have aromaticity.
  • the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of carbon and hydrogen (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, etc. Can be mentioned.
  • the “aliphatic cyclic group” in the “acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group” is a hydroxyalkyl having a fluorinated hydrogen atom, which may be monocyclic or polycyclic. It may or may not be substituted with a ru group.
  • ⁇ Monocyclic aliphatic cyclic group '' means a monocyclic group that does not have aromaticity
  • ⁇ polycyclic aliphatic cyclic group '' does not have aromaticity! /, Means a polycyclic group.
  • An aliphatic cyclic group is a hydrocarbon group composed of carbon and hydrogen (an alicyclic group), and some of the carbon atoms constituting the ring of the alicyclic group are oxygen atoms, nitrogen atoms, sulfur atoms, etc. Heterocyclic groups and the like substituted with a tetro atom are included. As the aliphatic cyclic group, an alicyclic group is preferable.
  • the aliphatic cyclic group may be either saturated or unsaturated, but is preferably saturated because it is highly transparent to ArF excimer laser, etc., and has excellent resolution and depth of focus (DOF). .
  • the aliphatic cyclic group preferably has 3 to 20 carbon atoms, preferably 4 to; more preferably 15 to 5; and even more preferably 15.
  • aliphatic cyclic group examples include a monocyclic group obtained by removing one or more hydrogen atoms from a cycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from cyclopentane or cyclohexane, and groups in which one or more hydrogen atoms have been removed from cyclohexane are preferred.
  • Examples of the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like. More specifically, groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.
  • monocyclic groups are preferably groups in which one or more hydrogen atoms have been removed from cyclopentane or cyclohexane, particularly one or more hydrogen atoms from cyclohexane. Excluded groups are preferred.
  • the polycyclic group is preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane 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, examples thereof include 2 methylol 2-adamantyl group and 2-ethyl-2-adamantyl group. Alternatively, a group having an aliphatic cyclic group such as an adamantyl group and a branched alkylene group having a tertiary carbon atom bonded thereto is exemplified.
  • Acetal type acid dissociable, dissolution inhibiting group is generally bonded to an oxygen atom by substituting a hydrogen atom at the end 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, ⁇ represents an integer of 0 to 3, and ⁇ represents a lower alkyl group or an aliphatic cyclic group.
  • ⁇ is preferably an integer of 0 to 2, 0 or 1 is more preferable, and 0 is most preferable.
  • R 1 ′ and R 2 ′ are a hydrogen atom or a lower alkyl group.
  • the lower alkyl group of R 1 ′ and R 2 ′ is an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, ⁇ butyl group, isobutyl group, tert Lower linear or branched alkyl groups such as butyl, pentyl, isopentyl, and neopentyl are listed. I can get lost.
  • As the lower alkyl group for R 1 ′ and R 2 ′ a methyl group or an ethyl group is preferred, and a methyl group is most preferred.
  • the acid dissociable, dissolution inhibiting group (pi) force is preferably a group represented by the following general formula (pi-1).
  • Examples of the lower alkyl group for ⁇ include those similar to the lower alkyl group for R 1 'above.
  • aliphatic cyclic group of ⁇ it can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups that have been proposed in a number of conventional ArF resists. Examples thereof are the same as those in the formula group.
  • the acetal type acid dissociable, dissolution inhibiting group includes a group represented by the following general formula (p2).
  • R 17 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 are bonded to form a ring! / /. ]
  • R 17, R 18, carbon atoms in the alkyl group is preferably 1 to; of 15, linear, branched either Yogu Echiru group, is preferred instrument methyl group methyl group is most preferable.
  • one of R 17 and R 18 is a hydrogen atom and the other is a methyl group.
  • R 19 is a linear, branched or cyclic alkyl group, preferably having carbon numbers;! To 15 and may be any of 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 S having 4 to 15 carbon atoms, preferably S having 4 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms.
  • 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.
  • the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuranyl group.
  • the tertiary alkyl ester type acid-releasing dissolution inhibiting group is preferably a tertiary alkyl having 4 to 8 carbon atoms.
  • the tert butyl group is particularly preferred, with the group being more preferred.
  • R 12 ⁇ R 14 are independently a hydrogen atom or a hydroxyl group.
  • R 12 to R 14 is a hydroxyl group. It is particularly preferable that R 12 is a hydroxyl group.
  • compound (C) a compound represented by the following general formula (c 1 1) (c 1-1), a compound represented by the following general formula (c 1 2) (c 1 2), a compound represented by the following general formula (c 1 3) (c 1 3), a compound represented by the following general formula (c 1 4) (c 1 4), a compound (c 15) represented by the following general formula (c 15) and the like.
  • Compound (C) can be produced by substituting the hydrogen atom at the terminal of the carboxy group of compound (C ') represented by the following general formula (1) with an acid-dissociable group by a well-known method.
  • each of the above compounds (c 1 one ;!) to (c—15) has, as the compound (C ′), lithocholic acid (wherein R 12 in the formula (c′—1) is a hydroxyl group, R 13 And a compound in which R 14 is a hydrogen atom), cholic acid (a compound in which R 12 to R 14 in formula (1) are hydroxyl groups), deoxycholate (in which R 12 and R 14 in formula (1) are A compound having a hydroxyl group and R 13 being a hydrogen atom), cholanic acid (a compound having R 12 to R 14 in the formula (c ′ 1) being a hydrogen atom), hydroxycholic acid (in the formula (1)) In which R 12 and R 13 are a hydroxyl group, and R 14 is a hydrogen atom.
  • one type may be used alone, or two or more types may be used in combination.
  • the content of the compound (C) in the chemically amplified positive silicon resist composition is preferably 0 ⁇ ;! to 20 parts by mass with respect to 100 parts by mass of the component (A); 3 parts by mass is more preferred; 10 parts by mass is more preferred.
  • component (D) a nitrogen-containing organic compound (hereinafter referred to as “component (D)”) as the optional component.
  • any known (D) component can be used arbitrarily.
  • the component (D) include secondary aliphatic amines and tertiary aliphatics. Examples thereof include aliphatic amines such as amines and aromatic amines.
  • aliphatic is a relative concept with respect to aromatics, as described above, and is defined as meaning no aromaticity! /, Group, compound, etc. .
  • the “aliphatic amine” is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms! /.
  • At least one hydrogen atom of ammonia NH is linear or Is branched chain carbon number;! ⁇ 12 alkyl or hydroxyalkyl substituted amine (alkylamine or alkyl alcoholamine); aliphatic cyclic amine having an aliphatic cyclic group in its structure, etc. Is mentioned.
  • the “aliphatic cyclic group” indicates that it is aromatic, monocyclic group or polycyclic group.
  • alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc .; jetylamine, di-n-propylamine, di-n-heptylamine, di- n Dialkylamines such as octylamine and dicyclohexylamine; Trialkylamines such as otatilamine, tri-n nonenoleamine, tri-n-decaninoleamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropaline Examples include alkyl alcohol amines such as noramine, di-n-octanolamine, and tri-n-octanolamine.
  • Examples of the aliphatic cyclic amine include an aliphatic bicyclic compound 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. 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.
  • “Aromatic amine” means that at least one hydrogen atom of ammonia NH has aromaticity.
  • aromatic group examples include an aromatic hydrocarbon group and an aromatic heterocyclic group.
  • the aromatic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms.
  • an aromatic hydrocarbon group specifically, a group obtained by removing one hydrogen atom from an aromatic ring such as benzene, naphthalene, anthracene, etc.
  • a phenyl group, a naphthyl group, an anthracenyl group, etc. a group in which a hydrogen atom of a straight chain or branched alkyl group having a carbon number of !!-5 is substituted with an aromatic ring (for example, a benzyl group, a phenylethyl group (CH- CH 2 -CH 1), naphthylmethyl group (CH 2 -CH 1), naphth
  • the aromatic ring may have a substituent.
  • substituents include an alkyl group having!
  • An aromatic heterocyclic group is an aromatic cyclic group having a ring skeleton composed of carbon atoms and hetero atoms other than carbon atoms (nitrogen atoms, oxygen atoms, sulfur atoms, etc.). And a group obtained by removing one hydrogen atom from an aromatic heterocycle such as coumarin.
  • These aromatic heterocyclic groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
  • an aromatic heterocyclic group is preferred because it is excellent in high-definition and high-aspect-ratio pattern formation on the support, which is an effect of the present invention. Remove one! /, Prefer the group! /.
  • the aromatic amine is particularly preferably a tertiary amine, preferably a secondary amine and / or a tertiary amine.
  • the secondary amine and / or tertiary amine may contain at least one aromatic group. Besides, it is a linear, branched or cyclic aliphatic hydrocarbon group having 5 to 5 carbon atoms; A group in which a part of carbon atoms of the aliphatic hydrocarbon group is substituted with a hetero atom such as a nitrogen atom, or the like.
  • aromatic amine a compound represented by the following general formula (d-1) is particularly preferable.
  • R 41 to R 42 are each independently an alkyl group having 1 to 10 carbon atoms
  • R 43 is an alkenoquinole group having! To 5 carbon atoms
  • n is an integer of 0 to 2.
  • the component (D) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (D) in the chemically amplified positive silicon resist composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). Mashiro 0.01 to 5 parts by mass are more preferable.
  • the optional component further contains a sulfone compound (E) represented by the following general formula (e-1) (hereinafter also referred to as component (E)).
  • E sulfone compound represented by the following general formula (e-1)
  • component (E) As a result, pH fluctuations during storage of the resist composition as a solution are suppressed, and storage stability is improved.
  • the positive silicon resist composition contains the component (D) described above, it is preferable to use the component (E) in combination because the pH tends to change during storage as a solution.
  • R 21 to R 23 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. ]
  • the alkyl group for R 21 to R 23, particularly limited Nag example carbon atoms;! ⁇ 10 linear, include alkyl groups such as branched or cyclic. Specifically, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, n pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, Noel group, decanyl group, etc.
  • the alkyl group may have a substituent. That is, some or all of the hydrogen atoms in the alkyl group may be substituted with substituents. Examples of the substituent that the alkyl group may have!
  • the substituent is most preferably a methyl group, an ethyl group, a propyl group, an n butyl group, or a tert butyl group, particularly preferably an alkyl group having!
  • the aryl group of R 21 to R is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms, specifically, a phenyl group and a naphthyl group.
  • the aryl group may have a substituent. That is, some or all of the hydrogen atoms of the aryl group may be substituted with substituents. Examples of the substituent that the aryl group has! / May be the same as those described as the substituent that the alkyl group may have.
  • Preferable examples of the component (E) include triphenyl compounds represented by the following general formula (e-2), tricyclohexyl compounds represented by the following general formula (e-3), and the like.
  • a triphenyl compound represented by the general formula (e-2) is preferable, and a compound in which R 20 to 15 are all hydrogen atoms is preferable.
  • R to R lb are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 221 to R ⁇ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms.
  • component (E) one type may be used alone, or two or more types may be used in combination.
  • the content of the (E) component in the chemically amplified positive silicon resist composition is 0.0;! To 5 parts by mass with respect to 100 parts by mass of the (A) component. Preferred 0.05 to 4 parts by weight is more preferred 0.;! To 3 parts by weight is even more preferred.
  • component (F) for the purpose of further preventing sensitivity deterioration and improving the resist pattern shape, retention time stability, etc., the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof At least one compound (F) selected from (hereinafter referred to as component (F)) 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. Of these, malonic acid is particularly preferable.
  • phosphorus oxoacids and derivatives thereof include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
  • Derivatives of phosphorus oxoacid include, for example, the above hydrogen atom of oxoacid as a hydrocarbon. And esters substituted with a group.
  • the hydrocarbon group include an alkyl group having! To 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, and the like.
  • phosphoric acid derivatives examples include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate.
  • phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethylolestenole, phosphonic acid diol n-butyl ester, fenenorephosphonic acid, phosphonic acid diphenenoresestenole, and phosphonic acid dibenzyl ester.
  • phosphinic acid derivatives examples include phosphinic acid esters such as phenylphosphinic acid.
  • component (F) one type may be used alone, or two or more types may be used in combination.
  • Component (F) is usually used at a ratio of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • an additive that is miscible for example, an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, a dissolution inhibitor, a plasticizer.
  • Agents, stabilizers, colorants, antihalation agents, dyes and the like can be added and contained as appropriate.
  • the chemically amplified positive silicon resist composition used in the present invention can be produced by dissolving a material in an organic solvent (hereinafter, also 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.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol
  • a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate
  • the polyhydric alcohol or the compound having an ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ether or monophenyl ether, such as monomethyl etherate, monoethinore etherol, monopropinore etherol, monobutinole
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether acetate
  • PGME
  • organic solvents may 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, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. 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, and most preferably 5: 5-8: 2.
  • the amount of component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating thickness. Generally, it is used so that the solid content concentration of the resist composition is in the range of 2 to 20% by mass, preferably 5 to 15% by mass.
  • the hard mask used in the present invention is not particularly limited as long as it is formed using a silicon-based hard mask forming material as the resist underlayer film.
  • a composition containing a siloxane polymer is preferred (BH) siloxane polymer and a mass average molecular weight of 300
  • a composition containing 0 or less (AH) siloxane compound (hereinafter sometimes referred to as a composition for forming a hard mask) is more preferred.
  • a composition for forming a hard mask will be described in detail.
  • the (AH) siloxane compound has a mass average molecular weight of 3000 or less. By setting the mass average molecular weight within such a range, it is possible to reduce the tailing of the resist pattern formed on the hard mask and to improve the pattern shape.
  • Examples of the (AH) siloxane compound include the following general formulas (ah-1), (ah-2) and
  • R lh , R 3h , R 4h , R 5h , R 6h are each independently a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, and R 2h are each independently a linear or branched group.
  • R lh and R 3h and / or R 4h and R 5h may be combined to form one O—, and m is 1 to 8 And n is 2 forces, et al. ]
  • alkyl group and “alkoxy group” of R lh , R 3h , R 4h , R 5h , R 6h , carbon It is preferred to be of the number 1 to 3! /.
  • alkyl groups examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • alkoxy groups examples include a methoxy group, an ethoxy group, and a propoxy group.
  • R lh, R 3h is preferably more than 25 mol% of the sum of R 4h and R 5h is a hydroxyl group.
  • the hydrocarbon group for R 2h is preferably a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an aromatic hydrocarbon group.
  • the linear or branched hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, Alkyl groups such as undecyl group and dodecyl group; alkenyl groups such as bur group, arinole group and propenyl group; cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, norbornyl group, norbornenyl group and adamantyl group; Can be mentioned.
  • aromatic hydrocarbon group examples include phenyl group, naphthyl group, methylphenyl group, ethenylphenyl group, trinole group, chlorophenyl group, bromophenyl group, fluorophenyl group and the like; benzyl group, phenethyl group, naphthyl group, etc. Examples thereof include aralkyl groups such as a methyl group, a diphenylmethyl group, a triphenylmethyl group, and a 1-methyl-1-phenylethyl group. These hydrocarbon groups may have a substituent. Examples of the substituent include a hydroxyl group and an alkoxy group having 1 to 3 carbon atoms.
  • R 2h is a norbornyl group or a group represented by the following formula (ah-4).
  • the group represented by the formula (ah-4) is preferable because of excellent compatibility with the later-described (BH) component and the organic solvent.
  • the group represented by the formula (ah-4) is 10 mol% or more, more preferably 25 mol% or more of R 2h. Preferably included. Further, in the siloxane compound represented by the formula (ah-3), the group represented by the formula (ah-4) is contained in 12.5 mol% or more, more preferably 25 mol% or more of R 2h. I like it. By setting it to the above value or more, the compatibility of the (AH) siloxane compound with the organic solvent can be particularly improved.
  • R lh and the R 3h and / or R 4h and R 5h together - may be O.
  • a cage structure is obtained.
  • m is preferably an approximately cubic T8 structure, an approximately pentagonal T10 structure, or an approximately hexagonal T12 structure, preferably 2 to 4.
  • siloxane compounds represented by the above general formulas (ah-1) and (ah-3) include the following structural formulas (ah-1-11), (ah-1-2) and ( ah— 3— 1) is preferred.
  • the upper limit of the weight average molecular weight of the (AH) siloxane compound is 3000, and 2800 Being force S is preferable.
  • the lower limit value is preferably 300, preferably S, and more preferably 500. By setting the lower limit value to 300, evaporation of the siloxane compound can be suppressed, and the film forming property of the hard mask composition can be improved.
  • the (BH) siloxane polymer has a structural unit represented by the general formula (bh-1).
  • R h represents a light absorbing group
  • R Sh represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group
  • r is 0 or 1.
  • the light absorbing group is a group having absorption in the wavelength range of 150 nm to 300 nm.
  • Examples of the light absorbing group include groups having a light absorbing portion such as a benzene ring, an anthracene ring, and a naphthalene ring.
  • the light absorbing part is interrupted by one or more —O— and —O (CO) —! /, May! /, And the main skeleton Si via an alkylene group having 1 to 20 carbon atoms. It may be bonded to an atom.
  • one or more light absorbing portions such as a benzene ring, an anthracene ring, and a naphthalene ring may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a hydroxy group.
  • a benzene ring is preferable.
  • a group having a light absorbing portion having a Si—Si bond can also be used. Further, these light absorbing portions may be included in the main skeleton of the siloxane polymer.
  • Examples of the light absorbing group include phenyl group, naphthyl group, methylphenyl group, ethenylphenyl group, trinole group, chlorophenyl group, bromophenyl group, fluorophenyl group and other aryl groups; benzinole group, phenethyl group, naphthylmethyl group, Examples thereof include aralkyl groups such as diphenylmethyl group, triphenylmethyl group, and 1-methyl-1-phenylethyl group. Of these, a phenyl group is preferable.
  • the (BH) siloxane-based polymer preferably has at least one structural unit represented by the general formula (bh-2).
  • R 9h represents a hydrogen atom, an alkyl group, or a monovalent organic group having at least one functional group selected from carbonyl, ester, rataton, amide, ether, nitrile
  • R 1Qh represents A hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, s is 0 or 1; the functional group has 1 to 6 carbon atoms, and the monovalent organic group has a carbon number of ;! ⁇ 6.
  • the lower limit of the mass average molecular weight of the (BH) siloxane copolymer is 8000, more preferably 10,000. By making the mass average molecular weight of the (BH) component 8000 or more, the film formability of the hard mask can be improved. Further, the upper limit of the mass average molecular weight of the component (BH) is preferably 50000 force S, more preferably 30000 force S. By setting the mass average molecular weight of the (BH) component to 50000 or less, the applicability of the hard mask forming composition can be improved.
  • the (BH) siloxane copolymer is produced by hydrolyzing and copolymerizing each monomer containing each structural unit, as in the case of the (AH) component.
  • the ratio of the (AH) component to the (BH) component in the composition for forming a hard mask is preferably 1: 9 to 7: 3 in terms of a mass ratio of 3: 7 to 6: 4. 5: 5 is the most preferred.
  • the composition for forming a hard mask also contains a (CH) solvent (hereinafter also referred to as a (CH) component).
  • a (CH) solvent hereinafter also referred to as a (CH) component.
  • monovalent vinylols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyranolol; ethylene glycolol, diethyleneglycolanol, propyleneglycolanol, glycerin, trimethylololepropane, hexanetriolanol, etc .; ethylene Glycolic Monomethinoleetenore, Ethylene Glyconole Monopropenoleetenore, Ethylene Glyconole Monopropinoleetenore, Ethylene Glyconole Monobutinoleetenore, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Enotere, Diethylene Glyconore Monopropino
  • organic solvents may be used alone or in combination of two or more.
  • 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 Is preferably in the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. More specifically, when EL is used as a polar solvent, the mass ratio of PGMEA: EL is
  • the ratio is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • PGM as a polar solvent
  • the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7: 3.
  • This solvent is used in an amount of 1 to 100 times, more preferably 2 to 20 times the total mass of the components (AH) and (BH). By making it within this range, the applicability of the hard mask forming composition can be improved.
  • the composition for forming a hard mask may contain a (DH) crosslinking agent (hereinafter also referred to as a (DH) component).
  • a (DH) crosslinking agent By adding a (DH) cross-linking agent, the film formability of the hard mask can be improved.
  • the crosslinking agent those generally used may be used.
  • epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol nopolac type epoxy resin, and cresol nopolac type epoxy resin.
  • dibutene benzene, divinyl sulfone, triacryl formal, glyoxal, and polyhydric alcohol acrylate or methacrylate are also used.
  • At least two groups of melamine, urea, benzoguanamine, glycoluril, and two or more reactive groups such as a compound substituted with S methylol group, lower alkoxymethyl group or lower acyloxymethyl group And the like.
  • the lower alkoxymethyl group and the lower acyloxymethyl group preferably have 2 to 6 carbon atoms.
  • the compounds in which at least two of the melamine amino groups are replaced with a methylol group or a lower alkoxymethyl group include hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, and six others. Methoxymethylated compounds and mixtures thereof; hexethoxymethino melamine, hexacyloxy methino melamine, hexamethylone melamine, one of the methylol groups, five of which are acyloxymethylated Or a mixture thereof.
  • At least two of the urea amino groups are substituted with a methylol group or a lower alkoxymethyl group.
  • the compound include tetramethylolurea, tetramethoxymethylurea, tetraethoxymethylurea, tetramethylolurea, one compound having four or more methylol group S-methoxymethyl groups, or a mixture thereof.
  • Examples of the compound in which at least two of the amino groups of benzoguanamine are substituted with a methylol group, a lower alkoxymethyl group or a lower acyloxymethyl group include tetramethylol guanamine, tetramethoxymethyl dianamine, and tetramethylol guanamine. From 1 to 4 methylol groups methoxymethylated and mixtures thereof; tetraethoxymethylanolamine, tetraacyloxyguanamine, tetramethylolguanamine 1 to 4 methylol groups acyloxymethylated compounds and mixtures thereof Etc.
  • Compounds in which at least two of the amino groups of glycoluril are substituted with a methylol group, a lower alkoxymethyl group or a lower acyloxymethyl group include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl.
  • Dalicolurinole a compound in which one to four of the methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof; one of the methylol groups of tetramethylol glycoluril, four of which are acyloxymethyl Compound or a mixture thereof.
  • crosslinking agents may be used alone or in combination of two or more.
  • the addition amount of the crosslinking agent is 0.1 to 50 parts by mass and 0.5 to 40 parts by mass with respect to 100 parts by mass of the (AH) component and the siloxane polymer. It is more preferable.
  • the composition for forming a hard mask may contain (EH) acid generator (hereinafter also referred to as (EH) component).
  • EH acid generator
  • Examples of the acid generator include onium salts, diazomethane derivatives, darioxime derivatives, bissulfone derivatives, ⁇ -ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, and sulfonic acids of ⁇ ⁇ ⁇ ⁇ ⁇ -hydroxyimide compounds.
  • a known acid generator such as an ester derivative can be used.
  • onium salts include tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, and tetra ⁇ a nonafluorobutanesulfonate.
  • Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluene senorephoninore) diazomethane, bis (xylene senorephoninore) diazomethane, bis (cyclohexenolesnorenoninore) diazomethane, bis (cyclopentino) Lesnolehoninole) diazomethane, bis ( sec butylsulfonole) diazomethane, bis (n-propylsulfonino) diazomethane, bis (n amylsulfonino) diazomethane, bis (isoaminoresulphoninole) diazomethane, bis (sec amylsulfonino) diazomethane, bis (Tert-amylsulfoninole) diazomethane, 1-cyclohexenolesnorehoninole 1-
  • the glyoxime derivatives include bis-l-O- (p-toluenesulfonyl) ⁇ -dimethyl glyoxime, bis-l- ⁇ - ( ⁇ -toluenesulfonyl) ⁇ -diphenyldarioxime, bis-l- ⁇ - ( ⁇ -toluenesulfonyl) ⁇ - Dicyclohexylglyoxime, bis-one ⁇ — ( ⁇ Toluenesulfonyl) 2, 3 Pentanedione glyoxime, bis-one ⁇ — ( ⁇ Toleneene sulfonyl) -one 2 Methyl 3, 4 Pentanedione glyoxime, bis-one ⁇ — ( ⁇ — Butanesulfonyl) a-dimethyldarioxime, bis O— (n-butanesulfonyl) a-diphenyldarioxime, bis O— (n-buta
  • Examples of the bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethyl sulphononinomethane, bismethinolesnorenoninomethane, biscetenoresnorenoninomethane, bispro Examples thereof include pinoles norehoninoremethane, bisisopropinolesnorehonenomethane, bis-p-to-norenosenorethanolmethane, and bisbenzenesulfonylmethane.
  • Examples of the ⁇ -ketosulfone derivative include 2-cyclohexylcarbonyl 2- ( ⁇ toluenesulfonole) propane, 2-isopropylcarbonyl 2- ( ⁇ toluenesulfonyl) propane, and the like.
  • disulfone derivatives examples include disulfone derivatives such as diphenyldisulfone derivatives and dicyclohexyldisulfone derivatives.
  • nitrobenzyl sulfonate derivatives examples include nitrobenzyl sulfonate derivatives such as ⁇ toluenesulfonic acid 2,6 dinitrobenzyl and ⁇ toluenesulfonic acid 2,4 dinitrobenzil.
  • Examples of the sulfonic acid ester derivatives include 1, 2, 3 tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris.
  • Examples thereof include sulfonic acid ester derivatives such as ( ⁇ toluenesulfonyloxy) benzene.
  • ⁇ ⁇ ⁇ ⁇ Derivatives of hydroxyimide compounds include ⁇ Hydroxysuccinimide methanesulfonate, ⁇ Hydroxysuccinimide trifluoromethanesulfonate, ⁇ Hydroxysuccinimide ethanesulfonate, ⁇ Hydroxysuccinimide 1 propane Sulfonic acid ester, ⁇ ⁇ ⁇ ⁇ ⁇ Hydroxysuccinimide 2-Propanesulfonic acid ester, ⁇ ⁇ ⁇ ⁇ Hydroxysuccinimide 1 Pentanesulfonic acid ester, ⁇ ⁇ ⁇ ⁇ Hydroxysuccinimide 1-octane sulfonic acid ester, ⁇ Hydroxysuccinimide ⁇ - Toluene sulfonic acid ester, ⁇ Hydroxysuccinimide ⁇ Methoxy Benzene sulfonic acid ester, ⁇ Hydroxysuccinimide 2-chlor
  • the amount of the acid generator added is from 0.1 to 50 parts by mass and from 0.5 to 40 parts by mass with respect to 100 parts by mass of the (AH) component and the (BH) component. More preferably.
  • the composition for forming a hard mask of the present invention is obtained by mixing the necessary components (EH) to (AH).
  • the resulting resist underlayer film composition is preferably filtered with a filter.
  • a spin coater, a slit nozzle coater or the like is used on the film to be processed (in some cases, the bottom layer formed on the film to be processed). It is sufficient to apply, dry and heat.
  • a single-stage heating or a multi-stage heating method can be used. In the case of using the multi-stage heating method, for example, it is preferable to first heat at 100 ° C. to 120 ° C. for 60 seconds to 120 seconds, and then at 200 ° C. force at 250 ° C. for 60 seconds to 120 seconds.
  • the thickness of the hard mask thus formed is preferably 20 nm to 150 nm. Thereafter, a resist film composition is provided on the hard mask in a thickness of, for example, lOOnm to 200 nm to produce a resist film. [0165] [Support]
  • the support is not particularly limited, and a conventionally known support can be used.
  • a substrate for an electronic component or a substrate on which a predetermined wiring pattern is formed More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given.
  • a material for the wiring pattern for example, copper, aluminum, nickel, gold or the like can be used.
  • the lower layer film a conventionally known film can be used. Either an inorganic film or an organic film may be used, but an organic film that can be dry-etched is preferred. For example, it is used in a normal multilayer resist method or the like. An organic film can be used.
  • a material capable of forming an organic film capable of etching such as oxygen plasma etching is preferable.
  • Such a material for forming an organic film may be a material conventionally used for forming an organic film such as an organic antireflection film (organic BARC).
  • organic BARC organic antireflection film
  • examples include the ARC series manufactured by Brew Sciences, the AR series manufactured by Rohm and Haas, and the SWK series manufactured by Tokyo Ohka Kogyo.
  • the organic film is etched by oxygen plasma etching and is applied to halogen gas, specifically, a fluorocarbon gas such as CF gas or CHF gas.
  • halogen gas specifically, a fluorocarbon gas such as CF gas or CHF gas.
  • etching of a substrate or the like is performed using a halogen gas such as a fluorocarbon-based gas. Therefore, by forming an organic film from such a material, oxygen plasma etching is performed when forming an organic film pattern. In the subsequent process using a halogen gas such as a fluorocarbon gas for etching the substrate or the like, the etching resistance can be improved with a force s.
  • the organic film-forming material further contains, if desired, miscible additives such as an additional resin for improving the performance of the organic film, a surfactant for improving the coating property, a dissolution inhibitor, Plasticizers, stabilizers, colorants, antihalation agents and the like can be appropriately contained.
  • miscible additives such as an additional resin for improving the performance of the organic film, a surfactant for improving the coating property, a dissolution inhibitor, Plasticizers, stabilizers, colorants, antihalation agents and the like can be appropriately contained.
  • the organic film forming material can be manufactured by dissolving the above-described resin components and the like in an organic solvent.
  • organic solvent the same organic solvents as those exemplified as the component (S) of the chemically amplified positive silicon resist composition described above can be used.
  • Conventionally known chemical amplification negative resist compositions can be used and are not particularly limited.
  • an alkali-soluble resin, an acid generator that generates an acid upon exposure, and a crosslinking agent are blended, and when an acid is generated by exposure at the time of resist pattern formation, the exposed portion acts to react with the alkali-soluble resin and the crosslinking agent.
  • Cross-linking occurs between the two and alkali-insoluble.
  • the alkali-soluble resin include a resin having a unit derived from at least one selected from a lower alkyl ester of a (hydroxyalkyl) acrylic acid or ⁇ (hydroxyalkyl) acrylic acid, and a resin having a fluorinated alcohol. It is preferable because a good resist pattern with less swelling can be formed.
  • ⁇ (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 a carbon number of 1 to One or both ⁇ -hydroxyalkylacrylic acids to which 5 hydroxyalkyl groups) are bonded.
  • crosslinking agent for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group because a good resist pattern with less swelling can be formed.
  • the compounding amount of the crosslinking agent is preferably from! To 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the pattern forming method of the present invention includes a step of forming a lower layer film on a support using a lower layer film forming material, and a hard mask using a silicon-based hard mask forming material on the lower layer film. Forming a first resist film by applying a chemically amplified negative resist composition on the hard mask, and forming a first mask pattern on the hard mask. A step of selectively exposing and developing the first resist pattern, and a step of forming a first pattern by etching the hard mask using the first resist pattern as a mask (until now).
  • the film is selectively exposed through a second mask pattern and developed to form a second resist pattern, and the lower layer film is etched using the second resist pattern as a mask.
  • FIGS. 1A to 1E are schematic process diagrams illustrating a patterning process (1) in a preferred embodiment of the pattern forming method of the present invention.
  • a lower layer film 2 is formed on a support 1 using the lower layer film forming material, and the silicon hard mask is formed on the lower layer film 2.
  • a hard mask 3 is formed using a material, and a chemically amplified negative resist composition is applied on the hard mask 3 to form a first resist film 4.
  • a conventionally known method may be applied to the step of forming the lower layer film 2, the hard mask 3, and the first resist film 4.
  • the method of applying the lower layer film-forming material on the support 1 is not particularly limited, and, for example, according to the lower layer film-forming material, for example, a spray method, a roll coating method, a spin coating method. Laws and the like can be selected as appropriate.
  • the thickness of the lower layer film 2 can be appropriately selected from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the lower layer film 2, and is preferably 150 nm or more and 500 nm or less, more preferably 200 nm or more 350 nm or less, more preferably 200 nm or more and 300 nm or less. By setting the thickness of the lower layer film 2 within this range, a resist pattern having a high aspect ratio can be formed.
  • the aspect ratio here refers to the resist pattern width X on the support.
  • the pattern width X of the resist pattern is the same as the pattern width after transfer to the lower layer film.
  • the pattern width means the width of a ridge (line) when the resist pattern is a line pattern such as a line and space pattern or an isolated line pattern.
  • the pattern width refers to the inner diameter of the formed hole (hole). If the resist pattern is a cylindrical dot pattern, enter the diameter.
  • all of these pattern widths are widths below the pattern (support side).
  • the method for applying the silicon-based hard mask forming material onto the lower layer film 2 is not particularly limited, and the hard mask is formed using the preferable hard mask forming composition described above. It is the same as the method of forming.
  • the thickness of the hard mask 3 is preferably 20 nm or more and 150 nm or less, more preferably 30 nm or more and 50 nm or less.
  • the silicon content of the silicon-based hard mask forming material is preferably 20% or more, more preferably 30% or more because the high aspect ratio pattern can be satisfactorily formed.
  • a chemically amplified negative resist composition is hard masked with a spinner or the like.
  • the first resist film 4 may be formed by applying a beta treatment (pre-beta) on the coating film formed on the substrate 3.
  • the thickness of the first resist film 4 can be appropriately selected from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the hard mask 3, and is preferably 50 nm to 200 nm. More preferably, it is lOOnm or more and 200nm or less. By setting the thickness to 200 nm or less, the resist pattern can be formed with high resolution, and by setting the thickness to 50 nm or more, there are effects such as sufficient resistance to dry etching.
  • the first resist film 4 is selectively exposed through the first mask pattern 5 and, optionally, the resist film 4 is further subjected to a beta treatment (post-etaspot). 1 jar beta (PEB)), the resist film 4 is developed, and the first resist pattern 4 ' Form.
  • a conventionally known method may be applied for the selective exposure and development.
  • the first mask pattern 5 used here may be appropriately selected in consideration of a desired pattern.
  • the force exemplified for the space width d and the pitch 2d is not limited to this.
  • the selective exposure conditions are not particularly limited. Depending on the light source and method used for exposure, the exposure region, exposure time, exposure intensity, and the like can be appropriately selected.
  • the exposure light source is not particularly limited. ArF excimer laser, KrF excimer laser, F
  • Excimer laser extreme ultraviolet
  • VUV vacuum ultraviolet
  • EB electron beam
  • X-ray soft X-ray, etc.
  • the alkali developer used for development is not particularly limited.
  • an aqueous tetramethylammonium hydroxide solution having a concentration of 0.05% by mass to 10% by mass, preferably 0.05% by mass to 3% by mass can be used.
  • the first resist pattern 4 is a line-and-space resist pattern (hereinafter referred to as an L / S pattern) having a line width d / 2, a space width 3d / 2, and a pitch 2d. .
  • the beta treatment conditions are not particularly limited. For example, it is desirable to heat the calorie under the temperature condition of 70 ° C or higher and 130 ° C or lower for 40 seconds to 180 seconds, preferably 60 seconds to 90 seconds.
  • the hard mask 3 is etched using the first resist pattern 4 as a mask to form a first pattern. That is, the first resist pattern 4 ′ is transferred to the hard mask 3.
  • a conventionally known method can be applied to the etching. For example, it can be performed by irradiation with plasma and / or reactive ions. Etching conditions can be appropriately selected according to the type of gas used.
  • the plasma and / or reactive ion gas used for etching is dry ethyne.
  • the gas is not particularly limited as long as it is a gas usually used in the field of gas.
  • the force that can mention oxygen, halogen, sulfur dioxide, etc. Halogen such as CF, CHF, etc.
  • the etching method is not particularly limited.
  • chemical etching such as down-flow etching or chemical dry etching
  • physical etching such as sputter etching ion beam etching
  • chemical / physical etching such as RIE (reactive ion etching).
  • the most common dry etching is parallel plate RIE.
  • a laminated body on which a resist pattern is formed is placed in a chamber of an RIE apparatus, and a necessary etching gas is introduced.
  • the gas is turned into plasma.
  • charged particles such as positive and negative ions and electrons, and neutral active species exist as etching species.
  • these etching species are adsorbed on the lower organic layer, a chemical reaction occurs, the reaction product is detached from the surface and exhausted to the outside, and etching proceeds.
  • the first resist pattern 4 ' may be removed, and the hard mask pattern 3' on the lower layer film 2 may be used as the first pattern.
  • the first resist pattern 4 may be left, and the first resist pattern 4 and the hard mask pattern 3 may be used as the first pattern.
  • a second pattern is formed.
  • 2A to 2D are schematic process diagrams illustrating the patterning process (2) in a preferred embodiment of the pattern forming method of the present invention.
  • 2A to 2D show an example in which the first resist pattern 4 'is removed and the hard mask pattern 3' is used as the first pattern.
  • the first resist pattern 4 ' Even when the first pattern is left, the second pattern can be formed by the same procedure.
  • the pattern may be peeled off using a known method such as a method using a stripping solution.
  • a second resist film 6 is formed by applying the chemically amplified positive silicon resist composition. Similar to the first resist film 4, the second resist film 6 may be formed by a conventionally known method.
  • the thickness of the second resist film 6 can be selected as appropriate from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the lower layer film 2, and is preferably lOOnm or more and 200 nm. It is as follows. By setting the thickness to 200 nm or less, the resist pattern can be formed with high resolution, and by setting it to lOO nm or more, there is an effect that sufficient resistance to dry etching can be obtained.
  • the silicon content of the chemical amplification type positive silicon resist composition is preferably 10% or more, preferably 20% or more, because a pattern with a high aspect ratio can be formed satisfactorily. Is more preferable.
  • the second resist film 6 is selectively exposed through the second mask pattern 7 and developed to form a second resist pattern 6 ′.
  • a conventionally known method may be applied as in the case of forming the first resist pattern 4 ′.
  • the second mask pattern 7 used here may be appropriately selected in consideration of a desired pattern like the first mask pattern 5.
  • the case where the same pattern as the first resist pattern 4 ′ is formed as the second resist pattern 6 ′ is illustrated, and the second mask pattern 7 is the same as the first mask pattern 5. , Space width d, pitch 2d.
  • the first mask pattern 5 is used as the second mask pattern 7, and the mask pattern is used during the selective exposure of the first resist film 4.
  • the second resist film 6 can be selectively exposed at a position different from the above.
  • the second resist pattern 6 is an L / S pattern having a line width d / 2, a space width 3d / 2, and a pitch 2d.
  • the hard mask pattern 3 ' which is the first pattern, is Adjacent with a source width of d / 2.
  • the lower layer film 2 is etched using the first pattern 3 ′ and the second resist pattern 6 as a mask, and the first pattern 3 ′ and the second pattern 2 are etched on the lower layer film 2. Transfer the second resist pattern 6 '. Then, the obtained pattern 2 ′ of the lower layer film 2 is used as a second pattern.
  • a conventionally known method can be applied to the method of etching the lower layer film 2 in the same manner as the method of etching the hard mask 3.
  • the plasma and / or reactive ion gas used for etching is not particularly limited, and can include, for example, oxygen, halogen, sulfur dioxide and the like. It is preferable to use oxygen-containing plasma and / or reactive ions because the resulting pattern has high resolution and is used for general purposes.
  • the L / S pattern has a line width of d / 2, a space width of d / 2, and a pitch of d.
  • d is 180 nm
  • a high-definition pattern having a line width and a space width of 90 nm can be formed according to the present invention.
  • the line width and space width may slightly vary depending on the conditions of each step.
  • the pattern formed on the substrate in the present invention has a high aspect ratio, and the shape that does not collapse is also excellent in high perpendicularity.
  • conventional patterns obtained through single-layer resist patterning cannot achieve such high definition and high aspect ratio.
  • the double patterning method that has been proposed in the past cannot be obtained with high precision because of the mixed pattern with poor pattern accuracy and patterns with low verticality.
  • a siloxane copolymer represented by the following chemical formula (1) was synthesized according to the synthesis method described in WO 2006/065321 pamphlet. 120 g of PGMEA, 5.29 g (0.025 monole) of phenolinotrichlorosilane, 6.77 g (0.050 monole) of trichlorosilane, 22.43 g (0.150 monole) of methylolene chlorosilane and 5. 54g (0. 025 mono) 2-force force A mixture of bomethoxyethyl chlorosilane was placed in the reactor under a nitrogen atmosphere. 200 g of PGMEA solution and 10 g (0.555 mol) of water were added to the trichlorosilane solution over 1 hour.
  • the reaction was stirred for 1 hour at 20 ° C. Thereafter, the resin solution was concentrated to about 10 wt% by a rotary evaporator at 40 ° C. About 40 g of ethanol was added to the resin solution. The solution was stripped again to 20 wt%. The flask was again removed, PGMEA was added to dilute the solution to 10 wt%, and filtered through a 0.20 micron PTFE filter.
  • Toximethylated glycoluril MX270 manufactured by Sanwa Chemical Co., Ltd.
  • PGMEA / PGME 6/4 (mass ratio)
  • TSAM ruene sulfonic acid monohydrate
  • PGMEA / PGME solution of the above siloxane-based copolymer (containing 100 parts by mass of siloxane-based copolymer in terms of solid content), component (B) of the types and blending amounts shown in Table 1 below, and compounds Components (C), (D), (E), and (F) were mixed and dissolved in the blending amounts shown in Table 1 below to prepare a resist composition.
  • BLC730 (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on an 8-inch silicon wafer as a lower layer film forming material, and beta treatment is performed at 250 ° C for 90 seconds to form a lower layer film with a thickness of 250 nm. Formed.
  • the hard mask forming material was applied onto the lower layer film, and baked at 250 ° C for 90 seconds to form a hard mask with a film thickness of 45 nm.
  • the negative resist composition was spin-coated on the hard mask, and 8 A first resist film having a thickness of 160 nm was formed by performing pre-beta (PAB) at 0 ° C. for 60 seconds.
  • PAB pre-beta
  • PEB post-exposure heating
  • the hard mask was etched.
  • the first resist pattern was transferred to the hard mask, and the first pattern was formed.
  • SEM scanning electron microscope
  • the resist film was peeled off by immersing it in a stripping solution at 40 ° C for 6 minutes.
  • the chemically amplified positive silicon resist composition is spin-coated on the first pattern, and pre-beta (PAB) is performed at 85 ° C. for 60 seconds to obtain a second film having a thickness of 130 ⁇ m.
  • the resist film was formed.
  • PEB post-exposure heating
  • the lower layer film was etched to form a second pattern.
  • the cross-sectional shape of this L / S pattern was observed by SEM (scanning electron microscope). As a result, it was confirmed that the line width was 90 nm at the portion masked with the hard mask, the portion masked with the second resist film was 89 nm, and the space width was 92 nm.
  • the aspect ratio after the second pattern was formed was about 3.2, it was confirmed that a pattern with a high aspect ratio was obtained.

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Abstract

A method of forming a pattern, comprising the steps of forming an underlayer film on a support with the use of a material for underlayer film formation; forming a hard mask on the underlayer film with the use of a silicon base material for hard mask formation; coating the hard mask with a chemical amplification type negative resist composition to thereby form a first resist film; subjecting the first resist film to selective exposure via a first mask pattern and development to thereby form a first resist pattern; with the use of the first resist pattern as a mask, etching the hard mask to thereby form a first pattern; coating the first pattern and underlayer film with a chemical amplification type positive silicon resist composition to thereby form a second resist film; subjecting the second resist film to selective exposure via a second mask pattern and development to thereby form a second resist pattern; and with the use of the first pattern and second resist pattern as a mask, etching the underlayer film to thereby form a second pattern.

Description

明 細 書  Specification
パターン形成方法  Pattern formation method
技術分野  Technical field
[0001] 本発明は、化学増幅型レジスト組成物を用いて、ダブルパターユング法によりパタ ーンを形成するパターン形成方法に関する。  [0001] The present invention relates to a pattern forming method for forming a pattern by a double patterning method using a chemically amplified resist composition.
本願 (ま、 2006年 9月 29曰 ίこ、 曰本 ίこ出願された特願 2006— 267848号 ίこ基づき 優先権を主張し、その内容をここに援用する。  This application (September 2006, 29-2006, Japanese patent application No. 2006-267848, filed with Japanese Patent Application No. 2006-267848, claiming priority, the contents of which are incorporated herein by reference.
背景技術  Background art
[0002] 基板の上に微細なパターンを形成し、これをマスクとしてエッチングを行うことによつ て前記パターンの下層を加工する技術 (パターン形成技術）は、半導体産業の IC作 成等に広く採用され、大きな注目を浴びている。  [0002] Technology that forms a fine pattern on a substrate and processes the lower layer of the pattern by etching using this as a mask (pattern formation technology) is widely used for IC creation in the semiconductor industry. Adopted and attracted great attention.
微細パターンは、通常、有機材料からなり、例えばリソグラフィ一法やナノインプリン ト法等の技術によって形成される。たとえばリソグラフィ一法においては、基板等の支 持体の上に、樹脂等の基材成分を含むレジスト組成物からなるレジスト膜を形成し、 前記レジスト膜に対し、所定のパターンが形成されたマスク（マスクパターン)を介して 、光、電子線等の放射線にて選択的露光を行い、現像処理を施すことにより、前記レ ジスト膜に所定形状のレジストパターンを形成する工程が行われる。露光した部分が 現像液に溶解する特性に変化するレジスト組成物をポジ型、露光した部分が現像液 に溶解しな!/、特性に変化するレジスト組成物をネガ型とレ、う。  The fine pattern is usually made of an organic material, and is formed by a technique such as a lithography method or a nanoimprint method. For example, in a lithography method, a resist film made of a resist composition containing a base material component such as a resin is formed on a support such as a substrate, and a mask in 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 such as light or an electron beam through (mask pattern) and performing development. A resist composition that changes its characteristics so that the exposed part dissolves in the developer is positive, and a resist composition that changes its characteristics does not dissolve in the developer!
そして、上記レジストパターンをマスクとして、基板をエッチングにより加工する工程 を経て半導体素子等が製造される。  Then, a semiconductor element or the like is manufactured through a process of processing the substrate by etching using the resist pattern as a mask.
[0003] 近年、リソグラフィー技術の進歩により急速にパターンの微細化が進んでいる。微細 化の手法としては、一般に、露光光源の短波長化が行われている。具体的には、従 来は、 g線、 i線に代表される紫外線が用いられていた力 現在では、 KrFエキシマレ 一ザ一や、 ArFエキシマレーザーを用いた半導体素子の量産が開始されており、た とえば ArFエキシマレーザーを用いたリソグラフィ一により、 45nmレベルの解像性で のパターン形成が可能となっている。また、解像性の更なる向上のために、これらェ キシマレーザーより短波長の Fエキシマレーザー、電子線、 EUV (極紫外線）や X線 [0003] In recent years, pattern miniaturization has rapidly progressed due to advances in lithography technology. As a technique for miniaturization, 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 lasers and ArF excimer lasers has started. For example, lithography with an ArF excimer laser enables pattern formation with a resolution of 45 nm. In addition, in order to further improve resolution, F excimer laser, electron beam, EUV (extreme ultraviolet) and X-ray with shorter wavelength than the excimer laser
2  2
などにつ!/、ても検討が行われて!/、る。  It ’s been reviewed! /
レジスト組成物には、これらの露光光源に対する感度、微細な寸法のパターンを再 現できる解像性等のリソグラフィー特性が求められる。このような要求を満たすレジス ト組成物として、酸の作用によりアルカリ溶解性が変化する基材成分と、露光により酸 を発生する酸発生剤とを含有する化学増幅型レジスト組成物が用いられている（たと えば特許文献 1参照）。たとえばポジ型の化学増幅型レジストは、通常、基材成分とし て、酸の作用によりアルカリ溶解性が増大する樹脂を含有しており、レジストパターン 形成時に、露光によって酸発生剤から酸が発生すると、露光部がアルカリ可溶性とな  Resist compositions are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist composition satisfying such requirements, a chemically amplified resist composition containing a base material component whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used. (For example, see Patent Document 1). For example, a positive chemically amplified resist usually contains, as a base material component, a resin whose alkali solubility is increased by the action of an acid. When a resist pattern is formed, an acid is generated from an acid generator by exposure. The exposed part becomes alkali-soluble
[0004] 最近、新しく提案されているリソグラフィー技術の 1つとして、パターユングを 2回以 上行ってパターンを形成するダブルパターユング法がある（たとえば非特許文献 2〜 3参照。）。このダブルパターユング法によれば、 1回のパターユングで形成されるパ ターンよりも微細なパターンが形成できるとされている。 [0004] Recently, as one of newly proposed lithography techniques, there is a double patterning method in which a pattern is formed by performing patterning twice or more (see, for example, Non-Patent Documents 2 to 3). According to this double patterning method, a finer pattern can be formed than a pattern formed by one patterning.
特許文献 1 :特開 2003— 241385号公報  Patent Document 1: Japanese Patent Laid-Open No. 2003-241385
非特許文献 1 :プロシーデイングスォブエスピーアイイ（Proceeding of SPIE)第 5 256巻、第 985〜994頁（2003年）.  Non-Patent Document 1: Proceeding of SPIE, Volume 5, 256, 985-994 (2003).
非特許文献 2 :プロシーデイングスォブエスピーアイイ（Proceedings of SPIE)第 6 153巻、第 61531K；!〜 7頁（2006年）.  Non-Patent Document 2: Proceedings of SPIE, Vol. 6 153, 61531K;! To p. 7 (2006).
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] しかしながら、非特許文献 1〜2で提案されている方法をはじめ従来のダブルバタ 一ユング法で実際に基板上に形成できるパターンは、パターン倒れや垂直性が高く なレ、形状のものが混在するなどし、高精細かつ高アスペクト比のパターン形成には、 まだ課題の残るものであった。 [0005] However, the patterns that can be actually formed on the substrate by the conventional double-battered-lung method including the methods proposed in Non-Patent Documents 1 and 2 are those that have a pattern collapse or high verticality and shape. There were still problems in forming high-definition and high-aspect-ratio patterns.
本発明は、上記事情に鑑みてなされたものであり、支持体上に高精細かつ高ァス ぺクト比のパターンを形成できるパターン形成方法を提供することを目的とする。 課題を解決するための手段 [0006] 上記の目的を達成するために、本発明は以下の構成を採用した。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of forming a high-definition and high aspect ratio pattern on a support. Means for solving the problem In order to achieve the above object, the present invention employs the following configuration.
すなわち、本発明は、化学増幅型レジスト組成物を用いてパターンを形成するバタ ーン形成方法であって、支持体上に、下層膜形成材料を用いて下層膜を形成する 工程と、前記下層膜上にシリコン系ハードマスク形成材料を用いてハードマスクを形 成する工程と、前記ハードマスク上に化学増幅型ネガ型レジスト組成物を塗布して第 一のレジスト膜を形成する工程と、前記第一のレジスト膜を、第一のマスクパターンを 介して選択的に露光し、現像して第一のレジストパターンを形成する工程と、前記第 一のレジストパターンをマスクとして、ハードマスクをエッチングして第一のパターンを 形成する工程と、前記第一のパターン及び下層膜の上に化学増幅型ポジ型シリコン 系レジスト組成物を塗布して第二のレジスト膜を形成する工程と、前記第二のレジスト 膜を、第二のマスクパターンを介して選択的に露光し、現像して第二のレジストバタ ーンを形成する工程と、前記第一のパターン及び第二のレジストパターンをマスクと して、下層膜をエッチングして第二のパターンを形成する工程とを含むことを特徴と する。  That is, the present invention is a pattern forming method for forming a pattern using a chemically amplified resist composition, the method comprising: forming a lower layer film using a lower layer film forming material on a support; and Forming a hard mask using a silicon-based hard mask forming material on the film; applying a chemically amplified negative resist composition on the hard mask; and forming a first resist film; The first resist film is selectively exposed through a first mask pattern and developed to form a first resist pattern, and the hard mask is etched using the first resist pattern as a mask. A step of forming a first pattern, and a step of forming a second resist film by applying a chemically amplified positive silicon resist composition on the first pattern and the lower layer film. A step of selectively exposing and developing the second resist film through a second mask pattern to form a second resist pattern; and the first pattern and the second resist pattern. And a step of etching the lower layer film to form a second pattern using the mask as a mask.
発明の効果  The invention's effect
[0007] 本発明によれば、支持体上に高精細かつ高アスペクト比のパターンを形成できる。  [0007] According to the present invention, a pattern with high definition and a high aspect ratio can be formed on a support.
図面の簡単な説明  Brief Description of Drawings
[0008] [図 1A]〜 [0008] [Fig. 1A] ~
[図 IE]本発明のパターン形成方法の好ましい実施態様のうち、パターユング工程（1 )を例示する概略工程図である。  FIG. IE is a schematic process diagram illustrating a patterning process (1) in a preferred embodiment of a pattern forming method of the present invention.
[図 2A]〜  [Figure 2A]
[図 2D]本発明のパターン形成方法の好ましい実施態様のうち、パターユング工程（2 )を例示する概略工程図である。  FIG. 2D is a schematic process diagram illustrating a patterning process (2) in a preferred embodiment of the pattern forming method of the present invention.
符号の説明  Explanation of symbols
[0009] 1···支持体、 2···下層膜、 2'···下層膜のパターン、 3···ハードマスク、 3'···ハ ードマスクのパターン、 4· ··第一のレジスト膜、 4， · ··第一のレジストパターン、 5· · · 第一のマスクパターン、 6· ··第二のレジスト膜、 6， · ··第二のレジストパターン、 7· · · 第二のマスクパターン 発明を実施するための最良の形態 [0009] 1 ... support, 2 ... lower layer film, 2 '... lower layer film pattern, 3 ... hard mask, 3' ... hard mask pattern, 4 ... first Resist film, 4, ... first resist pattern, 5 ... first mask pattern, 6 ... second resist film, 6, ... second resist pattern, 7 ... Second mask pattern BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 以下、まず本発明において用いる材料について説明する。 [0010] Hereinafter, materials used in the present invention will be described.
《化学増幅型ポジ型シリコン系レジスト組成物》  << Chemically Amplified Positive Silicon Resist Composition >>
本発明において、化学増幅型ポジ型シリコン系レジスト組成物は、特に限定される ものではないが、通常、酸の作用によりアルカリ溶解性が増大する成分および露光に より酸を発生する酸発生剤成分を含有するものが用いられる。そして、後述する下層 膜のパターン形成に汎用される酸素プラズマエッチングに対して耐性を有するものが 好ましい。  In the present invention, the chemically amplified positive silicon resist composition is not particularly limited, but is usually a component that increases alkali solubility by the action of an acid and an acid generator component that generates an acid upon exposure. The thing containing is used. And what has resistance with respect to the oxygen plasma etching generally used for pattern formation of the lower layer film mentioned later is preferable.
[0011] なかでも好ましいものとして、酸の作用によりアルカリ溶解性が増大する樹脂成分（ A) (以下、（A)成分という。）および露光により酸を発生する酸発生剤成分 (B) (以下 、（B)成分という。）を含有するレジスト組成物であって、前記樹脂成分 (A)が、下記 一般式 (al)で表される構成単位 (al)と、下記一般式 (a2)で表される構成単位 (a2) とを有する樹脂 (A1)を含有するレジスト組成物が挙げられる。  Among these, a resin component (A) whose alkali solubility is increased by the action of an acid (hereinafter referred to as “component (A)”) and an acid generator component (B) (hereinafter referred to as “acid generator” which generates an acid upon exposure) are preferable. And the resin component (A) is a structural unit (al) represented by the following general formula (al) and the following general formula (a2): And a resist composition containing a resin (A1) having the structural unit (a2) represented.
[0012] [化 1]
Figure imgf000006_0001
[0012] [Chemical 1]
Figure imgf000006_0001
[式 (a2)中、 R1は下記一般式 (I)で表される酸分解性基である。 ] [In the formula (a2), R 1 is an acid-decomposable group represented by the following general formula (I). ]
[0013] [化 2] [0013] [Chemical 2]
"~ ~~"{R2)g~~~L* Ζ , , , , (い "~ ~~" {R 2 ) g ~~~ L * Ζ,,,, (Yes
[式 (I)中、 R2〜R3はそれぞれ独立に連結基であり； Lは炭素数 1〜； 10の直鎖状また は分岐鎖状アルキレン基、炭素数 2〜20の直鎖状または分岐鎖状フルォロアルキレ ン基、置換または無置換のァリーレン基、置換または無置換の環状アルキレン基、お よび置換または無置換のアルカリ一レン基からなる群から選択される基であり； Zは酸 解離性基であり； gは 0または 1であり； hは 0または 1である。 ] [In the formula (I), R 2 to R 3 are each independently a linking group; L is a C 1 -C; linear or branched alkylene group having 10 carbons, and a linear chain having 2 to 20 carbons. Or a group selected from the group consisting of a branched fluoralkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted cyclic alkylene group, and a substituted or unsubstituted alkali monoylene group; A dissociable group; g is 0 or 1; h is 0 or 1. ]
[0014] 力、かるレジスト組成物は、露光前はアルカリ不溶性であり、露光により（B)成分から 酸が発生すると、前記酸が (A)成分に作用してそのアルカリ溶解性を増大させる。そ のため、レジストパターンの形成において、前記レジスト組成物を用いて得られるレジ スト膜を選択的に露光すると、露光部はアルカリ可溶性へ転じる。一方で、未露光部 はアルカリ不溶性のまま変化しないため、アルカリ現像を行うことにより、レジストパタ ーンを形成することができる。 [0014] The resist composition, which is strong, is insoluble in alkali before exposure, and is exposed to the component (B) by exposure. When an acid is generated, the acid acts on the component (A) to increase its alkali solubility. For this reason, in the formation of the resist pattern, when the resist film obtained using the resist composition is selectively exposed, the exposed portion becomes alkali-soluble. On the other hand, since the unexposed area remains insoluble in alkali and does not change, a resist pattern can be formed by performing alkali development.
[0015] < (A)成分〉 [0015] <(A) component>
[樹脂 (A1) ]  [Resin (A1)]
構成単位（al)は、樹脂 (A1)の透明性、特に 200nm以下の波長の光に対する透 明性の向上に寄与し、それによつてレジスト組成物の感度、解像性等を向上させる。 樹脂 (A1)中、構成単位 (al)の割合は、樹脂 (A1)を構成する全構成単位の合計 に対し、 20〜90モノレ0 /0カ好ましく、 30〜80モノレ0 /0カより好ましく、 40〜60モノレ0 /0カ さらに好ましい。構成単位（al)の割合が 20モル％以上であると、 200nm以下の波 長の光に対する透明性が向上する。また、 90モル％以下であると、構成単位（a2)等 の他の構成単位とのバランスが良好である。 The structural unit (al) contributes to the improvement of the transparency of the resin (A1), in particular, the transparency to light having a wavelength of 200 nm or less, thereby improving the sensitivity and resolution of the resist composition. Resin (A1), the proportion of the structural unit (al), based on the combined total of all the structural units that constitute the resin (A1), 20 to 90 Monore 0/0 Ca Preferably, preferably from 30 to 80 Monore 0/0 Ca , 40-60 Monore 0/0 mosquitoes further preferred. When the proportion of the structural unit (al) is 20 mol% or more, transparency to light having a wavelength of 200 nm or less is improved. If it is 90 mol% or less, the balance with other structural units such as the structural unit (a2) is good.
[0016] 構成単位（a2)は、上記一般式 (I)で表される酸分解性基 R1を有する。 R1は、露光 により（B)成分から酸が発生すると、前記基中の Zと Zに結合した原子との間の結合が 切断され、 Zと、それ以外の部分とに分解する。 The structural unit (a2) has an acid-decomposable group R 1 represented by the above general formula (I). When an acid is generated from the component (B) by exposure to R 1 , the bond between Z and the atom bonded to Z in the group is cleaved and decomposes into Z and other parts.
式 (I)中、 R2〜R3はそれぞれ独立に連結基である。前記連結基としては、特に限定 されない。好ましくは炭素数 1〜 5の直鎖状または分岐鎖状のアルキレン基であり、よ り好ましくはメチレン基及びエチレン基である。 In formula (I), R 2 to R 3 are each independently a linking group. The linking group is not particularly limited. A linear or branched alkylene group having 1 to 5 carbon atoms is preferable, and a methylene group and an ethylene group are more preferable.
[0017] Lは直鎖状または分岐鎖状アルキレン基、直鎖状または分岐鎖状フルォロアルキレ ン基、ァリーレン基、環状アルキレン基、またはアルカリ一レン基を表す。 [0017] L represents a linear or branched alkylene group, a linear or branched fluoroalkylene group, an arylene group, a cyclic alkylene group, or an alkali monolene group.
Lの直鎖状または分岐鎖状アルキレン基は、炭素数 1〜； 10であることが好ましぐ炭 素数 1〜5の直鎖状または分岐鎖状のアルキレン基がさらに好ましぐ特にメチレン基 、エチレン基が好ましい。  The linear or branched alkylene group of L is preferably 1 to 10 carbon atoms, more preferably a linear or branched alkylene group having 1 to 5 carbon atoms, particularly a methylene group. An ethylene group is preferred.
Lの炭素数 2〜20の直鎖状または分岐鎖状フルォロアルキレン基は、炭素数 2〜2 0の直鎖状または分岐鎖状アルキル基の水素原子の一部または全部がフッ素原子 で置換された基である。 Lのァリーレン基は、無置換のァリーレン基であってもよぐ前記無置換のァリーレン 基の環を構成する炭素原子に結合した水素原子の一部または全部が置換基で置換 された置換ァリーレン基であってもよい。無置換のァリーレン基としては、たとえばべ ンゼン、ナフタレン、アントラセン等から 2個の水素原子を除いた基が挙げられる。こ の無置換のァリーレン基の炭素数は 6〜； 14が好ましい。置換ァリーレン基における置 換基としては、アルキル基、アルコキシ基、ァリール基等が挙げられる。これら置換基 の炭素数は 1〜； 10であることが好ましい。 In the linear or branched fluoroalkylene group having 2 to 20 carbon atoms of L, part or all of the hydrogen atoms of the linear or branched alkyl group having 2 to 20 carbon atoms are fluorine atoms. A substituted group. The arylene group of L may be an unsubstituted arylene group, or a substituted arylene group in which some or all of the hydrogen atoms bonded to the carbon atoms constituting the ring of the unsubstituted arylene group are substituted with a substituent. It may be. Examples of the unsubstituted arylene group include groups in which two hydrogen atoms have been removed from benzene, naphthalene, anthracene and the like. The unsubstituted arylene group preferably has 6 to 14 carbon atoms. Examples of the substituent in the substituted arylene group include an alkyl group, an alkoxy group, and an aryl group. These substituents preferably have 1 to 10 carbon atoms.
Lの環状アルキレン基は、無置換の環状アルキレン基であってもよぐ前記環状ァ ルキレン基の環を構成する炭素原子に結合した水素原子の一部または全部が置換 基で置換された置換アルキレン基であってもよ!/、。無置換の環状アルキレン基として は、炭素数 4〜； 12の環状アルキレン基が好ましぐたとえばシクロペンタン、シクロへ キサン等のモノシクロアルカンから 2個の水素原子を除!/、た基；ァダマンタン、ノルボ ノレナン、ノルボルネン、メチルノルボルナン、ェチルノルボルナン、メチルノルボルネ ン、ェチルノルボルネン、イソボルナン、トリシクロデカン、テトラシクロドデカン等のポ リシクロアルカンから 2個の水素原子を除!/、た基などが挙げられる。置換環状アルキ レン基における置換基としては、上記置換ァリーレン基における置換基として挙げた ものと同様のものが挙げられる。  The cyclic alkylene group of L may be an unsubstituted cyclic alkylene group, or a substituted alkylene in which part or all of the hydrogen atoms bonded to the carbon atoms constituting the ring of the cyclic alkylene group are substituted with a substituent. It may be a group! / As the unsubstituted cyclic alkylene group, a cyclic alkylene group having 4 to 12 carbon atoms is preferable. For example, two hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane; , Norbornenenes, norbornene, methylnorbornane, ethylnorbornane, methylnorbornene, ethylnorbornene, isobornane, tricyclodecane, tetracyclododecane, etc. Can be mentioned. Examples of the substituent in the substituted cyclic alkylene group include the same groups as those described above as the substituent in the substituted arylene group.
Lのアルカリ一レン基は、ベンゼン、ナフタレン、アントラセン等の芳香族環に、 2個 のアルキレン基が結合してなる基である。前記芳香族環の炭素数は 6〜； 14が好まし い。前記アルキレン基としては、上記 R2〜 のアルキレン基として挙げたものと同様 のものが挙げられ、 2個のアルキレン基はそれぞれ同じであっても異なっていてもよい 。無置換のアルカリ一レン基としては、たとえば下記式 (AL— 1)で表される基が挙げ られる。置換のアルカリ一レン基は、前記無置換のアルカリ一レン基の芳香族環を構 成する炭素原子に結合した水素原子の一部または全部が置換基で置換された基が 挙げられ、前記置換基としては、上記置換ァリーレン基における置換基として挙げた ものと同様のものが挙げられる。 The alkali monolene group of L is a group formed by bonding two alkylene groups to an aromatic ring such as benzene, naphthalene or anthracene. The aromatic ring preferably has 6 to 14 carbon atoms. Examples of the alkylene group include the same groups as those described above for R 2 to, and the two alkylene groups may be the same or different. Examples of the unsubstituted alkali monolene group include a group represented by the following formula (AL-1). Examples of the substituted alkali monolene group include groups in which part or all of the hydrogen atoms bonded to the carbon atoms constituting the aromatic ring of the unsubstituted alkali monolene group are substituted with a substituent. Examples of the group include the same groups as those described above as the substituent in the substituted arylene group.
[化 3]
Figure imgf000009_0001
* · - - (Aし一 r) [Chemical 3]
Figure imgf000009_0001
* ·--(A one r)
[0019] Lとしては、メチレン基、エチレン基、環状アルキレン基、アルカリ一レン基が好まし く、無置換の環状アルキレン基がより好ましぐノルボルナンから 2個の水素原子を除 V、た基（ノルボルネン基）が特に好まし!/、。 [0019] L is preferably a methylene group, an ethylene group, a cyclic alkylene group, or an alkali monolene group, and an unsubstituted cyclic alkylene group is more preferred. (Norbornene group) is particularly preferred!
[0020] Zは酸解離性基である。 [0020] Z is an acid-dissociable group.
ここで、本発明において、「酸解離性基」とは、露光により（B)成分力 発生した酸 の作用により解離する基を意味する。  Here, in the present invention, the “acid-dissociable group” means a group that is dissociated by the action of an acid generated by (B) component force by exposure.
力、かる酸解離性基を有する構成単位 (a2)を含有する樹脂 (A1)と (B)成分とを含 有するレジスト組成物においては、露光により（B)成分から発生した酸力 を解離さ せ、その結果、樹脂 (A1)のアルカリ可溶性が増大する。  In the resist composition containing the resin (A1) containing the structural unit (a2) having a carboxylic acid-dissociable group and the component (B), the acid force generated from the component (B) by the exposure is dissociated. As a result, the alkali solubility of the resin (A1) increases.
Zの酸解離性基としては、（B)成分から発生した酸の作用により樹脂 (A1)のポリマ 一主鎖から解離し得る基であれば特に制限はない。たとえば従来からポジ型レジスト 組成物の基材成分の酸解離性溶解抑制基として提案されているものを使用すること ができる。  The acid dissociable group of Z is not particularly limited as long as it is a group that can be dissociated from the polymer main chain of the resin (A1) by the action of the acid generated from the component (B). For example, those conventionally proposed as acid dissociable, dissolution inhibiting groups for the base component of the positive resist composition can be used.
ここで、「酸解離性溶解抑制基」とは、解離前は前記化合物全体をアルカリ不溶と するアルカリ溶解抑制性を有するとともに、解離後は前記化合物全体をアルカリ可溶 性へ変化させる酸解離性基である。  Here, the “acid-dissociable, dissolution-inhibiting group” means an acid-dissociation property that has an alkali-dissolution inhibitory property that renders the entire compound insoluble in alkali before dissociation, and changes the entire compound to alkali-soluble after dissociation. It is a group.
酸解離性基の具体例としては、特に限定されるものではないが、たとえば一般式 COOR7で表される基、一般式一 OCOOR8で表される基、一般式一 OR9で表される 基等が挙げられる。 Specific examples of the acid dissociable group are not particularly limited. For example, the group represented by the general formula COOR 7 ; the group represented by the general formula 1 OCOOR 8 ; and the general formula 1 OR 9 Groups and the like.
上記式中、 R7〜R9は、それぞれ、 COOR7で表される基、 OCOOR8で表され る基、—OR9で表される基に酸解離性を付与する作用を有する有機基である。ここで 、有機基とは、少なくとも炭素原子とそれ以外の 1種以上の原子とを有する基を意味 する。 In the above formula, R 7 to R 9 are each an organic group having an action of imparting acid dissociation to the group represented by COOR 7 , the group represented by OCOOR 8 , and the group represented by —OR 9. is there. Here, the organic group means a group having at least a carbon atom and one or more other atoms.
[0021] R7としては、たとえば、鎖状の第 3級アルキル基;環上に第 3級炭素原子を含む脂 肪族環式基； 2—トリアルキルェチル基等が挙げられる。 鎖状の第 3級アルキル基としては、炭素数 4〜； 10が好ましぐ 4〜8がより好ましい。 鎖状第 3級アルキル基として、より具体的には、 tert ブチル基、 tert アミル基等 が挙げられる。 [0021] Examples of R 7 include a chain-like tertiary alkyl group; an aliphatic cyclic group containing a tertiary carbon atom on the ring; a 2-trialkylethyl group. The chain-like tertiary alkyl group is preferably 4 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. More specific examples of the chain-like tertiary alkyl group include a tert butyl group and a tert amyl group.
本発明において、「脂肪族環式基」とは、芳香族性を持たない単環式基または多環 式基を示す。環上に第 3級炭素原子を含む脂肪族環式基としては、炭素数 4〜； 14が 好ましぐ 5〜； 10がより好ましい。前記脂肪族環式基として、より具体的には、ァダマ ンチル基、ノノレボノレ二ノレ基、イソボルニル基、 2—メチルー 2—ァダマンチル基、 2— ェチルー 2—ァダマンチル基、 2—メチルー 2—イソボルニル基、 2—ブチルー 2—ァ ダマンチル基、 2—プロピルー2—イソボルニル基、 2—メチルー 2—テトラシクロデセ 二ノレ基、 2—メチノレー 2—ジヒドロジシクロペンタジェニノレーシクロへキシノレ基、 1ーメ チルー 1ーシクロペンチル基、 1ーェチルー 1ーシクロペンチル基、 1ーメチルー 1 シクロへキシル基、 1ーェチルー 1ーシクロへキシル基等が挙げられる。  In the present invention, the “aliphatic cyclic group” refers to a monocyclic group or polycyclic group having no aromaticity. As the aliphatic cyclic group containing a tertiary carbon atom on the ring, 4 to 14 carbon atoms are preferable, 5 to 10 carbon atoms are more preferable. More specific examples of the aliphatic cyclic group include an adamantyl group, a nonolebonorinole group, an isobornyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 2-methyl-2-isobornyl group, 2-butyl-2-adamantyl group, 2-propyl-2-isobornyl group, 2-methyl-2-tetracyclodece 2-nore group, 2-methylolene 2-dihydrodicyclopentageninole cyclohexylene group, 1-methyl-1-cyclopentyl Group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, and the like.
2—トリアルキルェチル基としては、 2—トリメチノレシリノレエチノレ基、 2—トリエチノレシリ ルェチル基等が挙げられる。  Examples of the 2-trialkylethyl group include a 2-trimethinoresilinoreethinole group and a 2-triethinorecyleethyl group.
[0022] R8としては、上記 R7と同様のものが挙げられる。 [0022] Examples of R 8 include the same as R 7 described above.
R9としては、テトラヒドロビラニル基、 1—ァダマントキシメチル基、 1—シクロへキシ ノレォキシメチル基、トリアルキルシリル基等が挙げられ、前記トリアルキルシリル基とし ては、トリメチルシリル基等が挙げられる。 Examples of R 9 include a tetrahydrobiranyl group, a 1-adamantoxymethyl group, a 1-cyclohexylanoloxymethyl group, and a trialkylsilyl group. Examples of the trialkylsilyl group include a trimethylsilyl group. .
[0023] Zとしては、上記のなかでも、一般式一 COOR7で表される基が好ましぐ R7が鎖状 の第 3級アルキル基である基がより好ましぐ R7が tert ブチル基である基、すなわ ち tert ブトキシカルボニル基が最も好まし!/、。 [0023] Among the above, Z is preferably a group represented by the general formula 1 COOR 7 ; R 7 is more preferably a chain-like tertiary alkyl group; and R 7 is tert butyl. The group which is the group, ie the tert butoxycarbonyl group is most preferred!
[0024] gは 0であってもよぐ 1であってもよぐ 0であることが好ましい。  [0024] g may be 0 or 1 and is preferably 0.
hは 0であってもよく、 1であってもよく、 0であることが好ましい。  h may be 0, may be 1, and is preferably 0.
[0025] 本発明において、 R1は、特に、下記一般式 (1—1)で表される基であることが好まし い。 In the present invention, R 1 is particularly preferably a group represented by the following general formula (1-1).
[0026] [化 4] [0026] [Chemical 4]
Figure imgf000011_0001
Figure imgf000011_0001
[式中、 R'は水素原子または炭素数 1〜5のアルキル基であり、 Z'は鎖状の第 3級ァ ルキル基である。 ] [Wherein, R ′ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z ′ is a chain-like tertiary alkyl group. ]
[0027] 構成単位（a2)は、 1種を単独で用いてもよぐ 2種以上を併用してもよい。  As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.
樹脂 (A1)中、構成単位 (a2)の割合は、樹脂 (A1)を構成する全構成単位の合計 に対し、 10〜80モノレ0 /0カ好ましく、 20〜60モノレ0 /0カより好ましく、 30〜50モノレ0 /0カ さらに好ましい。構成単位（a2)の割合が 10モル％以上であると、レジスト組成物とし た際にパターンを得ることができ、上限以下であると、他の構成単位とのバランスが良 好である。 Resin (A1), the proportion of the structural unit (a2), based on the combined total of all the structural units that constitute the resin (A1), 10 to 80 Monore 0/0 Ca Preferably, preferably from 20 to 60 Monore 0/0 Ca , 30-50 Monore 0/0 mosquitoes further preferred. When the proportion of the structural unit (a2) is 10 mol% or more, a pattern can be obtained when the resist composition is used, and when it is less than the upper limit, the balance with other structural units is good.
[0028] また、本発明においては、樹脂 (A1)中、構成単位（al)および (a2)の合計の割合  [0028] In the present invention, the total proportion of the structural units (al) and (a2) in the resin (A1)
1S 樹脂 (A1)を構成する全構成単位の合計に対し、 50モル％以上であることが好 ましぐ 70モル0 /0以上がより好ましぐ 100モル0 /0であってもよい。 Based on the combined total of all structural units constituting the 1S resin (A1), it is good Mashigu 70 mole 0/0 or more and 50 mol% or more may be more preferable instrument 100 mole 0/0.
[0029] 樹脂 (A1)は、本発明の効果を損なわない範囲で、上記構成単位 (al)および (a2) 以外の他の構成単位を含有してもよ!/、。 [0029] The resin (A1) may contain other structural units other than the structural units (al) and (a2) as long as the effects of the present invention are not impaired!
構成単位（al)および（a2)以外の他の構成単位としては、たとえば下記式（a3)で 表される構成単位（a3)が挙げられる。  Examples of the structural unit other than the structural units (al) and (a2) include the structural unit (a3) represented by the following formula (a3).
[0030] [化 5]
Figure imgf000011_0002
' ' ' · ( a 3 ) [0030] [Chemical 5]
Figure imgf000011_0002
'''· (A 3)
[0031] 式（a3)中、 R15は、炭素数 1〜20のアルキル基、またはァリール基である。 In the formula (a3), R 15 is an alkyl group having 1 to 20 carbon atoms or an aryl group.
R15のアルキル基としては、直鎖状、分岐鎖状または環状のいずれであってもよぐ 炭素数;!〜 6の直鎖状または分岐鎖状のアルキル基、または炭素数 5〜； 12の環状ァ ルキル基が好ましぐ具体的には、メチル基、ェチル基、 n—プロピル基、イソプロピ ノレ基、 n—ブチル基、 tert—ブチル基、シクロペンチル基、シクロへキシル基等が挙 げられる。 The alkyl group for R 15 may be linear, branched, or cyclic. Carbon number;! -6 to 6 linear or branched alkyl group, or 5 to 6 carbon atoms; Specific examples of preferred cyclic alkyl groups include methyl, ethyl, n-propyl, isopropylene, n-butyl, tert-butyl, cyclopentyl, and cyclohexyl groups. I can get lost.
R15のァリール基としては、フエニル基、ナフチル基等が挙げられ、これらは置換基 としてアルキル基等を有して!/、てもよ!/、。 Examples of the aryl group of R 15 include a phenyl group and a naphthyl group, and these have an alkyl group or the like as a substituent!
[0032] 樹脂 (A1)の製造は、公知の水素シルセスキォキサン樹脂の製造方法を用いて行 うこと力 Sできる。一例を挙げると、まず、トリクロロシラン (HSiCl )等のトリハロゲン化 [0032] The resin (A1) can be produced using a known method for producing a hydrogen silsesquioxane resin. One example is trihalogenation such as trichlorosilane (HSiCl).
3  Three
シランの加水分解縮合を行うことによって、構成単位（al)を含有する水素シルセスキ ォキサン樹脂（以下、前駆体樹脂という。）を合成する。このようにして製造される前駆 体樹脂中には、構成単位（al)が含まれる。また、力、かる合成方法においては、通常 、反応時に、構成単位（al)のほかに、（Si (OH) O )、（HSi (OH)〇 ）、（SiO  By performing hydrolytic condensation of silane, a hydrogen silsesquioxane resin (hereinafter referred to as precursor resin) containing the structural unit (al) is synthesized. The precursor resin produced in this way contains the structural unit (al). In addition, in the synthesis method of force and kara, usually, in addition to the structural unit (al), (Si (OH) O), (HSi (OH) 0), (SiO
3/2 2/2 4/ 3/2 2/2 4 /
)等の構成単位も副生することが多い。また、このようにして合成された前駆体樹脂) Etc. are often produced as by-products. The precursor resin synthesized in this way
2 2
中には、通常、ラダー型、ランダム型、カゴ型等の種々の網目状の構造のポリマーが p¾よれ 。  Among them, polymers having various network structures such as ladder type, random type, and cage type are usually used.
ついで、前駆体樹脂中に含まれる水素原子 (たとえば構成単位 (al)の水素原子） の一部を R1で置換することにより、前駆体樹脂に R1を導入する。これにより、構成単 位（a 1)の一部が構成単位（a2)となり、構成単位（a 1)および構成単位（a2)を含有 する樹脂 (A1)が得られる。また、このとき、前駆体樹脂中に（Si (OH) O )、 (HSi ( Then, a part of hydrogen atoms contained in the precursor resin (for example, a hydrogen atom of the structural unit (al)) by replacing R 1, introducing R 1 to precursor resin. Thereby, a part of the structural unit (a 1) becomes the structural unit (a2), and the resin (A1) containing the structural unit (a 1) and the structural unit (a2) is obtained. At this time, (Si (OH) O), (HSi (
3/2  3/2
OH) O )等の構成単位が含まれる場合は、それらの構成単位中の水素原子が R1 When a structural unit such as OH) O) is included, the hydrogen atom in the structural unit is R 1
2/2  2/2
で置換された構成単位等も形成される。  A structural unit or the like substituted with is also formed.
R1は、たとえば、触媒の存在下、ヒドロシリル化反応により、導入しょうとする R1に対 応する化合物（たとえばビシクロ [2, 2, 1]ヘプトー 5—ェンー 2— tert—ブチルカル ボキシレート等）と、前記前駆体樹脂とを反応させることにより導入できる。 R 1 is, for example, a compound corresponding to R 1 to be introduced by hydrosilylation reaction in the presence of a catalyst (for example, bicyclo [2, 2, 1] hept-5-ene-2-tert-butylcarboxylate, etc.) Can be introduced by reacting with the precursor resin.
また、このとき、導入しょうとする R1に対応する化合物の使用量、反応条件等を調節 することにより、樹脂 (A1)中の構成単位 (al)、（a2)等の割合を調節できる。 At this time, the proportion of the structural units (al), (a2), etc. in the resin (A1) can be adjusted by adjusting the amount of the compound corresponding to R 1 to be introduced and the reaction conditions.
[0033] 樹脂（A1)においては、構成単位（al)：構成単位（a2) = 90 : 10〜10〜90 (モル 匕）であること力《好ましく、 80 : 20〜30： 70であることカさらに好ましく、 70 : 30〜35：[0033] In the resin (A1), the structural unit (al): the structural unit (a2) = 90: 10 to 90 to 90 (mol 匕), preferably: 80: 20 to 30: 70 More preferably, 70:30 to 35:
65であることカ特に好ましく、 65： 35-40： 60であることカ最も好まし!/、。 65 is particularly preferred, and 65: 35-40: 60 is most preferred! /.
[0034] 樹脂 (A1)の質量平均分子量 (Mw) (ゲルパーミエーシヨンクロマトグラフィー（以下[0034] Mass average molecular weight (Mw) of resin (A1) (gel permeation chromatography
、 GPCと略記することもある）によるポリスチレン換算、以下同様。）は、特に限定され るもので (まなレヽ力 好まし < (ま 1500〜20000、より好まし < (ま 6000〜6500である。 上限以下であると有機溶剤への溶解性が良好であり、下限値以上であると、形成さ れるレジストパターンの形状が向上する。 , Sometimes abbreviated as GPC) in terms of polystyrene, and so on. ) Is particularly limited (Mana repulsive power is preferable <(1500-20000, more preferably <(6000-6500. If it is below the upper limit, the solubility in organic solvents is good, and if it is above the lower limit) As a result, the shape of the formed resist pattern is improved.
また、 Mw/Mnは、特に限定されるものではないが、好ましくは 1. 0〜6. 0、さらに 好ましくは 1. 0〜2· 5である。  Mw / Mn is not particularly limited, but is preferably 1.0 to 6.0, and more preferably 1.0 to 2.5.
[0035] 樹脂 (A1)は、 1種を単独で用いてもよぐ 2種以上を併用してもよい。  As the resin (A1), one type may be used alone, or two or more types may be used in combination.
(Α)成分中、樹脂 (A1)の割合は、本発明の効果である支持体上における高精細 かつ高アスペクト比のパターン形成に優れることから、（Α)成分の総質量に対し、 50 質量％以上が好ましぐ 70質量％以上がより好ましぐ 100質量％であってもよい。  The proportion of the resin (A1) in the component (る こ と) is excellent in forming a high-definition and high aspect ratio pattern on the support, which is the effect of the present invention. % Or more is preferred 70 mass% or more may be 100 mass%.
[0036] 本発明において、（Α)成分は、本発明の効果を損なわない範囲で、上記樹脂 (A1 )以外の樹脂成分 (Α2) (以下、（Α2)成分という。）を含有してもよい。力、かる (Α2)成 分としては、特に制限はなぐレジストパターン形成時に使用する光源に応じ、一般 的に化学増幅型レジスト組成物のベース樹脂として提案されている多数の樹脂の中 から任意に選択して用いることができる。  [0036] In the present invention, the component (し て も) may contain a resin component (Α2) other than the resin (A1) (hereinafter referred to as the component (で 2)) as long as the effects of the present invention are not impaired. Good. There are no particular restrictions on the strength and strength (Α2). Depending on the light source used when forming the resist pattern, any of a number of resins generally proposed as base resins for chemically amplified resist compositions can be used. It can be selected and used.
[0037] < (Β)成分〉  [0037] <(Β) component>
(Β)成分としては、特に限定されず、これまで化学増幅型レジスト用の酸発生剤とし て提案されてレ、る任意のものを使用すること力 Sできる。  The component (ii) is not particularly limited, and any component that has been proposed as an acid generator for chemically amplified resists can be used.
そのような（Β)成分としては、これまで、ョードニゥム塩やスルホニゥム塩などのォニ ゥム塩系酸発生剤、ォキシムスルホネート系酸発生剤、ビスアルキルまたはビスァリ 一ルスルホニルジァゾメタン類、ポリ（ビススルホ二ノレ）ジァゾメタン類などのジァゾメタ ン系酸発生剤、ニトロべンジルスルホネート系酸発生剤、イミノスルホネート系酸発生 剤、ジスルホン系酸発生剤など多種のものが知られている。  Such (Β) components have so far included onium salt-based acid generators such as odonium salts and sulfonium salts, oxime sulfonate-based acid generators, bisalkyl or bis-sulfonylsulfonyl diazomethanes. There are various known diazomethane acid generators such as poly (bissulfonino) diazomethanes, nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators.
[0038] ォニゥム塩系酸発生剤としては、例えば下記一般式 (b— 0)で表される酸発生剤が 挙げられる。  [0038] Examples of the onium salt-based acid generator include an acid generator represented by the following general formula (b-0).
[0039] [化 6] [0039] [Chemical 6]
( b ~~ 0 )(b ~~ 0)
Figure imgf000013_0001
[式中、 R51は、直鎖、分岐鎖若しくは環状のアルキル基、または直鎖、分岐鎖若しく は環状のフッ素化アルキル基を表し; R52は、水素原子、水酸基、ハロゲン原子、直 鎖若しくは分岐鎖状のアルキル基、直鎖若しくは分岐鎖状のハロゲン化アルキル基
Figure imgf000013_0001
[Wherein R 51 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, a halogen atom, a straight Chain or branched alkyl group, linear or branched alkyl halide group
、または直鎖若しくは分岐鎖状のアルコキシ基であり； R53は置換基を有していてもよ ぃァリール基であり； u"は 1〜3の整数である。 ] Or a linear or branched alkoxy group; R 53 is an aryl group which may have a substituent; u ″ is an integer of 1 to 3. ]
[0040] 一般式 (b— 0)において、 R51は、直鎖、分岐鎖若しくは環状のアルキル基、または 直鎖、分岐鎖若しくは環状のフッ素化アルキル基を表す。 In the general formula (b-0), R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
前記直鎖若しくは分岐鎖状のアルキル基としては、炭素数 1〜； 10であることが好ま しぐ炭素数 1〜8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。 前記環状のアルキル基としては、炭素数 4〜； 12であることが好ましぐ炭素数 5〜1 0であることがさらに好ましぐ炭素数 6〜； 10であることが最も好ましい。  The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. . The cyclic alkyl group preferably has 4 to 12 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 6 to 10 carbon atoms, and most preferably 10 to 10 carbon atoms.
前記フッ素化アルキル基としては、炭素数 1〜； 10であることが好ましぐ炭素数；!〜 8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。また、前記フッ 化アルキル基のフッ素化率（アルキル基中全水素原子の個数に対する置換したフッ 素原子の個数の割合）は、好ましくは 10〜； 100%、さらに好ましくは 50〜； 100%であ り、特に水素原子をすベてフッ素原子で置換したもの力 酸の強度が強くなるので好 ましい。  The fluorinated alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The fluorination rate of the alkyl fluoride 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%. Especially, all hydrogen atoms are substituted with fluorine atoms. This is preferable because the strength of the acid increases.
R51としては、直鎖状のアルキル基またはフッ素化アルキル基であることが最も好ま しい。 R 51 is most preferably a linear alkyl group or a fluorinated alkyl group.
[0041] R52は、水素原子、水酸基、ハロゲン原子、直鎖若しくは分岐鎖状のアルキル基、 直鎖若しくは分岐鎖状のハロゲン化アルキル基、または直鎖若しくは分岐鎖状のァ ルコキシ基である。 [0041] 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. .
R52において、ハロゲン原子としては、フッ素原子、臭素原子、塩素原子、ヨウ素原 子などが挙げられ、フッ素原子が好ましい。 In R 52 , 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.
R52において、アルキル基は、直鎖または分岐鎖状であり、その炭素数は好ましくは ；!〜 5、特に;!〜 4、さらには 1〜3であることが望ましい。 In R 52 , the alkyl group is linear or branched, and the carbon number thereof is preferably;!-5, in particular;!-4, and more preferably 1-3.
R52において、ハロゲン化アルキル基は、アルキル基中の水素原子の一部または全 部がハロゲン原子で置換された基である。ここでのアルキル基は、前記 R52における「 アルキル基」と同様のものが挙げられる。置換するハロゲン原子としては上記「ノ、ロゲ ン原子」について説明したものと同様のものが挙げられる。ハロゲン化アルキル基に おいて、水素原子の全個数の 50〜； 100%がハロゲン原子で置換されていることが望 ましぐ全て置換されていることがより好ましい。 In R 52 , 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. Alkyl group here, "in the R 52 The same thing as an "alkyl group" is mentioned. Examples of the halogen atom to be substituted are the same as those described above for “no, log atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
R52において、アルコキシ基としては、直鎖状または分岐鎖状であり、その炭素数は 好ましくは 1〜5、特に;!〜 4、さらには 1〜3であることが望ましい。 In R 52 , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly preferably !! to 4, and more preferably 1 to 3.
R52としては、これらの中でも水素原子が好ましい。 Among these, R 52 is preferably a hydrogen atom.
[0042] R53は置換基を有して!/、てもよ!/、ァリール基であり、置換基を除!/、た基本環（母体環 )の構造としては、ナフチル基、フエニル基、アントラセニル基などが挙げられる。本発 明の効果や ArFエキシマレーザーなどの露光光の吸収の観点から、フエニル基が望 ましい。 [0042] R 53 has a substituent! /, May! /, An aryl group, and the structure of the basic ring (matrix ring) is a naphthyl group or a phenyl group. And anthracenyl group. From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
置換基としては、水酸基、低級アルキル基（直鎖または分岐鎖状であり、その好まし い炭素数は 5以下であり、特にメチル基が好ましい）などを挙げることができる。この明 細書及び請求の範囲において「低級」は炭素数 1〜 5であることを意味する。  Examples of the substituent include a hydroxyl group and a lower alkyl group (straight chain or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group). In this description and in the claims, “lower” means 1 to 5 carbon atoms.
R53のァリール基としては、置換基を有しな!/、ものがより好まし!/、。 The aryl group of R 53 has no substituent! /, More preferably! / ,.
u"は 1〜3の整数であり、 2または 3であることが好ましぐ特に 3であることが望まし い。  u "is an integer of 1 to 3, 2 or 3 is preferred and 3 is particularly desirable.
[0043] 一般式 (b— 0)で表される酸発生剤の好ましいものは以下の様なものを挙げること ができる。  [0043] Preferable examples of the acid generator represented by the general formula (b-0) include the following.
[0044] [化 7] [0044] [Chemical 7]
4「9。。3
Figure imgf000016_0001
4 “9.3.
Figure imgf000016_0001
[0045] また上記以外の他のォニゥム塩系酸発生剤としては、例えば下記一般式 (b— 1)ま たは (b— 2)で表される化合物が挙げられる。 [0045] Examples of other onium salt acid generators other than the above include compounds represented by the following general formula (b-1) or (b-2).
[0046] [化 8] [0046] [Chemical 8]
Figure imgf000016_0002
Figure imgf000016_0002
[式中、 ，，〜 "， R5"〜R6"は、それぞれ独立に、ァリール基またはアルキル基を 表し; R4"は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表し;[Wherein, ,, to “, R 5 ” to 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 alkyl group; Representation;
R 〜R' )一ル基を表し、 R5 "〜 "のうち少なくとも 1つは ァリール基を表す。 ] R to R ') represents one group, and at least one of R 5 "to" represents an aryl group. ]
式 (b— 1)中、 1"〜!^"は、それぞれ独立にァリール基またはアルキル基を表す。 ！^，，〜 3"のうち、少なくとも 1っはァリール基を表す。 1"〜!^3"のうち、 2以上がァリ ール基であることが好ましぐ 1"〜!^"のすべてがァリール基であることが最も好まし い。 Ri"〜 "のァリール基としては、特に制限はなぐ例えば、炭素数 6〜20のァリー ル基であって、前記ァリール基は、その水素原子の一部または全部がアルキル基、 アルコキシ基、ハロゲン原子等で置換されていてもよぐされていなくてもよい。ァリー ル基としては、安価に合成可能なことから、炭素数 6〜； 10のァリール基が好ましい。 具体的には、たとえばフエニル基、ナフチル基が挙げられる。 In formula (b— 1), 1 “˜! ^” Each independently represents an aryl group or an alkyl group. ! ^ ,, to 3 "out of, representing at least 1 Tsu is Ariru group. 1" ~! ^ 3 "out of, 2 or more preferably be a § Li Lumpur based tool 1" ~! ^ "Of Most preferably all are aryl. The aryl group of Ri "to" 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. It does not need to be substituted with an atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group.
前記ァリール基の水素原子が置換されて!/、てもよ!/、アルキル基としては、炭素数 1 〜5のアルキル基が好ましぐメチル基、ェチル基、プロピル基、 n ブチル基、 tert ブチル基であることが最も好ましい。  The hydrogen atom of the aryl group is substituted! /, May! /, And the alkyl group is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert. Most preferred is a butyl group.
前記ァリール基の水素原子が置換されていてもよいアルコキシ基としては、炭素数 ；!〜 5のアルコキシ基が好ましぐメトキシ基、エトキシ基が最も好ましい。  As the alkoxy group that may be substituted for the hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having from 5 to 5 carbon atoms being preferred.
前記ァリール基の水素原子が置換されていてもよいハロゲン原子としては、フッ素 原子であることが好ましい。  The halogen atom with which the hydrogen atom of the aryl group may be substituted is preferably a fluorine atom.
R1"〜R3"のアルキル基としては、特に制限はなぐ例えば炭素数;!〜 10の直鎖状R1 as alkyl group "to R 3", Nag particularly limited for example, the number of carbon atoms;! A ~ 10 linear
、分岐状または環状のアルキル基等が挙げられる。解像性に優れる点から、炭素数 1 〜5であることが好ましい。具体的には、メチル基、ェチル基、 n—プロピル基、イソプ 口ピル基、 n ブチル基、イソブチル基、 n ペンチル基、シクロペンチル基、へキシ ル基、シクロへキシル基、ノエル基、デカニル基等が挙げられる。解像性に優れ、ま た安価に合成可能なことから好まし!/、ものとして、メチル基を挙げること力 Sできる。 これらの中で、 1"〜!^"は、それぞれ、フエニル基またはナフチル基であることが 最も好ましい。 And a branched or cyclic alkyl group. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. 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, Noel group, decanyl group Etc. It is preferred because it is excellent in resolution and can be synthesized at low cost! Of these, 1 “˜! ^” Is most preferably a phenyl group or a naphthyl group, respectively.
R4"は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表す。 前記直鎖のアルキル基としては、炭素数 1〜； 10であることが好ましぐ炭素数；!〜 8 であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。 R 4 ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group. The linear alkyl group preferably has 1 to 10 carbon atoms; preferably 8 to 8 carbon atoms; Most preferably, it is 1 to 4 carbon atoms.
前記環状のアルキル基としては、前記 R1"で示したような環式基であって、炭素数 4 〜； 15であることが好ましぐ炭素数 4〜； 10であることがさらに好ましぐ炭素数 6〜； 10 であることが最も好ましい。 The cyclic alkyl group is a cyclic group as indicated by R 1 ″ and preferably has 4 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Most preferably, it has 6 to 10 carbon atoms.
前記フッ素化アルキル基としては、炭素数 1〜； 10であることが好ましぐ炭素数；!〜 8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。また。該フッ化 アルキル基のフッ素化率（アルキル基中のフッ素原子の割合）は、好ましくは 10〜； 10 0%、さらに好ましくは 50〜； 100%であり、特に水素原子をすベてフッ素原子で置換 したものが、酸の強度が強くなるので好ましい。 The fluorinated alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Also. The fluoride The fluorination rate of the alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to; 100%, more preferably 50 to 100%. Particularly, all the hydrogen atoms were substituted with fluorine atoms. It is preferable because the strength of the acid is increased.
R4"としては、直鎖または環状のアルキル基、またはフッ素化アルキル基であること が最も好ましい。 R 4 ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
[0049] 式 (b— 2)中、 R5"〜R6"は、それぞれ独立にァリール基またはアルキル基を表す。 In formula (b-2), R 5 ″ to R 6 ″ each independently represents an aryl group or an alkyl group.
R5"〜R6"のうち、少なくとも 1っはァリール基を表す。 R5"〜R6"のすべてがァリール 基であることが好ましい。 At least one of R 5 "to R 6 " represents an aryl group. All of R 5 "to R 6 " are preferably aryl groups.
R5"〜R6"のァリール基としては、 1"〜!^"のァリール基と同様のものが挙げられるExamples of R 5 "~ R 6 " arele groups are the same as those for 1 "~! ^"
〇 Yes
R5"〜R6"のアルキル基としては、 1"〜!^"のアルキル基と同様のものが挙げられ これらの中で、 R5"〜R6"はすべてフエニル基であることが最も好ましい。 式 (b— 2)中の R4"としては上記式 (b—1)の R4"と同様のものが挙げられる。 As the alkyl group for R 5 "~R 6", 1 "~! ^" Among these include the same alkyl groups, most that all R 5 "~R 6" is a phenyl group preferable. "The R 4 in the formula (b-1)" Formula (b-2) R 4 in the same groups as those described above for.
[0050] 式 (b— 1)、（b— 2)で表されるォニゥム塩系酸発生剤の具体例としては、ジフエ二 [0050] Specific examples of the onion salt acid generators represented by the formulas (b-1) and (b-2) include diphenols.
、ビス（4 tert ブチルフエニル）ョードニゥムのトリフルォロメタンスルホネートまた Bis (4 tert butylphenyl) odonitrium trifluoromethanesulfonate or
ノレホネート、トリ（4 メチルフエ二ノレ）スルホ二ゥムのトリフルォロメタンスルホネート、 Norefonate, tri (4 methylphenyl) sulfurium trifluoromethanesulfonate,
モノフエニルジメチルスルホニゥムのトリフルォロメタンスルホネート、そのヘプタフノレ ノレホネートまたはそのノナフルォロブタンスルホネート、 （4 メチルフエ二ノレ）ジフエ二 ネートまたはそのノナフルォロブタンスルホネート、 （4ーメトキシフエニル）ジフエニル ートまたはそのノナフノレォロブタンスノレホネート、トリ（4 tert ブチノレ）フエニノレスノレ またはそのノナフルォロブタンスルホネート、ジフエニル（1一（4ーメトキシ）ナフチル） ートまたはそのノナフルォロブタンスルホネート、ジ（1 ナフチノレ）フエニルスルホニ はそのノナフルォロブタンスルホネートなどが挙げられる。また、これらのォニゥム塩 のァニオン部がメタンスルホネート、 n—プロパンスルホネート、 n—ブタンスルホネー K n—オクタンスルホネートに置き換えたォニゥム塩も用いることができる。 Monophenyldimethylsulfonium trifluoromethanesulfonate, its heptafunole sulfonate, or its nonafluorobutane sulfonate, (4 methylphenylenodi) diphenyl Or its nonafluorobutanesulfonate, (4-methoxyphenyl) diphenylate or its nonafnorenobutanesulfonate, tri (4 tertbutinore) phenenolesnore or its nonafrobutanesulfonate, diphenyl (1 Examples of mono (4-methoxy) naphthyl) ate or nonafluorobutanesulfonate thereof, and di (1naphthinore) phenylsulfonate include nonafrobutanesulfonate. Further, onium salts in which the anion portion of these onium salts is replaced by methanesulfonate, n-propanesulfonate, or n-butanesulfonate Kn-octanesulfonate can also be used.
[0051] また、前記一般式 (b— 1)又は（b— 2)において、ァニオン部を下記一般式 (b— 3) 又は (b— 4)で表されるァニオン部に置き換えたォニゥム塩系酸発生剤も挙げられる (カチオン部は (b— 1)又は (b— 2)と同様）。  [0051] Further, in the general formula (b-1) or (b-2), an anion salt system in which an anion is replaced with an anion represented by the following general formula (b-3) or (b-4) Also included are acid generators (the cation moiety is the same as (b-1) or (b-2)).
[0052] [化 9]  [0052] [Chemical 9]
Figure imgf000019_0001
Figure imgf000019_0001
[式中、 X"は、少なくとも 1つの水素原子がフッ素原子で置換された炭素数 2〜6のァ ノレキレン基を表し; Υ"、 Ζ"は、それぞれ独立に、少なくとも 1つの水素原子がフッ素 原子で置換された炭素数;!〜 10のアルキル基を表す。 ] [In the formula, X "represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Υ" and Ζ "are each independently at least one hydrogen atom is fluorine. The number of carbon atoms substituted with an atom; represents an alkyl group having! -10.
[0053] X"は、少なくとも 1つの水素原子がフッ素原子で置換された直鎖状または分岐状の アルキレン基であり、前記アルキレン基の炭素数は 2〜6であり、好ましくは炭素数 3 〜5、最も好ましくは炭素数 3である。 [0053] X "is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5, most preferably 3 carbon atoms.
Υ"、 Ζ"は、それぞれ独立に、少なくとも 1つの水素原子がフッ素原子で置換された 直鎖状または分岐状のアルキル基であり、前記アルキル基の炭素数は 1〜； 10であり 、好ましくは炭素数 1〜7、より好ましくは炭素数 1〜3である。 X"のアルキレン基の炭素数または Y"、 Ζ"のアルキル基の炭素数は、上記炭素数 の範囲内において、レジスト溶媒への溶解性も良好である等の理由により、小さいほ ど好ましい。 Υ "and Ζ" are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably Has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms. The number of carbons in the alkylene group of X ″ or the number of carbons in the alkyl group of Y ″ and 小 さ い ″ is preferably as small as possible because the solubility in a resist solvent is good within the above-mentioned range of carbon numbers.
また、 X"のアルキレン基または Υ"、 Ζ"のアルキル基において、フッ素原子で置換さ れている水素原子の数が多いほど、酸の強度が強くなり、また 200nm以下の高エネ ルギ一光や電子線に対する透明性が向上するので好ましい。前記アルキレン基また はアルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは 70〜； 100 %、さらに好ましくは 90〜； 100%であり、最も好ましくは、全ての水素原子がフッ素原 子で置換されたパーフルォロアルキレン基またはパーフルォロアルキル基である。  In addition, in the alkylene group of X "or the alkyl group of Υ" and Ζ ", the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength and the higher the energy of 200 nm or less. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
[0054] また、下記一般式 (b— 5)で表されるァニオン部を有するォニゥム塩系酸発生剤（ 以下、（b— 5)成分ということがある。）も好ましいものとして挙げられる。 [0054] Preferable examples also include an ion salt-based acid generator having an anion moiety represented by the following general formula (b-5) (hereinafter also referred to as component (b-5)).
近年、レジストパターンの微細化がますます進むにつれ、高解像性とともに、種々 のリソグラフィー特性の向上が求められている。なかでも、パターン形成の際のプロセ スマージン等の向上のため、露光量マージン（ELマージン）の向上が求められて!/ヽ  In recent years, as the miniaturization of resist patterns further progresses, it is required to improve various lithography characteristics as well as high resolution. In particular, in order to improve the process margin during pattern formation, an improvement in exposure margin (EL margin) is required! / ヽ
ELマージンは、露光量を変化させて露光した際に、ターゲット寸法に対するずれが 所定の範囲内となる寸法でレジストパターンを形成できる露光量の範囲、すなわちマ スクに忠実なレジストパターンが得られる露光量の範囲のことであり、 ELマージンは 大きいほど好ましい。 The EL margin is an exposure range that can form a resist pattern with a dimension within which the deviation from the target dimension is within a specified range when exposure is performed with different exposure amounts, that is, an exposure that provides a resist pattern that is faithful to the mask. It is a range of quantity, and the larger the EL margin, the better.
本発明にお!/、ては、下記一般式 (b— 5)で表されるァニオン部を有するォニゥム塩 系酸発生剤を用いることで、レジストパターン形状を悪化させることなく ELマージンを 向上させること力 Sでさる。  In the present invention, the EL margin is improved without deteriorating the resist pattern shape by using an onion salt acid generator having an anion portion represented by the following general formula (b-5). That's the power S.
[0055] [化 10] [0055] [Chemical 10]
Figure imgf000020_0001
Figure imgf000020_0001
[式 (b— 5)中、 U"、 V"、 W"は、それぞれ独立に、少なくとも 1つの水素原子がフッ 素原子で置換された炭素数;!〜 10のアルキル基を表す。 ] [In formula (b-5), U ", V", and W "each independently represent at least one hydrogen atom. Represents an alkyl group having from 10 to 10 carbon atoms substituted with a primary atom; ]
[0056] 式（b— 5)において、 U"、 V"、 W "は、それぞれ独立に、少なくとも 1つの水素原子 力 ッ素原子で置換された炭素数 1〜； 10のアルキル基である。前記アルキル基は、 直鎖状または分岐状であることが好ましい。前記アルキル基の炭素数は、好ましくは 炭素数 1〜7であり、より好ましくは炭素数 1〜3である。 [0056] In the formula (b-5), U ", V", and W "each independently represent an alkyl group having 1 to 10 carbon atoms substituted with at least one hydrogen atom or a hydrogen atom. The alkyl group is preferably linear or branched, and the alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
U"、 V"、 W"のアルキル基の炭素数は、上記炭素数の範囲内において、レジスト溶 媒への溶解性も良好である等の理由により、小さいほど好ましい。  The carbon number of the alkyl group of U ", V", and W "is preferably as small as possible for reasons such as good solubility in a resist solvent within the above carbon number range.
また、 U"、 V"、 W"のアルキル基において、フッ素原子で置換されている水素原子 の数が多いほど、酸の強度が強くなり、また 200nm以下の高エネルギー光や電子線 に対する透明性が向上するので好ましい。  In addition, in the alkyl groups of U ", V", and W ", the greater the number of hydrogen atoms that are substituted with fluorine atoms, the stronger the acid, and the transparency to high-energy light and electron beams below 200 nm. Is preferable.
前記アルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは 70〜1 00%、さらに好ましくは 90〜； 100%であり、最も好ましくは 100%である。すなわち、 U"、 V"、 W"のアルキル基としては、全ての水素原子がフッ素原子で置換されたパ 一フルォロアルキル基が最も好ましレ、。  The proportion of fluorine atoms in the alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably 100%. That is, as the alkyl group of U ", V", and W ", a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms is most preferable.
[0057] (b— 5)成分のカチオン部は、特に限定されず、これまで提案されている酸発生剤 のカチオン部と同様のものが挙げられる。  [0057] The cation part of the component (b-5) is not particularly limited, and examples thereof include those similar to the cation part of acid generators proposed so far.
(b— 5)成分のカチオン部としては、特に、上記一般式 (b— 1)または (b— 2)で表さ れるォ二ゥム塩系酸発生剤のカチオン部、すなわち下記一般式 ( ー 1)または (b' 2)で表されるカチオン部が好ましい。  As the cation part of the component (b-5), in particular, the cation part of the onium salt acid generator represented by the general formula (b-1) or (b-2), that is, the following general formula ( -The cation moiety represented by 1) or (b '2) is preferred.
[0058] [化 11] [0058] [Chemical 11]
( b ' , ， . ， ， ：（ — 2)(b ',,.,,: (— 2)
Figure imgf000021_0001
Figure imgf000021_0001
[式 (b'— 1)中、 1"〜!^"はそれぞれ独立にァリール基またはアルキル基を表し、 少なくとも 1っはァリール基を表す。式 (b' - 2)中、 R5"〜R6"はそれぞれ独立にァリ ール基またはアルキル基を表し、少なくとも 1っはァリール基を表す。 ] [In the formula (b'—1), 1 "~! ^" Each independently represents an aryl group or an alkyl group, and at least one represents an aryl group. In formula (b′-2), R 5 ″ to R 6 ″ each independently represents an aryl group or an alkyl group, and at least one represents an aryl group. ]
[0059] 式（ ー 1 )中の "〜R3"、式（b '— 2)中の R5"〜R6"は、それぞれ、上記式（b— 1 )中の 1"〜!^3"、式（b— 2)中の R5"〜R6"と同様である。 [0059] Formula (-1) in the "to R 3", the formula (b '- 2) R 5 "~R 6" in each the above formula (b-1 ) 1 "~! ^ 3" in, it is the same as that of R 5 "~R 6" in the formula (b- 2).
式 (b'—1)または（b '—2)で表されるカチオン部の具体例としては、ジフエ二ルョ 一ドニゥムイオン、ビス（4— tert ブチルフエ二ノレ）ョードニゥムイオン、トリフエニルス ノレホニゥムイオン、トリ（4 メチルフエ二ノレ）スルホニゥムイオン、ジメチル（4ーヒドロキ シナフチノレ）スルホニゥムイオン、モノフエニルジメチルスルホニゥムイオン、ジフエ二 ノレモノメチルスルホニゥムイオン、 （4 メチルフエ二ノレ）ジフエニルスルホニゥムイオン 、（4ーメトキシフエ二ノレ）ジフエニルスルホニゥムイオン、トリ（4— tert ブチノレ）フエ二 ノレスルホニゥムイオン、ジフエニル（1一（4ーメトキシ）ナフチノレ）スルホニゥムイオン、 ジフエニルモノナフチルスルホニゥムイオン、ジ（1 ナフチル）モノフエニルスルホニ ゥムイオン等が挙げられる。  Specific examples of the cation moiety represented by the formula (b′—1) or (b′—2) include diphenylsulfonyl ion, bis (4-tert-butylphenyl) iodonium ion, and triphenylsnorephoni. Ion, tri (4 methylphenol) sulfonium ion, dimethyl (4-hydroxycinnaphinoleol) sulfonium ion, monophenyldimethylsulfonium ion, diphenylmonomethylsulfonium ion, (4 methylphenolinole) diphenylsulfonium ion , (4-methoxyphenyl) diphenylsulfonium ion, tri (4-tert-butynole) phenylsulfonium ion, diphenyl (1- (4-methoxy) naphthinole) sulfonium ion, diphenylmononaphthylsulfonium ion, di (1 naphthyl) monophenylsulfonium Emissions, and the like.
[0060] (b— 5)成分としては、特に、下記一般式 (b— 5— 1 )で表されるォニゥム塩が好まし い。 [0060] As the component (b-5), an onium salt represented by the following general formula (b-5-1) is particularly preferable.
[0061] [化 12]  [0061] [Chemical 12]
Figure imgf000022_0001
Figure imgf000022_0001
[式 (b— 5— l)中、 Rbl〜Rbdはそれぞれ独立に、アルキル基であり； a、b、 cは 0〜2の 整数である。 ] [In the formula (b-5-l), R bl to R bd are each independently an alkyl group; a, b and c are integers of 0 to 2. ]
式 (b— 5— l)中、 R61〜R63はそれぞれ独立に、アルキル基であり、前記アルキル 基としては、前記 1"〜!^"のァリール基の水素原子が置換されていてもよいアルキ ル基として挙げたアルキル基と同様のものが挙げられ、メチル基および/または tert ブチル基が好ましぐ tert ブチル基が特に好ましい。 In the formula (b-5-l), R 61 to R 63 are each independently an alkyl group, and the alkyl group may be substituted with a hydrogen atom of the above 1 "~! ^" Aryl group. Examples of the alkyl group mentioned as a preferable alkyl group include methyl and / or tert-butyl group, and tert-butyl group is particularly preferable.
aは 0〜2の整数であり、 0または 1が好ましぐ 1が特に好ましい。 bは 0 2の整数であり、 0または 1が好ましぐ 1が特に好ましい。 a is an integer of 0 to 2, 0 or 1 is preferred, and 1 is particularly preferred. b is an integer of 0, 0 or 1 is preferred, and 1 is particularly preferred.
cは 0 2の整数であり、 0または 1が好ましぐ 1が特に好ましい。  c is an integer of 0, 0 or 1 is preferred, and 1 is particularly preferred.
[0063] 本明細書において、ォキシムスルホネート系酸発生剤とは、下記一般式 (B— 1)で 表される基を少なくとも 1つ有する化合物であって、放射線の照射によって酸を発生 する特性を有するものである。この様なォキシムスルホネート系酸発生剤は、化学増 幅型レジスト組成物用として多用されているので、任意に選択して用いることができる [0063] In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and generates 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.
[0064] [化 13]
Figure imgf000023_0001
[0064] [Chemical 13]
Figure imgf000023_0001
(式 (B— 1)中、 R31 R32はそれぞれ独立に有機基を表す。 ) (In Formula (B-1), R 31 R 32 each independently represents an organic group.)
[0065] R31 R32の有機基は、炭素原子を含む基であり、炭素原子以外の原子（たとえば水 素原子、酸素原子、窒素原子、硫黄原子、ハロゲン原子 (フッ素原子、塩素原子等） 等）を有していてもよい。 [0065] The organic group of R 31 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 (fluorine atom, chlorine atom, etc.)) Etc.).
R31の有機基としては、直鎖、分岐または環状のアルキル基またはァリール基が好 ましい。これらのアルキル基、ァリール基は置換基を有していても良い。前記置換基 としては、特に制限はなぐたとえばフッ素原子、炭素数;!〜 6の直鎖、分岐または環 状のアルキル基等が挙げられる。ここで、「置換基を有する」とは、アルキル基または ァリール基の水素原子の一部または全部が置換基で置換されていることを意味する アルキル基としては、炭素数 1 20が好ましぐ炭素数 1〜； 10がより好ましぐ炭素 数 1 8がさらに好ましぐ炭素数;!〜 6が特に好ましぐ炭素数 1 4が最も好ましい。 アルキル基としては、特に、部分的または完全にハロゲン化されたアルキル基（以下 、ハロゲン化アルキル基ということがある）が好ましい。なお、部分的にハロゲン化され たアルキル基とは、水素原子の一部がハロゲン原子で置換されたアルキル基を意味 し、完全にハロゲン化されたアルキル基とは、水素原子の全部がハロゲン原子で置 換されたアルキル基を意味する。ハロゲン原子としては、フッ素原子、塩素原子、臭 素原子、ヨウ素原子等が挙げられ、特にフッ素原子が好ましい。すなわち、ハロゲン 化アルキル基は、フッ素化アルキル基であることが好まし!/、。 As the organic group for R 31 , a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 6 to 6 carbon atoms. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent. The alkyl group preferably has 120 carbon atoms. Carbon number 1 to; 10 is more preferable carbon number 18 is more preferable carbon number;! To 6 is particularly preferable carbon number 14 is most preferable. As the alkyl group, 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 fully halogenated alkyl group means that all the hydrogen atoms are halogen atoms. It means an alkyl group substituted by. Halogen atoms include fluorine, chlorine, odor Elementary atoms, iodine atoms and the like can be mentioned, and fluorine atoms are particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
ァリール基は、炭素数 4〜20が好ましぐ炭素数 4〜； 10がより好ましぐ炭素数 6〜1 The aryl group is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 1 carbon atoms.
0が最も好ましい。ァリール基としては、特に、部分的または完全にハロゲン化された ァリール基が好ましい。なお、部分的にハロゲン化されたァリール基とは、水素原子 の一部がハロゲン原子で置換されたァリール基を意味し、完全にハロゲン化されたァ リール基とは、水素原子の全部がハロゲン原子で置換されたァリール基を意味する。 0 is most preferred. As the aryl group, 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. An aryl group substituted with an atom.
R31としては、特に、置換基を有さない炭素数 1〜4のアルキル基、または炭素数 1As R 31 , in particular, an alkyl group having 1 to 4 carbon atoms having no substituent, or 1 carbon atom
〜4のフッ素化アルキル基が好まし!/、。 A fluorinated alkyl group of ~ 4 is preferred!
[0066] R32の有機基としては、直鎖、分岐または環状のアルキル基、ァリール基またはシァ ノ基が好ましい。 R32のアルキル基、ァリール基としては、前記 R31で挙げたアルキル 基、ァリール基と同様のものが挙げられる。 As the organic group for R 32 , a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable. 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 .
R32としては、特に、シァノ基、置換基を有さない炭素数 1〜8のアルキル基、または 炭素数 1〜8のフッ素化アルキル基が好ましい。 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.
[0067] ォキシムスルホネート系酸発生剤として、さらに好ましいものとしては、下記一般式（[0067] As the oxime sulfonate-based acid generator, more preferred are those represented by the following general formula (
B- 2)または (B— 3)で表される化合物が挙げられる。 Examples thereof include compounds represented by B-2) or (B-3).
[0068] [化 14] [0068] [Chemical 14]
* - - ( 8 -- 2 }*--(8-2}
Figure imgf000024_0001
Figure imgf000024_0001
[式 (B— 2)中、 R33は、シァノ基、置換基を有さないアルキル基またはハロゲン化ァ ルキル基である； R34はァリール基である； R35は置換基を有さな!/、アルキル基または ハロゲン化アルキル基である。 ] [In the formula (B-2), R 33 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R 34 is an aryl group; R 35 is not having a substituent. ! /, An alkyl group or a halogenated alkyl group. ]
[0069] [化 15]  [0069] [Chemical 15]
( B— 3 )(B— 3)
Figure imgf000024_0002
[式 (B— 3)中、 Rdbはシァノ基、置換基を有さないアルキル基またはハロゲン化アル キル基である； R37は 2または 3価の芳香族炭化水素基である； R38は置換基を有さな いアルキル基またはハロゲン化アルキル基である； p"は 2または 3である。 ]
Figure imgf000024_0002
[In the formula (B-3), R db is a cyano group, 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 unsubstituted alkyl group or a halogenated alkyl group; p "is 2 or 3.]
[0070] 前記一般式 (B— 2)において、 R33の置換基を有さないアルキル基またはハロゲン 化アルキル基は、炭素数が 1〜； 10であることが好ましぐ炭素数 1〜8がより好ましぐ 炭素数 1〜6が最も好ましい。 In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent for R 33 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Is more preferred. Carbon number 1 to 6 is most preferred.
R33としては、ハロゲン化アルキル基が好ましぐフッ素化アルキル基がより好ましいR 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
〇 Yes
R33におけるフッ素化アルキル基は、アルキル基の水素原子が 50%以上フッ素化さ れていることが好ましぐより好ましくは 70%以上、さらに好ましくは 90%以上フッ素 化されていることが好ましい。 The fluorinated alkyl group for R 33 preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. .
[0071] R34のァリール基としては、フエニル基、ビフエニル（biphenyl)基、フルォレニル（Π uorenyl)基、ナフチル基、アントラセル（anthracyl)基、フエナントリル基等の、芳香 族炭化水素の環から水素原子を 1つ除いた基、およびこれらの基の環を構成する炭 素原子の一部が酸素原子、硫黄原子、窒素原子等のへテロ原子で置換されたへテ ロアリール基等が挙げられる。これらのなかでも、フルォレニル基が好ましい。 [0071] The aryl group of R 34 includes a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group. And a heteroaryl group in which a 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. Among these, a fluorenyl group is preferable.
R34のァリール基は、炭素数 1〜10のアルキル基、ハロゲン化アルキル基、アルコキ シ基等の置換基を有していても良い。前記置換基におけるアルキル基またはハロゲ ン化アルキル基は、炭素数が 1〜8であることが好ましぐ炭素数 1〜4がさらに好まし い。また、前記ハロゲン化アルキル基は、フッ素化アルキル基であることが好ましい。 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 is preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.
[0072] R35の置換基を有さないアルキル基またはハロゲン化アルキル基は、炭素数が；!〜 [0072] The alkyl group or halogenated alkyl group having no substituent of R 35 has carbon number;
10であることが好ましぐ炭素数 1〜8がより好ましぐ炭素数 1〜6が最も好ましい。  A carbon number of 1 to 6 which is preferably 10 is most preferable, and a carbon number of 1 to 6 is more preferable.
R35としては、ハロゲン化アルキル基が好ましぐフッ素化アルキル基がより好ましぐ 部分的にフッ素化されたアルキル基が最も好ましい。 R 35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and more preferably a partially fluorinated alkyl group.
R35におけるフッ素化アルキル基は、アルキル基の水素原子が 50%以上フッ素化さ れていることが好ましぐより好ましくは 70%以上、さらに好ましくは 90%以上フッ素 化されていることが、発生する酸の強度が高まるため好ましい。最も好ましくは、水素 原子が 100%フッ素置換された完全フッ素化アルキル基である。 [0073] 前記一般式 (B— 3)において、 Rdbの置換基を有さないアルキル基またはハロゲン 化アルキル基としては、上記 R33の置換基を有さな!/、アルキル基またはハロゲン化ァ ルキル基と同様のものが挙げられる。 The fluorinated alkyl group in R 35 preferably has a hydrogen atom of the alkyl group of 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more. This is preferable because the strength of the generated acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted. [0073] In the general formula (B-3), the alkyl group or halogenated alkyl group having no R db substituent does not have the above R 33 substituent! /, Alkyl group or halogenated Examples are the same as the alkyl group.
R37の 2または 3価の芳香族炭化水素基としては、上記 R34のァリール基からさらに 1 または 2個の水素原子を除!/、た基が挙げられる。 Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups obtained by further removing 1 or 2 hydrogen atoms from the aryl group for R 34 .
R38の置換基を有さなレ、アルキル基またはハロゲン化アルキル基としては、上記 5 の置換基を有さないアルキル基またはハロゲン化アルキル基と同様のものが挙げら れる。 Examples of the alkyl group or halogenated alkyl group having no substituent of R 38 include those similar to the alkyl group or halogenated alkyl group having no substituent of the above 5 .
P"は好ましくは 2である。  P "is preferably 2.
[0074] ォキシムスルホネート系酸発生剤の具体例としては、 α （p トルエンスルホニル ォキシィミノ） ベンジルシアニド、 α （ρ クロ口ベンゼンスルホニルォキシィミノ） ベンジルシアニド、 α—（4一二トロベンゼンスルホニルォキシィミノ） ベンジルシ アニド、 α （4一二トロー 2 トリフルォロメチルベンゼンスルホニルォキシィミノ） ベンジルシアニド、 α （ベンゼンスルホニルォキシィミノ）ー4 クロ口べンジルシア ニド、 α—(ベンゼンスルホニルォキシィミノ）—2, 4—ジクロ口ベンジルシアニド、 α （ベンゼンスルホニルォキシィミノ） - 2 , 6—ジクロ口ベンジルシアニド、 α （ベン ゼンスルホニルォキシィミノ）ー4ーメトキシベンジルシアニド、 α （2 クロ口べンゼ ンスルホニルォキシィミノ） 4ーメトキシベンジルシアニド、 α （ベンゼンスルホ二 ノレォキシィミノ） チェン 2 ィルァセトニトリル、 α （4ードデシルベンゼンスルホ ニルォキシィミノ） ベンジルシアニド、 α [ (ρ トルエンスルホニルォキシィミノ） 4ーメトキシフエ二ノレ]ァセトニトリル、 α [ (ドデシルベンゼンスルホニルォキシィミノ ) 4ーメトキシフエニル]ァセトニトリル、 a （トシルォキシィミノ）ー4 チェ二ルシア ニド、 α （メチルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α （メチルスルホニルォキシィミノ） 1ーシクロへキセニルァセトニトリル、 a （メチ ノレスルホニルォキシィミノ） 1ーシクロヘプテュルァセトニトリル、 α （メチルスルホ ニルォキシィミノ） 1ーシクロオタテュルァセトニトリル、 α （トリフルォロメチルスル ホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α （トリフルォロメチルス ノレホニルォキシィミノ）ーシクロへキシルァセトニトリル、 α （ェチルスルホニルォキ シィミノ）ーェチルァセトニトリル、 a （プロピルスルホニルォキシィミノ） プロピルァ セトニトリノレ、 α （シクロへキシルスルホニルォキシィミノ）ーシクロペンチルァセトニ トリノレ、 α （シクロへキシルスルホニルォキシィミノ）ーシクロへキシルァセトニトリル、 a （シクロへキシルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 a （ェチルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α—(ィ ソプロピルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α— (η - ブチルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α （ェチルス ノレホニルォキシィミノ） 1ーシクロへキセニルァセトニトリル、 α （イソプロピルスル ホニルォキシィミノ） 1ーシクロへキセニルァセトニトリル、 α—（η ブチルスルホニ ノレォキシィミノ） 1ーシクロへキセニルァセトニトリル、 α （メチルスルホニルォキシ ィミノ） フエニノレアセトニトリノレ、 α （メチルスルホニルォキシィミノ） ρ メトキシフ ェニルァセトニトリル、 a （トリフルォロメチルスルホニルォキシィミノ） フエニルァ セトニトリル、 a （トリフルォロメチルスルホニルォキシィミノ） p メトキシフエニル ァセトニトリノレ、 α （ェチルスルホニルォキシィミノ） ρ メトキシフエ二ルァセトニト リル、 α—(プロピルスルホニルォキシィミノ） ρ メチルフエ二ルァセトニトリル、 α （メチルスルホニルォキシィミノ） ρ ブロモフエ二ルァセトニトリルなどが挙げられ また、特開平 9 208554号公報 (段落 [0012]〜[0014]の [化 18]〜[化 19] )に 開示されているォキシムスルホネート系酸発生剤、 WO2004/074242A2 (65〜8 5頁目の Example；!〜 40)に開示されているォキシムスルホネート系酸発生剤も好適 に用いることができる。 [0074] Specific examples of the oxime sulfonate acid generator include α (p-toluenesulfonyloxyimino) benzyl cyanide, α (ρ chlorobenzenesulfonyloxyimino) benzylcyanide, α- (4 Benzenesulfonyloxymino) Benzyl cyanide, α (4 12 tallow 2 trifluoromethylbenzenesulfonyloxymino) benzyl cyanide, α (benzenesulfonyloxyimino) -4 clonal benzil cyanide, α — (Benzenesulfonyloxyimino) -2, 4-dichlorodiphenylcyanide, α (benzenesulfonyloxyimino) -2,6-dichlorodiethylcyanide, α (benzenesulfonyloxyimino) -4-Methoxybenzyl cyanide, α (2-chlorobenzyl sulfonyloxymino) 4-methoxybenzyl cyanide , Α (Benzenesulfonyloxymino) Chen 2 ylacetonitrile, α (4-Dodecylbenzenesulfonyloxymino) Benzyl cyanide, α [(ρ Toluenesulfonyloxyimino) 4-methoxyphenoxy] acetonitrile, α [( Dodecylbenzenesulfonyloxyimino) 4-methoxyphenyl] acetonitrile, a (tosyloxymino) -4 cenyl cyanide, α (methylsulfonyloxyimino) 1-cyclopentenylacetonitrile, α (methylsulfonyloxy) (Xiximino) 1-cyclohexenylacetonitrile, a (methenylsulfonyloxyximino) 1-cyclohepturacetonitrile, α (methylsulfonoxyximino) 1-cyclootatulacetonitrile, α (trifluoro) Methyl sulfonyloxy Roh) 1 Shikuropente two Ruasetonitoriru, alpha (triflate Ruo B methyl scan Honoré Honi Ruo key Consequences amino) hexyl § Seto nitrile to Shikuro, alpha (E chill sulfonyl O key Simino) -ethylacetonitrile, a (propylsulfonyloxyximino) propylacetonitolinole, α (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrinole, α (cyclohexylsulfonyloxyimino) -cyclo Hexylacetonitrile, a (Cyclohexylsulfonyloximino) 1-Cyclopentenylrucetonitrile, a (Ethylsulfonyloxyximino) 1-Cyclopentenylacetonitrile, α- (Isopropylsulfonyloxyimino) 1 -Cyclopentenylacetonitrile, α- (η-butylsulfonyloximino) 1-Cyclopentenylacetonitrile, α (Ethylsnorenyloximino) 1-Cyclohexenylacetonitrile, α (Isopropylsulfonyloxyimino) 1 - Rohexenylacetonitrile, α- (η butylsulfonyloximino) 1-cyclohexenylacetonitrile, α (methylsulfonyloxyimino) pheninoreacetonitrinole, α (methylsulfonyloxyimino) ρ methoxyphenylaceto Nitrile, a (trifluoromethylsulfonyloxyimino) phenylacetonitrile, a (trifluoromethylsulfonyloxyimino) p methoxyphenyl acetatenitriol, α (ethylsulfonyloxyximino) ρ methoxyphenylacetononitrile , Α- (propylsulfonyloxyimino) ρ methylphenylacetonitrile, α (methylsulfonyloxyimino) ρ bromophenylacetonitrile, etc. Also, JP-A-9 208554 (paragraphs [0012] to [0014] [Chemical 18]-[Chemical 1 9]), an oxime sulfonate acid generator disclosed in WO2004 / 074242A2 (Examples on pages 65 to 85; Examples 40! To 40) is also preferably used. Can do.
また、好適なものとして以下のものを例示することができる。  Moreover, the following can be illustrated as a suitable thing.
[化 16]
Figure imgf000028_0001
[Chemical 16]
Figure imgf000028_0001
[0076] 上記例示化合物の中でも、下記の 4つの化合物が好ましい [0076] Among the above exemplified compounds, the following four compounds are preferred:
[0077] [化 17]
Figure imgf000029_0001
[0077] [Chemical 17]
Figure imgf000029_0001
[0078] ジァゾメタン系酸発生剤のうち、ビスアルキルまたはビスァリールスルホニルジァゾメ タン類の具体例としては、ビス（イソプロピルスルホュル）ジァゾメタン、ビス（p トルェ ンスノレホニノレ）ジァゾメタン、ビス（1, 1ージメチノレエチルスノレホニノレ）ジァゾメタン、ビ ス（シクロへキシルスルホニノレ）ジァゾメタン、ビス（2, 4 ジメチノレフエニルスルホニル )ジァゾメタン等が挙げられる。 [0078] Among diazomethane-based acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfur) diazomethane, bis (p-toluenenolehoninore) diazomethane, bis (1 , 1-dimethylenoethylethylrephoninole) diazomethane, bis (cyclohexylsulfoninole) diazomethane, bis (2,4 dimethinophenylsulfonyl) diazomethane, and the like.
また、特開平 11— 035551号公報、特開平 11— 035552号公報、特開平 11— 03 5573号公報に開示されているジァゾメタン系酸発生剤も好適に用いることができる。 また、ポリ（ビススルホニル）ジァゾメタン類としては、例えば、特開平 11 322707 号公報に開示されている、 1, 3—ビス（フエニルスルホニルジァゾメチルスルホニル） プロパン、 1, 4 ビス（フエニルスルホニルジァゾメチルスルホニノレ）ブタン、 1 6 ビ ス（フエニノレスルホニルジァゾメチノレスノレホニル）へキサン、 1, 10—ビス（フエニルス ノレホニルジァゾメチルスルホニノレ）デカン、 1, 2—ビス（シクロへキシルスルホニルジ ァゾメチルスルホニノレ）ェタン、 1, 3—ビス（シクロへキシルスルホニルジァゾメチルス ノレホニノレ）プロパン、 1 6 ビス（シクロへキシノレスノレホニノレジァゾメチノレスノレホニノレ） へキサン、 1, 10—ビス（シクロへキシルスルホニルジァゾメチルスルホニノレ）デカンな どを挙げることができる。  Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used. Poly (bissulfonyl) diazomethanes include, for example, 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane, 1,4 bis (phenyl) disclosed in JP-A-11 322707. Sulfonyl diazomethylsulfoninole) butane, 1 6 bis (pheninosulphonyl diazomethinolesnolephonyl) hexane, 1,10-bis (phenylsulphonyl diazomethylsulfoninole) decane, 1 , 2-bis (cyclohexylsulfonyldiazomethylsulfoninole) ethane, 1,3-bis (cyclohexylsulfonyldiazomethylsulphoninole) propane, 1 6 bis (cyclohexinoresnorephoninoresi) Zomethinolesnorehoninole) Hexane, 1, 10-bis (cyclohexylsulfonyldiazomethylsulfoninole) decane Can do.
[0079] (B)成分としては、これらの酸発生剤を 1種単独で用いてもよいし、 2種以上を組み 合わせて用いてもよい。  [0079] As the component (B), one type of these acid generators may be used alone, or two or more types may be used in combination.
(B)成分としては、特に、得られるレジスト組成物のリソグラフィー特性に優れること 力、ら、（b— 5)成分が好ましい。また、（b— 5)成分と、フッ素化アルキルスルホン酸ィ オンをァニオン部に有するォニゥム塩系酸発生剤とを併用することも好ましレ、。中で も、（b— 5)成分と、上記一般式 (b— 1)で表されるォニゥム塩系酸発生剤とを併用す ることが特に好ましい。 As the component (B), the component (b-5) is particularly preferred because it has excellent lithography properties for the resulting resist composition. It is also preferable to use the component (b-5) in combination with an onium salt acid generator having a fluorinated alkylsulfonic acid ion in the anion part. Inside In particular, it is particularly preferable to use the component (b-5) in combination with the onium salt acid generator represented by the general formula (b-1).
本発明における（B)成分の含有量は、（A)成分 100質量部に対し、 0. 5〜30質量 部が好ましぐ；!〜 10質量部がより好ましい。上記範囲とすることでパターン形成が充 分に行われる。また、均一な溶液が得られ、保存安定性が良好となるため好ましい。 <任意成分〉  In the present invention, the content of the component (B) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A); more preferably 10 to 10 parts by mass. 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. <Optional component>
本発明におレ、て化学増幅型ポジ型シリコン系レジスト組成物は、以下に示す任意 成分を含有することが好ましレヽ。  In the present invention, the chemically amplified positive silicon resist composition preferably contains the following optional components.
<任意成分 1 : γ ブチロラタトン〉  <Optional component 1: γ-Butyloraton>
前記任意成分として、 Ί プチ口ラタトンを含有することにより、リソグラフィー特性を t なつことなく異物経時 (storage stability as a resist solution by particles)特十王を |口」 上させること力 Sできる。ここで「異物経時特性の向上」とは、化学増幅型ポジ型シリコン 系レジストを溶液とした際の保存安定性が高まることを指す。具体的には、経時的な 、前記溶液中における微細な粒子状異物の発生が抑制されることを指す。このような 異物経時は、特にシルセスキォキサン樹脂を用いる場合に生じ易い。そして、異物経 時の発生は、リソグラフィー特性の悪化や、形成されるレジストパターンのディフエタト (表面欠陥）等を生じさせるおそれがある。なお、ここで「ディフエタト」とは、例えば KL Aテンコール社の表面欠陥観察装置（商品名「KLA」）により、現像後のレジストバタ ーンを真上から観察した際に検知される不具合全般のことである。この不具合とは、 例えば現像後のスカム、泡、ゴミ、ブリッジ（レジストパターン間の橋掛け構造）、色む ら、析出物等である。 Wherein as an optional component, by containing Ί Petit port Rataton, the lithography properties of the storage stability (storage stability as a resist solution by particles) JP Juo without t summer | mouth "can be force S to above. Here, “improving foreign matter aging characteristics” refers to an increase in storage stability when a chemically amplified positive silicon resist is used as a solution. Specifically, it means that generation of fine particulate foreign matters in the solution is suppressed over time. Such foreign matter aging tends to occur particularly when a silsesquioxane resin is used. Further, the occurrence of foreign matter may cause deterioration of lithography characteristics, diffate (surface defect) of a formed resist pattern, and the like. Here, “diffetant” means, for example, general defects detected when the resist pattern after development is observed from directly above with a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. It is. Examples of defects include scum, bubbles, dust, bridges (bridge structures between resist patterns), uneven color, and precipitates after development.
異物経時特性を改善する方法としては、これまで、基材成分の組成を調整する方 法が一般的である。たとえば基材成分の有機溶剤への溶解性を高めることにより、溶 解している成分の析出による異物の発生を抑制できると考えられる。し力、しながら、シ リコン含有樹脂は、組成を変更すると、感度、解像性等のリソグラフィー特性が悪化し やすぐその組成を変更することは困難である。  As a method for improving foreign matter aging characteristics, a method of adjusting the composition of the base material component has been generally used. For example, by increasing the solubility of the base material component in an organic solvent, it is considered that the generation of foreign substances due to precipitation of the dissolved component can be suppressed. However, if the composition of the silicon-containing resin is changed, the lithography properties such as sensitivity and resolution deteriorate, and it is difficult to change the composition immediately.
本発明においては、前記ポジ型シリコン系レジスト組成物力 任意成分として γ— プチ口ラタトンを含有することにより、シリコン含有樹脂の組成を変更しなくても、リソグ ラフィー特性を損なうことなぐ異物経時特性を向上させることができる。 In the present invention, the positive silicon-based resist composition strength contains γ-petit-mouth ratatone as an optional component, so that the lithography can be performed without changing the composition of the silicon-containing resin. It is possible to improve foreign matter aging characteristics without impairing luffy characteristics.
[0081] 本発明において、前記ポジ型シリコン系レジスト組成物における γ ブチロラタトン の含有量は、（Α)成分 100質量部に対し、；!〜 600質量部が好ましぐ 3〜100質量 部がより好ましぐ 5〜30質量部がさらに好ましぐ 10〜20質量部が特に好ましい。 上記範囲の下限値以上とすることで上記効果に優れ、上限値以下とすることで、前 記レジスト組成物を用いてレジスト膜を形成する際の成膜性、塗布性等が向上する。 [0081] In the present invention, the content of γ-butyrolatatane in the positive silicon resist composition is preferably from 3 to 100 parts by mass; 5 to 30 parts by mass is more preferable and 10 to 20 parts by mass is particularly preferable. By setting it to the lower limit value or more of the above range, the above effect is excellent, and by setting it to the upper limit value or less, the film forming property, coating property, etc. when forming the resist film using the resist composition are improved.
[0082] <任意成分 2：化合物（C) > <Arbitrary component 2: Compound (C)>
本発明にお!/、ては、前記任意成分として下記一般式 (c 1)で表される化合物（C) を含有することにより、レジストパターン形成時のディフエタトの発生を抑制できる。ま た、形成されるレジストパターンの形状も向上する。  In the present invention, by containing the compound (C) represented by the following general formula (c 1) as the optional component, it is possible to suppress the occurrence of diffetats when forming a resist pattern. In addition, the shape of the formed resist pattern is improved.
「ディフエタト」とは、先に述べた通りである力 S、高解像性レジストパターンを形成する 際、特に、 ArFエキシマレーザー以降、すなわち ArFエキシマレーザー、 Fエキシマ  The term “diffeta” refers to the force S, as described above, when forming a high-resolution resist pattern, especially after the ArF excimer laser, that is, ArF excimer laser, F excimer.
2 レーザー、 EUV、 EB等を光源として微細パターン、たとえば 130nm以下のレジスト ノ ターンを形成する際には、その抑制が重要となる。ディフエタトを抑制する方法とし ては、これまで、基材成分の組成を調整する方法が一般的であるが、シリコン含有樹 脂の組成を変更することは、感度、解像性等のリソグラフィー特性の悪化を招きやす いことは先にも述べた通りである。  2 When forming a fine pattern, for example, a resist pattern of 130 nm or less, using laser, EUV, EB, etc. as a light source, the suppression is important. As a method of suppressing the diffetato, a method of adjusting the composition of the base material component has been generally used. However, changing the composition of the silicon-containing resin may affect the lithography properties such as sensitivity and resolution. As mentioned earlier, it is easy to cause deterioration.
本発明においては、前記ポジ型シリコン系レジスト組成物が、任意成分として化合 物（C)を含有することにより、シリコン含有樹脂の組成を変更しなくても、リソグラフィ 一特性を損なうことなぐディフエタトの発生を抑制することができる。  In the present invention, since the positive silicon resist composition contains the compound (C) as an optional component, it is possible to reduce the lithographic characteristics without impairing the lithography characteristics without changing the composition of the silicon-containing resin. Occurrence can be suppressed.
[0083] [化 18] [0083] [Chemical 18]
Figure imgf000031_0001
Figure imgf000031_0001
[式 (c 1)中、 R11は酸解離性基であり、 R"〜R14はそれぞれ独立に水素原子また は水酸基である。 ] [0084] 式 (c— 1 )中、 R11は酸解離性基である。 R11の酸解離性基としては、（B)成分から 発生した酸の作用により解離する基であれば特に制限はない。たとえば、これまで化 学増幅型レジスト用のベース樹脂の酸解離性溶解抑制基として提案されているもの を使用すること力できる。 [In the formula (c 1), R 11 is an acid-dissociable group, and R ″ to R 14 are each independently a hydrogen atom or a hydroxyl group.] In the formula (c— 1), R 11 is an acid dissociable group. The acid dissociable group for R 11 is not particularly limited as long as it is a group dissociable by the action of an acid generated from the component (B). For example, it is possible to use what has been proposed as an acid dissociable, dissolution inhibiting group for a base resin for a chemically amplified resist.
R11として好まし!/、酸解離性溶解抑制基の具体例としては、（メタ）アクリル酸等にお けるカルボキシ基と環状または鎖状の第 3級アルキルエステルを形成する基；アルコ キシアルキル基等のァセタール型酸解離性溶解抑制基などが挙げられる。なお、「（ メタ）アクリル酸」とは、 α位に水素原子が結合したアクリル酸と、 α位にメチル基が結 合したメタクリル酸の一方あるいは両方を意味する。「（メタ）アクリル酸エステル」とは 、 α位に水素原子が結合したアクリル酸エステルと、 α位にメチル基が結合したメタク リル酸エステルの一方あるいは両方を意味する。「（メタ）アタリレート」とは、 α位に水 素原子が結合したアタリレートと、 a位にメチル基が結合したメタタリレートの一方ある いは両方を意味する。 Preferred as R 11 ! /, Specific examples of the acid dissociable, dissolution inhibiting group include a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an alkoxyalkyl group And acetal type acid dissociable, dissolution inhibiting groups such as “(Meth) acrylic acid” means one or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position. “(Meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylate ester having a methyl group bonded to the α-position. The term “(meth) acrylate” means one or both of an arylate having a hydrogen atom bonded to the α-position and a metatalylate having a methyl group bonded to the a-position.
ここで、「第 3級アルキルエステル」とは、カルボキシ基の水素原子が、鎖状または環 状のアルキル基で置換されることによりエステルを形成しており、そのカルボ二ルォキ シ基（一 C (O)— O—）の末端の酸素原子に、前記鎖状または環状のアルキル基の 第 3級炭素原子が結合して!/、る構造を示す。この第 3級アルキルエステルにお!/、て は、酸が作用すると、酸素原子と第 3級炭素原子との間で結合が切断される。  Here, the “tertiary alkyl ester” is an ester formed by replacing the hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carboxy group (one C A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the oxygen atom at the terminal of (O) —O—). When an acid acts on this tertiary alkyl ester, the bond is broken between the oxygen atom and the tertiary carbon atom.
なお、前記鎖状または環状のアルキル基は置換基を有していてもよい。 以下、カルボキシ基と第 3級アルキルエステルを構成することにより酸解離性となつ ている基を、便宜上、「第 3級アルキルエステル型酸解離性溶解抑制基」という。 第 3級アルキルエステル型酸解離性溶解抑制基としては、脂肪族分岐鎖状酸解離 性溶解抑制基、脂肪族環式基を含有する酸解離性溶解抑制基が挙げられる。 ここで、本明細書において、「脂肪族」とは、芳香族性に対する相対的な概念であつ て、芳香族性を持たない基、化合物等を意味するものと定義する。  The chain or cyclic alkyl group may have a substituent. Hereinafter, a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester is referred to as “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience. Examples of 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. Here, in the present specification, “aliphatic” is a relative concept with respect to aromaticity, and is defined to mean a group, compound, or the like that does not have aromaticity.
[0085] 「脂肪族分岐鎖状酸解離性溶解抑制基」は、炭素および水素からなる基 (炭化水 素基）であることに限定はされないが、炭化水素基であることが好ましい。また、「炭化 水素基」は飽和または不飽和のいずれでもよいが、通常は飽和であることが好ましい 脂肪族分岐鎖状酸解離性溶解抑制基としては、炭素数 4〜8の第 3級アルキル基 が好ましぐ具体的には tert—ブチル基、 tert—ァミル基、 tert—へプチル基等が挙 げられる。 The “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. Further, the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. As the aliphatic branched acid dissociable, dissolution inhibiting group, 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.
「脂肪族環式基を含有する酸解離性溶解抑制基」における「脂肪族環式基」として は、単環であっても多環であってもよぐ水素原子がフッ素化されたヒドロキシアルキ ル基で置換されていてもよいし、されていなくてもよい。「単環式の脂肪族環式基」は 、芳香族性を持たない単環式基であることを意味し、「多環式の脂肪族環式基」は、 芳香族性を持たな!/、多環式基であることを意味する。  The “aliphatic cyclic group” in the “acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group” is a hydroxyalkyl having a fluorinated hydrogen atom, which may be monocyclic or polycyclic. It may or may not be substituted with a ru group. `` Monocyclic aliphatic cyclic group '' means a monocyclic group that does not have aromaticity, and `` polycyclic aliphatic cyclic group '' does not have aromaticity! /, Means a polycyclic group.
脂肪族環式基は、炭素及び水素からなる炭化水素基 (脂環式基）、および前記脂 環式基の環を構成する炭素原子の一部が酸素原子、窒素原子、硫黄原子等のへテ 口原子で置換されたへテロ環式基等が含まれる。脂肪族環式基としては、脂環式基 が好ましい。  An aliphatic cyclic group is a hydrocarbon group composed of carbon and hydrogen (an alicyclic group), and some of the carbon atoms constituting the ring of the alicyclic group are oxygen atoms, nitrogen atoms, sulfur atoms, etc. Heterocyclic groups and the like substituted with a tetro atom are included. As the aliphatic cyclic group, an alicyclic group is preferable.
脂肪族環式基は、飽和または不飽和のいずれでもよいが、 ArFエキシマレーザー 等に対する透明性が高ぐ解像性や焦点深度幅 (DOF)等にも優れることから、飽和 であることが好ましい。  The aliphatic cyclic group may be either saturated or unsaturated, but is preferably saturated because it is highly transparent to ArF excimer laser, etc., and has excellent resolution and depth of focus (DOF). .
脂肪族環式基の炭素数は 3〜20であることが好ましぐ 4〜； 15であることがより好ま しぐ 5〜； 15であることがさらに好ましい。  The aliphatic cyclic group preferably has 3 to 20 carbon atoms, preferably 4 to; more preferably 15 to 5; and even more preferably 15.
脂肪族環式基の具体例として、単環式基としては、シクロアルカンから、 1個以上の 水素原子を除いた基などが挙げられる。さらに具体的には、シクロペンタン、シクロへ キサンから 1個以上の水素原子を除いた基が挙げられ、シクロへキサンから 1個以上 の水素原子を除レ、た基が好まし!/、。  Specific examples of the aliphatic cyclic group include a monocyclic group obtained by removing one or more hydrogen atoms from a cycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from cyclopentane or cyclohexane, and groups in which one or more hydrogen atoms have been removed from cyclohexane are preferred.
多環式基としては、ビシクロアルカン、トリシクロアルカン、テトラシクロアルカンなど から 1個以上の水素原子を除いた基などが挙げられる。さらに具体的には、ァダマン タン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカンなどのポリシ クロアルカンから 1個以上の水素原子を除いた基などが挙げられる。  Examples of the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like. More specifically, groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.
なお、この様な多環式基は、例えば ArFエキシマレーザープロセス用のポジ型ホト レジスト組成物用樹脂にお!/、て、酸解離性溶解抑制基を構成するものとして多数提 案されて!/、るものの中から適宜選択して用いることができる。 Many such polycyclic groups have been proposed as constituting acid dissociable, dissolution inhibiting groups in, for example, resins for positive photoresist compositions for ArF excimer laser processes. It can be used by appropriately selecting from those that have been proposed!
工業上入手しやすいことから、単環式基としては、シクロペンタン、シクロへキサンか ら 1個以上の水素原子を除いた基が好ましぐ特にシクロへキサンから 1個以上の水 素原子を除いた基が好ましい。また、多環式基としては、ァダマンタン、ノルボルナン 、テトラシクロドデカンから 1個以上の水素原子を除いた基が好ましい。  Due to industrial availability, monocyclic groups are preferably groups in which one or more hydrogen atoms have been removed from cyclopentane or cyclohexane, particularly one or more hydrogen atoms from cyclohexane. Excluded groups are preferred. The polycyclic group is preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane or tetracyclododecane.
[0087] 「脂肪族環式基を含有する酸解離性溶解抑制基」としては、例えば環状のアルキル 基の環骨格上に第 3級炭素原子を有する基を挙げることができ、具体的には 2 メチ ノレ 2—ァダマンチル基や、 2—ェチルー 2—ァダマンチル基等が挙げられる。ある いは、ァダマンチル基等の脂肪族環式基と、これに結合する、第 3級炭素原子を有 する分岐鎖状アルキレン基とを有する基が挙げられる。  [0087] 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, Examples thereof include 2 methylol 2-adamantyl group and 2-ethyl-2-adamantyl group. Alternatively, a group having an aliphatic cyclic group such as an adamantyl group and a branched alkylene group having a tertiary carbon atom bonded thereto is exemplified.
[0088] 「ァセタール型酸解離性溶解抑制基」は、一般的に、カルボキシ基、水酸基等のァ ルカリ可溶性基末端の水素原子と置換して酸素原子と結合している。そして、露光に より酸が発生すると、この酸が作用して、ァセタール型酸解離性溶解抑制基と、前記 ァセタール型酸解離性溶解抑制基が結合した酸素原子との間で結合が切断される。 ァセタール型酸解離性溶解抑制基としては、たとえば、下記一般式 (pi)で表され る基が挙げられる。  [0088] "Acetal type acid dissociable, dissolution inhibiting group" is generally bonded to an oxygen atom by substituting a hydrogen atom at the end 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).
[0089] [化 19]  [0089] [Chemical 19]
Figure imgf000034_0001
' · - · ； & 1 )
Figure imgf000034_0001
'·-·;& 1)
[式中、 R1', R2'はそれぞれ独立して水素原子または低級アルキル基を表し、 ηは 0 〜3の整数を表し、 Υは低級アルキル基または脂肪族環式基を表す。 ] [Wherein, R 1 ′ and R 2 ′ each independently represent a hydrogen atom or a lower alkyl group, η represents an integer of 0 to 3, and Υ represents a lower alkyl group or an aliphatic cyclic group. ]
[0090] 上記式中、 ηは、 0〜2の整数であることが好ましぐ 0または 1がより好ましぐ 0が最 も好ましい。 In the above formula, η is preferably an integer of 0 to 2, 0 or 1 is more preferable, and 0 is most preferable.
R1', R2'は水素原子または低級アルキル基である。 R1', R2'の低級アルキル基は、 炭素原子数 1〜5のアルキル基であり、具体的には、メチル基、ェチル基、プロピル 基、イソプロピル基、 η ブチル基、イソブチル基、 tert ブチル基、ペンチル基、ィ ソペンチル基、ネオペンチル基などの低級の直鎖状または分岐状のアルキル基が挙 げられる。 R1', R2'の低級アルキル基としては、メチル基またはェチル基が好ましぐ メチル基が最も好ましい。 R 1 ′ and R 2 ′ are a hydrogen atom or a lower alkyl group. The lower alkyl group of R 1 ′ and R 2 ′ is an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, η butyl group, isobutyl group, tert Lower linear or branched alkyl groups such as butyl, pentyl, isopentyl, and neopentyl are listed. I can get lost. As the lower alkyl group for R 1 ′ and R 2 ′, a methyl group or an ethyl group is preferred, and a methyl group is most preferred.
本発明においては、 R1', R2'のうち少なくとも 1つが水素原子であることが好ましい。 すなわち、酸解離性溶解抑制基 (pi)力 下記一般式 (pi— 1)で表される基であるこ とが好ましい。 In the present invention, it is preferable that at least one of R 1 ′ and R 2 ′ is a hydrogen atom. That is, the acid dissociable, dissolution inhibiting group (pi) force is preferably a group represented by the following general formula (pi-1).
[0091] [化 20] 1' [0091] [Chemical 20] 1 '
— 0- CH . . . . （p卜 ) — 0- CH.... ( P卜)
[式中、
Figure imgf000035_0001
n、 Yは上記と同様である。 ] [Where
Figure imgf000035_0001
n and Y are the same as above. ]
[0092] Υの低級アルキル基としては、上記 R1'の低級アルキル基と同様のものが挙げられ [0092] Examples of the lower alkyl group for Υ include those similar to the lower alkyl group for R 1 'above.
Υの脂肪族環式基としては、従来 ArFレジスト等において多数提案されている単環 又は多環式の脂肪族環式基の中から適宜選択して用いることができ、たとえば上記「 脂肪族環式基」と同様のものが例示できる。 As the aliphatic cyclic group of Υ, it can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups that have been proposed in a number of conventional ArF resists. Examples thereof are the same as those in the formula group.
[0093] また、ァセタール型酸解離性溶解抑制基としては、下記一般式 (p2)で示される基 あ挙げられる。  [0093] The acetal type acid dissociable, dissolution inhibiting group includes a group represented by the following general formula (p2).
[0094] [化 21]  [0094] [Chemical 21]
.0 ~~~ O—— R . . , , (p2) .0 ~~~ O—— R..,, (P2 )
[式中、 R17、 R18はそれぞれ独立して直鎖状または分岐鎖状のアルキル基または水 素原子であり、 R19は直鎖状、分岐鎖状または環状のアルキル基である；または、 R17 および R19がそれぞれ独立に直鎖状または分岐鎖状のアルキレン基であって、 R17の 末端と R19の末端とが結合して環を形成して!/、てもよ!/、。 ] [Wherein R 17 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 are bonded to form a ring! / /. ]
[0095] R17、 R18において、アルキル基の炭素数は好ましくは 1〜； 15であり、直鎖状、分岐 鎖状のいずれでもよぐェチル基、メチル基が好ましぐメチル基が最も好ましい。 特に R17、 R18の一方が水素原子で、他方がメチル基であることが好ましい。 R19は直鎖状、分岐鎖状または環状のアルキル基であり、炭素数は好ましくは;!〜 1 5であり、直鎖状、分岐鎖状又は環状のいずれでもよい。 [0095] In R 17, R 18, carbon atoms in the alkyl group is preferably 1 to; of 15, linear, branched either Yogu Echiru group, is preferred instrument methyl group methyl group is most preferable. In particular, it is preferable that one of R 17 and R 18 is a hydrogen atom and the other is a methyl group. R 19 is a linear, branched or cyclic alkyl group, preferably having carbon numbers;! To 15 and may be any of linear, branched or cyclic.
R19が直鎖状、分岐鎖状の場合は炭素数 1〜5であることが好ましぐェチル基、メ チル基がさらに好ましく、特にェチル基が最も好まし!/、。 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! /.
R19が環状の場合は炭素数 4〜 15であること力 S好ましく、炭素数 4〜 12であること力 S さらに好ましぐ炭素数 5〜； 10が最も好ましい。具体的にはフッ素原子またはフッ素化 アルキル基で置換されていてもよいし、されていなくてもよいモノシクロアルカン、ビシ クロアルカン、トリシクロアルカン、テトラシクロアルカンなどのポリシクロアルカンから 1 個以上の水素原子を除いた基などを例示できる。具体的には、シクロペンタン、シク 口へキサン等のモノシクロアルカンや、ァダマンタン、ノルボルナン、イソボルナン、トリ シクロデカン、テトラシクロドデカンなどのポリシクロアルカンから 1個以上の水素原子 を除いた基などが挙げられる。中でもァダマンタンから 1個以上の水素原子を除いた 基が好ましい。 When R 19 is cyclic, it is preferably S having 4 to 15 carbon atoms, preferably S having 4 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms. Specifically, 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.
また、上記式においては、 R17及び R19がそれぞれ独立に直鎖状または分岐鎖状の アルキレン基（好ましくは炭素数 1〜5のアルキレン基）であって R19の末端と R17の末 端とが結合していてもよい。この場合、 R17と R19と、 R19が結合した酸素原子と、前記 酸素原子および R17が結合した炭素原子とにより環式基が形成されている。前記環式 基としては、 4〜7員環が好ましぐ 4〜6員環がより好ましい。前記環式基の具体例と しては、テトラヒドロビラニル基、テトラヒドロフラニル基等が挙げられる。 In the above formula, 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. In this case, 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. The cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuranyl group.
[0096] 本発明にお!/、て、 R11の酸解離性基としては、前記第 3級アルキルエステル型酸解 離性溶解抑制基が好ましぐ炭素数 4〜8の第 3級アルキル基がより好ましぐ特に te rt ブチル基が好ましい。 [0096] In the present invention, as the acid dissociable group of R 11 , the tertiary alkyl ester type acid-releasing dissolution inhibiting group is preferably a tertiary alkyl having 4 to 8 carbon atoms. The tert butyl group is particularly preferred, with the group being more preferred.
[0097] R12〜R14は、それぞれ独立に、水素原子または水酸基である。 [0097] R 12 ~R 14 are independently a hydrogen atom or a hydroxyl group.
本発明においては、 R12〜R14のうちの少なくとも 1つが水酸基であることが好ましぐ 特に、 R12が水酸基であることが好ましい。 In the present invention, it is preferable that at least one of R 12 to R 14 is a hydroxyl group. It is particularly preferable that R 12 is a hydroxyl group.
[0098] 化合物（C)として、より具体的には、下記一般式 (c 1 1)で表される化合物（c 1 - 1) ,下記一般式 (c 1 2)で表される化合物 (c 1 2)、下記一般式 (c 1 3)で表される化合物（c 1 3)、下記一般式 (c 1 4)で表される化合物（c 1 4)、下記一般式 (c 1 5)で表される化合物（c 1 5)等が挙げられる。 [0098] More specifically, as compound (C), a compound represented by the following general formula (c 1 1) (c 1-1), a compound represented by the following general formula (c 1 2) (c 1 2), a compound represented by the following general formula (c 1 3) (c 1 3), a compound represented by the following general formula (c 1 4) (c 1 4), a compound (c 15) represented by the following general formula (c 15) and the like.
[化 22]  [Chemical 22]
Figure imgf000037_0001
( c一 1一 3 )
Figure imgf000037_0001
(c 1 1 1 3)
Figure imgf000037_0002
Figure imgf000037_0002
( o— 1一-.。)  (o— 1 one-.)
[式中、 R11は上記と同じである。 ] [Wherein R 11 is the same as above. ]
[0100] 化合物（C)は、下記一般式 ( 1)で表される化合物（C' )のカルボキシ基末端の 水素原子を、周知の方法により、酸解離性基で置換することにより製造できる。 [0100] Compound (C) can be produced by substituting the hydrogen atom at the terminal of the carboxy group of compound (C ') represented by the following general formula (1) with an acid-dissociable group by a well-known method.
たとえば上記化合物（c 1一；!）〜（c— 1 5)は、それぞれ、化合物（C' )として、リ トコール酸（式 (c '—1)中の R12が水酸基であり、 R13および R14が水素原子である化 合物）、コール酸 (式 ( 1)中の R12〜R14が水酸基である化合物）、デォキシコー ル酸 (式 ( 1)中の R12および R14が水酸基であり、 R13が水素原子である化合物） 、コラン酸（式 (c' 1)中の R12〜R14が水素原子である化合物）、ヒォデォキシコール 酸 (式 ( 1)中の R12および R13が水酸基であり、 R14が水素原子である化合物）を 用いることにより製造でさる。 For example, each of the above compounds (c 1 one ;!) to (c—15) has, as the compound (C ′), lithocholic acid (wherein R 12 in the formula (c′—1) is a hydroxyl group, R 13 And a compound in which R 14 is a hydrogen atom), cholic acid (a compound in which R 12 to R 14 in formula (1) are hydroxyl groups), deoxycholate (in which R 12 and R 14 in formula (1) are A compound having a hydroxyl group and R 13 being a hydrogen atom), cholanic acid (a compound having R 12 to R 14 in the formula (c ′ 1) being a hydrogen atom), hydroxycholic acid (in the formula (1)) In which R 12 and R 13 are a hydroxyl group, and R 14 is a hydrogen atom.
[0101] [化 23] [0101] [Chemical 23]
Figure imgf000038_0001
Figure imgf000038_0001
[式 (c '—1)中、 R"〜Ri4は、それぞれ、上記式 (c l)中の R"〜Ri4と同じである。 ] [In the formula ( c′— 1), R ″ to R i4 are the same as R ″ to R i4 in the above formula (cl), respectively. ]
[0102] (C)成分としては、 1種を単独で用いてもよいし、 2種以上を組み合わせて用いても よい。  [0102] As the component (C), one type may be used alone, or two or more types may be used in combination.
本発明においては、上記の中でも、化合物（c 1 1)および/または化合物（c 1 - 2)を用いること力 S好ましく、特に化合物（c— 1— 1)が好ましレ、。  In the present invention, among the above, it is preferable to use the compound (c 1 1) and / or the compound (c 1 -2). S is preferable, and the compound (c-1-1) is particularly preferable.
本発明において、化学増幅型ポジ型シリコン系レジスト組成物における化合物（C) の含有量は、（A)成分 100質量部に対し、 0· ；!〜 20質量部が好ましぐ；!〜 15質量 部がより好ましぐ 3〜； 10質量部がさらに好ましい。上記範囲の下限値以上とすること で上記効果に優れ、上限値以下とすることで、感度が良好となる。  In the present invention, the content of the compound (C) in the chemically amplified positive silicon resist composition is preferably 0 · ;! to 20 parts by mass with respect to 100 parts by mass of the component (A); 3 parts by mass is more preferred; 10 parts by mass is more preferred. By making it above the lower limit of the above range, the above effect is excellent, and by making it below the upper limit, the sensitivity becomes good.
[0103] <任意成分 3 :含窒素有機化合物 (D)〉 [0103] <Optional component 3: Nitrogen-containing organic compound (D)>
本発明においては、前記任意成分として、さらに、含窒素有機化合物 (D) (以下、（ D)成分という）を含有することが好ましい。これにより、レジストパターン形状、引き置 き圣日守安 /£性 post exposure stability of the latent image formed by the pattern-wis e exposure of the resist layer)などカ向上する。  In the present invention, it is preferable to further contain a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) as the optional component. As a result, the resist pattern shape, post exposure stability of the latent image formation by the pattern-wishes exposure of the resist layer, etc. are improved.
この（D)成分は、既に多種多様なものが提案されているので、公知のものから任意 に用いれば良ぐかかる（D)成分としては、たとえば第 2級脂肪族ァミン、第 3級脂肪 族ァミン等の脂肪族ァミン、芳香族ァミン等が挙げられる。  Since a wide variety of components (D) have already been proposed, any known (D) component can be used arbitrarily. Examples of the component (D) include secondary aliphatic amines and tertiary aliphatics. Examples thereof include aliphatic amines such as amines and aromatic amines.
[0104] ここで、「脂肪族」とは、先に述べた通り、芳香族に対する相対的な概念であって、 芳香族性を持たな!/、基、化合物等を意味するものと定義する。 [0104] Here, "aliphatic" is a relative concept with respect to aromatics, as described above, and is defined as meaning no aromaticity! /, Group, compound, etc. .
「脂肪族ァミン」とは、 1つ以上の脂肪族基を有するァミンであり、前記脂肪族基は 炭素数が 1〜 12であることが好まし!/、。  The “aliphatic amine” is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms! /.
脂肪族ァミンとしては、アンモニア NHの水素原子の少なくとも 1つを、直鎖状また は分岐鎖状の炭素数;!〜 12のアルキル基またはヒドロキシアルキル基で置換したアミ ン（アルキルアミンまたはアルキルアルコールァミン）；その構造中に脂肪族環式基を 有する脂肪族環式ァミン等が挙げられる。ここで、「脂肪族環式基」は、芳香性を持た なレ、単環式基または多環式基であることを示す。 As an aliphatic amine, at least one hydrogen atom of ammonia NH is linear or Is branched chain carbon number;! ~ 12 alkyl or hydroxyalkyl substituted amine (alkylamine or alkyl alcoholamine); aliphatic cyclic amine having an aliphatic cyclic group in its structure, etc. Is mentioned. Here, the “aliphatic cyclic group” indicates that it is aromatic, monocyclic group or polycyclic group.
アルキルァミンおよびアルキルアルコールァミンの具体例としては、 n へキシルァ ミン、 n へプチルァミン、 n ォクチルァミン、 n ノニルァミン、 n—デシルァミン等 のモノアルキルァミン；ジェチルァミン、ジー n プロピルァミン、ジー n へプチルァ ミン、ジ n ォクチルァミン、ジシクロへキシルァミン等のジアルキルァミン；トリメチ ノレ ミン、卜リエチノレアミン、卜リー n プロピノレアミン、卜リー n フ"チノレアミン、卜リー n 一へキシルァミン、トリー n—ペンチルァミン、トリー n へプチルァミン、トリー n オタ チルァミン、トリー n ノニノレアミン、トリ一 n デカニノレアミン、トリ一 n ドデシルァミン 等のトリアルキルァミン；ジエタノールァミン、トリエタノールァミン、ジイソプロパノール ァミン、トリイソプロパノールァミン、ジ n ォクタノールァミン、トリー n ォクタノール ァミン等のアルキルアルコールァミンが挙げられる。  Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc .; jetylamine, di-n-propylamine, di-n-heptylamine, di- n Dialkylamines such as octylamine and dicyclohexylamine; Trialkylamines such as otatilamine, tri-n nonenoleamine, tri-n-decaninoleamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropaline Examples include alkyl alcohol amines such as noramine, di-n-octanolamine, and tri-n-octanolamine.
脂肪族環式ァミンとしては、たとえば、ヘテロ原子として窒素原子を含む脂肪族複 素環化合物が挙げられる。前記複素環化合物としては、単環式のもの（脂肪族単環 式ァミン）であっても多環式のもの (脂肪族多環式ァミン)であってもよ!/、。  Examples of the aliphatic cyclic amine include an aliphatic bicyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine)! /.
脂肪族単環式ァミンとして、具体的には、ピぺリジン、ピぺラジン等が挙げられる。 脂肪族多環式ァミンとしては、炭素数が 6〜； 10のものが好ましぐ具体的には、 1 , 5 ージァザビシクロ [4. 3. 0]— 5 ノネン、 1 , 8 ジァザビシクロ [5. 4. 0]— 7 ゥン デセン、へキサメチレンテトラミン、 1 , 4ージァザビシクロ [2· 2. 2]オクタン等が挙げ られる。  Specific examples of the aliphatic monocyclic amine 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.
「芳香族ァミン」は、アンモニア NHの水素原子の少なくとも 1つが、芳香族性を有  “Aromatic amine” means that at least one hydrogen atom of ammonia NH has aromaticity.
3  Three
する基 (以下、芳香族基ということがある。）で置換された化合物を意味する。 Means a compound substituted with a group (hereinafter sometimes referred to as an aromatic group).
芳香族基としては、芳香族炭化水素基、芳香族複素環式基等が挙げられる。  Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.
芳香族炭化水素基としては、炭素数が 4〜20であることが好ましぐ 5〜； 15であるこ と力 り好ましく、炭素数 6〜； 10が最も好ましい。芳香族炭化水素基として、具体的に は、ベンゼン、ナフタレン、アントラセン等の芳香環から水素原子を 1つ除いた基（たと えばフエニル基、ナフチル、アントラセニル基等）；炭素数;!〜 5の直鎖または分岐の アルキル基の水素原子の一部が芳香環で置換された基（たとえばベンジル基、フエ ニルェチル基（C H -CH -CH一）、ナフチルメチル基（C H -CH一）、ナフ The aromatic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. As an aromatic hydrocarbon group, specifically, a group obtained by removing one hydrogen atom from an aromatic ring such as benzene, naphthalene, anthracene, etc. For example, a phenyl group, a naphthyl group, an anthracenyl group, etc.); a group in which a hydrogen atom of a straight chain or branched alkyl group having a carbon number of !!-5 is substituted with an aromatic ring (for example, a benzyl group, a phenylethyl group (CH- CH 2 -CH 1), naphthylmethyl group (CH 2 -CH 1), naphth
6 5 2 2 10 7 2 チルェチル基（C H -CH -CH一）などが挙げられる。それらの基において、芳  6 5 2 2 10 7 2 Tylethyl group (CH 2 —CH 2 —CH 1) and the like. In those groups, Yoshi
10 7 2 2  10 7 2 2
香環は置換基を有していても良ぐ前記置換基としては、炭素数;!〜 5のアルキル基 等が挙げられる。  The aromatic ring may have a substituent. Examples of the substituent include an alkyl group having!
芳香族複素環式基は、炭素原子と、炭素原子以外のへテロ原子（窒素原子、酸素 原子、硫黄原子等）とから構成されている環骨格を有する芳香族環式基であり、たと えばクマリン等の芳香族複素環から 1個の水素原子を除いた基が挙げられる。これら の芳香族複素環式基は、置換基を有していてもよぐ前記置換基としては、炭素数 1 〜5のアルキル基等が挙げられる。  An aromatic heterocyclic group is an aromatic cyclic group having a ring skeleton composed of carbon atoms and hetero atoms other than carbon atoms (nitrogen atoms, oxygen atoms, sulfur atoms, etc.). And a group obtained by removing one hydrogen atom from an aromatic heterocycle such as coumarin. These aromatic heterocyclic groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
芳香族基としては、本発明の効果である支持体上における高精細かつ高アスペクト 比のパターン形成に優れることから、芳香族複素環式基が好ましぐ特に、置換基を 有するクマリンから水素原子を 1個除!/、た基が好まし!/、。  As the aromatic group, an aromatic heterocyclic group is preferred because it is excellent in high-definition and high-aspect-ratio pattern formation on the support, which is an effect of the present invention. Remove one! /, Prefer the group! /.
[0106] 芳香族ァミンとしては、特に、第 2級ァミンおよび/または第 3級ァミンが好ましぐ第 3級ァミンがより好ましい。前記第 2級ァミンおよび/または第 3級ァミンは、少なくとも 1つの芳香族基を含んでいればよぐそれ以外に、炭素数;!〜 5の直鎖、分岐または 環状の脂肪族炭化水素基、前記脂肪族炭化水素基の炭素原子の一部が窒素原子 等のへテロ原子で置換された基等を含んでレ、てもよレ、。 [0106] The aromatic amine is particularly preferably a tertiary amine, preferably a secondary amine and / or a tertiary amine. The secondary amine and / or tertiary amine may contain at least one aromatic group. Besides, it is a linear, branched or cyclic aliphatic hydrocarbon group having 5 to 5 carbon atoms; A group in which a part of carbon atoms of the aliphatic hydrocarbon group is substituted with a hetero atom such as a nitrogen atom, or the like.
[0107] 芳香族ァミンとしては、特に、下記一般式 (d—1)で表される化合物が好ましい。  [0107] As the aromatic amine, a compound represented by the following general formula (d-1) is particularly preferable.
[0108] [化 24] [0108] [Chemical 24]
Figure imgf000040_0001
Figure imgf000040_0001
[式中、 R41〜R42はそれぞれ独立に炭素数 1〜； 10のアルキル基であり、 R43は炭素数 ；!〜 5のァノレキノレ基であり、 nは 0〜2の整数である。 ] [Wherein, R 41 to R 42 are each independently an alkyl group having 1 to 10 carbon atoms, R 43 is an alkenoquinole group having! To 5 carbon atoms, and n is an integer of 0 to 2. ]
(D)成分は、 1種を単独で用いてもよいし、 2種以上を組み合わせて用いてもよい。 本発明にお!/、て、化学増幅型ポジ型シリコン系レジスト組成物における（D)成分の 含有量は、（A)成分 100質量部に対して、 0. 01〜； 10質量部が好ましぐ 0. 01〜5 質量部がより好ましい。 As the component (D), one type may be used alone, or two or more types may be used in combination. In the present invention, the content of the component (D) in the chemically amplified positive silicon resist composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). Mashiro 0.01 to 5 parts by mass are more preferable.
[0110] <任意成分 4 :スルホユウム化合物（E)〉  [0110] <Optional component 4: Sulphoyuum compound (E)>
本発明においては、前記任意成分として、さらに、下記一般式 (e— 1)で表されるス ルホニゥム化合物（E) (以下、（E)成分ということがある。）を含有すること力 S好ましい。 これにより、レジスト組成物を溶液として保管する間の pHの変動が抑制され、保存安 定性が向上する。特に、前記ポジ型シリコン系レジスト組成物が上述した（D)成分を 含有する場合、溶液として保管する間に pHの変動が生じやすいため、（E)成分を併 用することが好ましい。  In the present invention, it is preferable that the optional component further contains a sulfone compound (E) represented by the following general formula (e-1) (hereinafter also referred to as component (E)). . As a result, pH fluctuations during storage of the resist composition as a solution are suppressed, and storage stability is improved. In particular, when the positive silicon resist composition contains the component (D) described above, it is preferable to use the component (E) in combination because the pH tends to change during storage as a solution.
[0111] [化 25] 2—≤+ ΟΗ' [0111] [Chemical 25] 2—≤ + ΟΗ '
[式（e— 1)中、 R21〜R23は、それぞれ独立に、置換基を有してもよいアルキル基、ま たは置換基を有してもよいァリール基である。 ] [In the formula (e-1), R 21 to R 23 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. ]
[0112] R21〜R23のアルキル基としては、特に制限はなぐ例えば炭素数;!〜 10の直鎖状、 分岐状または環状のアルキル基等が挙げられる。具体的には、メチル基、ェチル基、 n プロピル基、イソプロピル基、 n ブチル基、イソブチル基、 n ペンチル基、シク 口ペンチル基、へキシル基、シクロへキシル基、ノエル基、デカニル基等が挙げられ 前記アルキル基は、置換基を有していてもよい。すなわち、アルキル基の水素原子 の一部又は全部が置換基で置換されてレ、てもよ!/、。前記アルキル基が有して!/、ても よい置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原 子；炭素数 1〜20のアルキル基等が挙げられる。前記置換基としては、特に、炭素数 ；!〜 5のアルキル基が好ましぐメチル基、ェチル基、プロピル基、 n ブチル基、 tert ブチル基であることが最も好ましい。 R21〜R のァリール基としては、特に制限はなぐ例えば、炭素数 6〜20のァリー ル基が挙げられ、具体的にはフエニル基、ナフチル基が挙げられる。前記ァリール基 は置換基を有していてもよい。すなわち、ァリール基の水素原子の一部又は全部が 置換基で置換されてレ、てもよ!/、。前記ァリール基が有して!/、てもよ!/、置換基としては 、前記アルキル基が有していてもよい置換基として挙げたものと同様のものが挙げら れる。 [0112] The alkyl group for R 21 to R 23, particularly limited Nag example carbon atoms;! ~ 10 linear, include alkyl groups such as branched or cyclic. Specifically, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, n pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, Noel group, decanyl group, etc. The alkyl group may have a substituent. That is, some or all of the hydrogen atoms in the alkyl group may be substituted with substituents. Examples of the substituent that the alkyl group may have! / May include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 20 carbon atoms, and the like. The substituent is most preferably a methyl group, an ethyl group, a propyl group, an n butyl group, or a tert butyl group, particularly preferably an alkyl group having! The aryl group of R 21 to R is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms, specifically, a phenyl group and a naphthyl group. The aryl group may have a substituent. That is, some or all of the hydrogen atoms of the aryl group may be substituted with substituents. Examples of the substituent that the aryl group has! / May be the same as those described as the substituent that the alkyl group may have.
[0113] (E)成分の好ましい例としては、下記一般式 (e— 2)で示されるトリフエニル化合物、 下記一般式 (e— 3)で示されるトリシクロへキシル化合物等が挙げられる。  [0113] Preferable examples of the component (E) include triphenyl compounds represented by the following general formula (e-2), tricyclohexyl compounds represented by the following general formula (e-3), and the like.
これらの中でも、一般式 (e— 2)で示されるトリフエニル化合物が好ましぐ特に、 R20 ェ〜 15がすべて水素原子である化合物が好ましい。 Among these, a triphenyl compound represented by the general formula (e-2) is preferable, and a compound in which R 20 to 15 are all hydrogen atoms is preferable.
[0114] [化 26]  [0114] [Chemical 26]
Figure imgf000042_0001
Figure imgf000042_0001
[式 (e— 2)中、 R 〜 R lbは、それぞれ独立に、水素原子、ハロゲン原子または炭 素数 1から 20のアルキル基である。 ] [In the formula (e-2), R to R lb are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms. ]
[0115] [化 27] [0115] [Chemical 27]
Figure imgf000043_0001
Figure imgf000043_0001
[式 (e— 3)中、 R221〜R ^は、それぞれ独立に、水素原子、ハロゲン原子または炭 素数 1から 20のアルキル基である。 ] [In the formula (e-3), R 221 to R ^ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms. ]
[0116] (E)成分は、 1種を単独で用いてもよいし、 2種以上を組み合わせて用いてもよい。 [0116] As the component (E), one type may be used alone, or two or more types may be used in combination.
本発明にお!/、て、化学増幅型ポジ型シリコン系レジスト組成物における（E)成分の 含有量は、（A)成分 100質量部に対して、 0. 0；!〜 5質量部が好ましぐ 0. 05〜4質 量部がより好ましぐ 0. ；!〜 3質量部がさらに好ましい。  In the present invention, the content of the (E) component in the chemically amplified positive silicon resist composition is 0.0;! To 5 parts by mass with respect to 100 parts by mass of the (A) component. Preferred 0.05 to 4 parts by weight is more preferred 0.;! To 3 parts by weight is even more preferred.
[0117] <任意成分 5 :化合物（F)〉 [0117] <Optional component 5: Compound (F)>
本発明においては、前記任意成分として、さらに、感度劣化の防止や、レジストバタ ーン形状、引き置き経時安定性等の向上の目的で、有機カルボン酸、ならびにリンの ォキソ酸およびその誘導体からなる群から選択される少なくとも 1種の化合物（F) (以 下、（F)成分という）を含有させることができる。  In the present invention, as the optional component, for the purpose of further preventing sensitivity deterioration and improving the resist pattern shape, retention time stability, etc., the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof At least one compound (F) selected from (hereinafter referred to as component (F)) can be contained.
有機カルボン酸としては、例えば、酢酸、マロン酸、クェン酸、リンゴ酸、コハク酸、 安息香酸、サリチル酸などが好適である。これらの中でも特にマロン酸が好ましい。 リンのォキソ酸およびその誘導体としては、リン酸、ホスホン酸、ホスフィン酸等が挙 げられ、これらの中でも特にホスホン酸が好ましい。  As the organic carboxylic acid, for example, acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Of these, malonic acid is particularly preferable. Examples of phosphorus oxoacids and derivatives thereof include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
リンのォキソ酸の誘導体としては、たとえば、上記ォキソ酸の水素原子を炭化水素 基で置換したエステル等が挙げられる。前記炭化水素基としては、炭素数;!〜 5のァ ルキル基、炭素数 6〜； 15のァリール基等が挙げられる。 Derivatives of phosphorus oxoacid include, for example, the above hydrogen atom of oxoacid as a hydrocarbon. And esters substituted with a group. Examples of the hydrocarbon group include an alkyl group having! To 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, and the like.
リン酸の誘導体としては、リン酸ジー n—ブチルエステル、リン酸ジフエニルエステル 等のリン酸エステルなどが挙げられる。  Examples of phosphoric acid derivatives include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate.
ホスホン酸の誘導体としては、ホスホン酸ジメチノレエステノレ、ホスホン酸ージー n— ブチルエステル、フエ二ノレホスホン酸、ホスホン酸ジフエニノレエステノレ、ホスホン酸ジ ベンジルエステル等のホスホン酸エステルなどが挙げられる。  Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethylolestenole, phosphonic acid diol n-butyl ester, fenenorephosphonic acid, phosphonic acid diphenenoresestenole, and phosphonic acid dibenzyl ester.
ホスフィン酸の誘導体としては、フエニルホスフィン酸等のホスフィン酸エステルなど が挙げられる。  Examples of the phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
(F)成分は、 1種を単独で用いてもよぐ 2種以上を併用してもよい。  As the component (F), one type may be used alone, or two or more types may be used in combination.
(F)成分は、通常、（A)成分 100質量部当り 0. 01-5. 0質量部の割合で用いら れる。  Component (F) is usually used at a ratio of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
[0118] <その他の任意成分〉  [0118] <Other optional components>
本発明においては、前記任意成分として、さらに所望により混和性のある添加剤、 例えばレジスト膜の性能を改良するための付加的樹脂、塗布性を向上させるための 界面活性剤、溶解抑制剤、可塑剤、安定剤、着色剤、ハレーション防止剤、染料など を適宜、添加含有させることができる。  In the present invention, as the above-mentioned optional component, if necessary, an additive that is miscible, for example, an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, a dissolution inhibitor, a plasticizer. Agents, stabilizers, colorants, antihalation agents, dyes and the like can be added and contained as appropriate.
[0119] 本発明で用いる化学増幅型ポジ型シリコン系レジスト組成物は、材料を有機溶剤（ 以下、（S)成分ということがある）に溶解させて製造することができる。  [0119] The chemically amplified positive silicon resist composition used in the present invention can be produced by dissolving a material in an organic solvent (hereinafter, also referred to as (S) component).
(S)成分としては、使用する各成分を溶解し、均一な溶液とすることができるもので あればよぐ従来、化学増幅型レジストの溶剤として公知のものの中から任意のものを 1種または 2種以上適宜選択して用いることができる。  As the component (S), 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.
例えば、アセトン、メチルェチルケトン、シクロへキサノン、メチルー n—アミルケトン、 メチルイソアミルケトン、 2—へプタノンなどのケトン類；エチレングリコール、ジェチレ ングリコール、プロピレングリコール、ジプロピレングリコールなどの多価アルコール類 ；エチレングリコーノレモノアセテート、ジエチレングリコーノレモノアセテート、プロピレン グリコールモノアセテート、またはジプロピレングリコールモノアセテート等のエステル 結合を有する化合物；前記多価アルコール類または前記エステル結合を有する化合 物のモノメチノレエーテノレ、モノエチノレエーテノレ、モノプロピノレエーテノレ、モノブチノレエ 一テル等のモノアルキルエーテルまたはモノフエニルエーテル等のエーテル結合を 有する化合物等の多価アルコール類の誘導体 [これらの中では、プロピレングリコー ルモノメチルエーテルアセテート（PGMEA)、プロピレングリコールモノメチルエーテ ル（PGME)が好ましい]；ジォキサンのような環式エーテル類；乳酸メチル、乳酸ェ チル（EU、酢酸メチル、酢酸ェチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸ェ チル、メトキシプロピオン酸メチル、エトキシプロピオン酸ェチルなどのエステル類；ァ ニソーノレ、ェチノレべンジノレエーテノレ、クレジノレメチノレエーテノレ、ジフエニノレエーテノレ、 ジベンジノレエーテノレ、フエネト一ノレ、ブチノレフエニノレエーテノレ、ェチノレベンゼン、ジェ チノレベンゼン、アミノレベンゼン、イソプロピノレベンゼン、トノレエン、キシレン、シメン、メ シチレン等の芳香族系有機溶剤などを挙げることができる。 For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol A compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the polyhydric alcohol or the compound having an ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ether or monophenyl ether, such as monomethyl etherate, monoethinore etherol, monopropinore etherol, monobutinole Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable]; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EU, methyl acetate, ethyl acetate, acetic acid) Esters such as butyl, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisonole, ethinoleveninoreethenore, crezinoremethinoreethenore, diphenenoreethenore, dibenzi Noreete Nore Fueneto one Norre, butyl Roh reflex Eni Honoré ether Honoré, Echinorebenzen can include oxygenate Chinorebenzen, amino Les benzene, isopropyl Honoré benzene, Tonoreen, xylene, cymene, and the like aromatic organic solvents such as main Shichiren.
これらの有機溶剤は単独で用いてもよく、 2種以上の混合溶剤として用いてもょレ、。 中でも、プロピレングリコールモノメチルエーテルアセテート（PGMEA)、プロピレン グリコールモノメチルエーテル（PGME)、 ELが好ましい。  These organic solvents may be used alone or as a mixed solvent of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.
また、 PGMEAと極性溶剤とを混合した混合溶媒は好ましい。その配合比（質量比 )は、 PGMEAと極性溶剤との相溶性等を考慮して適宜決定すればよいが、好ましく は 1： 9〜9 : 1、より好ましくは 2： 8〜8： 2の範囲内とする。  A mixed solvent in which PGMEA and a polar solvent are mixed is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Within range.
より具体的には、極性溶剤として ELを配合する場合は、 PGMEA : ELの質量比は 、好ましくは 1 : 9〜9 : 1、より好ましくは 2 : 8〜8： 2である。また、極性溶剤として PGM Eを配合する場合は、 PGMEA: PGMEの質量比は、好ましくは 1： 9〜9： 1、より好ま しくは 2： 8〜8： 2であり、最も好ましくは 5： 5〜8： 2である。  More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGM E is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and most preferably 5: 5-8: 2.
(S)成分の使用量は特に限定しないが、基板等に塗布可能な濃度で、塗布膜厚に 応じて適宜設定される。一般的にはレジスト組成物の固形分濃度が 2〜20質量％、 好ましくは 5〜； 15質量％の範囲内となる様に用いられる。  The amount of component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating thickness. Generally, it is used so that the solid content concentration of the resist composition is in the range of 2 to 20% by mass, preferably 5 to 15% by mass.
《ハードマスク》 《Hard Mask》
本発明で用いるハードマスクは、レジスト下層膜として、シリコン系ハードマスク形成 材料を用いて形成されるものであれば特に限定されない。中でもシロキサン系の重 合体を含む組成物が好ましぐ（BH)シロキサン系重合体と、質量平均分子量が 300 0以下の (AH)シロキサン系化合物とを含有する組成物（以下、ハードマスク形成用 組成物と言うことがある）がさらに好ましい。以下、このようなハードマスクについて詳 しく説明する。 The hard mask used in the present invention is not particularly limited as long as it is formed using a silicon-based hard mask forming material as the resist underlayer film. In particular, a composition containing a siloxane polymer is preferred (BH) siloxane polymer and a mass average molecular weight of 300 A composition containing 0 or less (AH) siloxane compound (hereinafter sometimes referred to as a composition for forming a hard mask) is more preferred. Hereinafter, such a hard mask will be described in detail.
[0121] < (AH)シロキサン系化合物〉 [0121] <(AH) Siloxane compound>
(AH)シロキサン系化合物は、質量平均分子量が 3000以下である。質量平均分 子量をこのような範囲とすることによって、ハードマスク上に形成されたレジストパター ンの裾引きを低減させるとともに、パターンの形状を改善することも可能となる。  The (AH) siloxane compound has a mass average molecular weight of 3000 or less. By setting the mass average molecular weight within such a range, it is possible to reduce the tailing of the resist pattern formed on the hard mask and to improve the pattern shape.
[0122] 上記（AH)シロキサン系化合物としては、下記の一般式（ah— 1)、（ah— 2)および [0122] Examples of the (AH) siloxane compound include the following general formulas (ah-1), (ah-2) and
(ah— 3)で示されるようなラダー状構造、環状構造もしくはかご型構造のいずれかの 構造を有するものが好ましレヽものとして挙げられる。  Those having a ladder-like structure, a cyclic structure or a cage structure as shown in (ah-3) are preferred.
[0123] [化 28] [0123] [Chemical 28]
Figure imgf000046_0001
Figure imgf000046_0001
[式中、 Rlh、 R3h、 R4h、 R5h、 R6hはそれぞれ独立して、水素原子、水酸基又はアルキ ル基、アルコキシ基であり、 R2hはそれぞれ独立して直鎖状、分岐状あるいは環状の 炭化水素基であり、（ah— 1)においては Rlhと R3hおよび/または R4hと R5hとが一緒に なって一 O—であってもよく、 mは 1から 8であり、 nは 2力、ら 8である。 ] [In the formula, R lh , R 3h , R 4h , R 5h , R 6h are each independently a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, and R 2h are each independently a linear or branched group. In (ah—1), R lh and R 3h and / or R 4h and R 5h may be combined to form one O—, and m is 1 to 8 And n is 2 forces, et al. ]
[0124] ここで、 Rlh、 R3h、 R4h、 R5h、 R6hの「アルキル基」及び「アルコキシ基」としては、炭素 数 1から 3のものであることが好まし!/、。 Here, as the “alkyl group” and “alkoxy group” of R lh , R 3h , R 4h , R 5h , R 6h , carbon It is preferred to be of the number 1 to 3! /.
これらのアルキル基としては、例えば、メチル基、ェチル基、プロピル基、イソプロピ ル基等が挙げられる。  Examples of these alkyl groups include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
これらのアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等が 挙げられる。  Examples of these alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group.
上記一般式（ah— 1)、（ah— 2)の化合物においては、 Rlh、 R3h、 R4hおよび R5hの 合計の 25モル％以上が水酸基であることが好ましい。 The general formula (AH-1), in the compounds of (ah- 2), R lh, R 3h, is preferably more than 25 mol% of the sum of R 4h and R 5h is a hydroxyl group.
また、一般式（ah— 3)の化合物においては、 R6hの 25モル％以上が水酸基である ことが好ましい。 In the compound of the general formula (ah-3), it is preferable that 25 mol% or more of R 6h is a hydroxyl group.
[0125] さらに、 R2hの炭化水素基としては、直鎖状、分岐状あるいは環状の炭素数 1から 1 8の脂肪族炭化水素、又は芳香族炭化水素基であることが好ましい。上記直鎖状又 は分岐状炭化水素基としては、メチル基、ェチル基、プロピル基、イソプロピル基、 t ブチル基、ペンチル基、ネオペンチル基、へキシル基、ォクチル基、ノニル基、デ シル基、ゥンデシル基、ドデシル基等のアルキル基；ビュル基、ァリノレ基、プロぺニル 基等のアルケニル基；シクロペンチル基、シクロへキシル基、ノルボルニル基、ノルボ ルネニル基、ァダマンチル基等の環状アルキル基；等が挙げられる。上記芳香族炭 化水素基としては、フエニル基、ナフチル基、メチルフエニル基、ェチルフエニル基、 トリノレ基、クロ口フエ二ル基、ブロモフエニル基、フルオロフェニル基等のァリール基； ベンジル基、フエネチル基、ナフチルメチル基、ジフエニルメチル基、トリフエ二ルメチ ル基、 1ーメチルー 1 フエニルェチル基等のァラルキル基等が挙げられる。これら の炭化水素基は、置換基を有していてもよぐこの置換基としては、例えば、水酸基、 炭素数 1から 3のアルコキシ基等が挙げられる。 Furthermore, the hydrocarbon group for R 2h is preferably a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an aromatic hydrocarbon group. Examples of the linear or branched hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, Alkyl groups such as undecyl group and dodecyl group; alkenyl groups such as bur group, arinole group and propenyl group; cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, norbornyl group, norbornenyl group and adamantyl group; Can be mentioned. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, methylphenyl group, ethenylphenyl group, trinole group, chlorophenyl group, bromophenyl group, fluorophenyl group and the like; benzyl group, phenethyl group, naphthyl group, etc. Examples thereof include aralkyl groups such as a methyl group, a diphenylmethyl group, a triphenylmethyl group, and a 1-methyl-1-phenylethyl group. These hydrocarbon groups may have a substituent. Examples of the substituent include a hydroxyl group and an alkoxy group having 1 to 3 carbon atoms.
このうち、 R2hとして好ましいものとしては、ノルボルニル基、または下記式（ah— 4) で表される基である。 Among these, preferred as R 2h is a norbornyl group or a group represented by the following formula (ah-4).
[0126] [化 29]
Figure imgf000048_0001
[0126] [Chemical 29]
Figure imgf000048_0001
[式中、 pは 0または 1であり、 qは 0力、ら 5である。 ] [Wherein p is 0 or 1 and q is 0 force, et al. 5. ]
[0127] 特に、式 (ah— 4)で表される基は、後述の（BH)成分、有機溶媒との相溶性に優れ 好ましい。 [0127] In particular, the group represented by the formula (ah-4) is preferable because of excellent compatibility with the later-described (BH) component and the organic solvent.
式（ah— 1)、 （ah— 2)で表されるシロキサン系化合物においては、式（ah— 4)で表 される基が、 R2hの 10モル％以上、より好ましくは 25モル％以上含まれることが好まし い。また、式（ah— 3)で表されるシロキサン系化合物においては、式（ah— 4)で表さ れる基が、 R2hの 12· 5モル％以上、より好ましくは 25モル％以上含まれることが好ま しい。上記値以上にすることにより、（AH)シロキサン系化合物の有機溶媒との相溶 性を特に向上させることができる。 In the siloxane-based compound represented by the formula (ah-1) or (ah-2), the group represented by the formula (ah-4) is 10 mol% or more, more preferably 25 mol% or more of R 2h. Preferably included. Further, in the siloxane compound represented by the formula (ah-3), the group represented by the formula (ah-4) is contained in 12.5 mol% or more, more preferably 25 mol% or more of R 2h. I like it. By setting it to the above value or more, the compatibility of the (AH) siloxane compound with the organic solvent can be particularly improved.
[0128] また、式 (ah— 1)の化合物において、 Rlhと R3hおよび/または R4hと R5hとが一緒に なって— O であってもよい。この場合、かご型構造となる。力、ご型構造の場合には、 mは、 2から 4であることが好ましぐ略立方体形状の T8構造、略五角柱形状の T10 構造、略六角柱形状の T12構造となる。 [0128] Further, in the compound of formula (ah- 1), R lh and the R 3h and / or R 4h and R 5h together - may be O. In this case, a cage structure is obtained. In the case of a force-type structure, m is preferably an approximately cubic T8 structure, an approximately pentagonal T10 structure, or an approximately hexagonal T12 structure, preferably 2 to 4.
[0129] 上記一般式（ah— 1)および（ah— 3)で示されるシロキサン系化合物としては、具体 的には下記の構造式（ah— 1 1)、 (ah- 1 - 2)及び（ah— 3— 1)で示されるものが 好ましい。  [0129] Specific examples of the siloxane compounds represented by the above general formulas (ah-1) and (ah-3) include the following structural formulas (ah-1-11), (ah-1-2) and ( ah— 3— 1) is preferred.
[0130] [化 30] [0130] [Chemical 30]
Figure imgf000049_0001
Figure imgf000049_0001
[0131] さらに、上記（ah— 1— 1)、（ah— 1 2)及び（ah— 3— 1)における水酸基の 25% 以上が、メトキシ基、エトキシ基等のアルコキシ基に置換されたものも好ましいものとし て挙げられる。 [0131] Further, those in which at least 25% of the hydroxyl groups in the above (ah-1-1), (ah-1 2) and (ah-3-1) are substituted with alkoxy groups such as methoxy groups and ethoxy groups Are also preferred.
[0132] (AH)シロキサン系化合物の質量平均分子量の上限値は、 3000であり、 2800で あること力 S好ましい。また、下限値としては、 300であること力 S好ましく、 500であること 力はり好ましい。下限値を 300にすることにより、このシロキサン系化合物の蒸発を抑 制することができ、斯カ、るハードマスク用組成物の成膜性を向上させることができる。 [0132] The upper limit of the weight average molecular weight of the (AH) siloxane compound is 3000, and 2800 Being force S is preferable. The lower limit value is preferably 300, preferably S, and more preferably 500. By setting the lower limit value to 300, evaporation of the siloxane compound can be suppressed, and the film forming property of the hard mask composition can be improved.
[0133] < (BH)シロキサン系重合体〉  [0133] <(BH) Siloxane Polymer>
(BH)シロキサン系重合体は、一般式 (bh— 1)で示される構造単位を有する。  The (BH) siloxane polymer has a structural unit represented by the general formula (bh-1).
[0134] [化 31]  [0134] [Chemical 31]
Figure imgf000050_0001
Figure imgf000050_0001
[式中、 R hは、光吸収基を示し、 RShは、水素原子、水酸基、炭素数 1から 6のアルキ ル基、アルコキシ基を示し、 rは 0または 1である。 ] [Wherein R h represents a light absorbing group, R Sh represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and r is 0 or 1. ]
[0135] 上記光吸収基とは、波長 150nmから 300nmの範囲で吸収を有する基である。この 光吸収基としては、例えばベンゼン環、アントラセン環、ナフタレン環等の光吸収部を 有する基が挙げられる。上記光吸収部は、 1個以上の—O—、—O (CO)—で中断さ れて!/、てもよ!/、炭素数 1から 20のアルキレン基を介して、主骨格の Si原子に結合さ れていてもよい。また、ベンゼン環、アントラセン環、ナフタレン環等の光吸収部は、 炭素数 1から 6のアルキル基、アルコキシ基、またはヒドロキシ基等の置換基で 1個以 上置換されていてもよい。これら光吸収基の中でも、ベンゼン環が好ましい。また、上 記吸収基の他に、 Si— Si結合を持つ光吸収部を有する基を用いることもできる。さら に、これらの光吸収部は、シロキサン系重合体の主骨格に含まれていてよい。上記光 吸収基としては、フエニル基、ナフチル基、メチルフエニル基、ェチルフエニル基、トリ ノレ基、クロ口フエニル基、ブロモフエニル基、フルオロフェニル基等のァリール基；ベン ジノレ基、フエネチル基、ナフチルメチル基、ジフエニルメチル基、トリフエニルメチル基 、 1ーメチルー 1 フエニルェチル基等のァラルキル基が挙げられる。中でも、フエ二 ル基が好ましい。特にフエニル基にする場合には、光吸収を良好にすることができる とともに、ハードマスクとしたときの酸素系プラズマに対するエッチング耐性を向上さ せること力 Sでさる。 さらに、上記 (BH)シロキサン系重合体は、一般式 (bh— 2)で表される構成単位の 少なくとも 1種を有することが好ましい。 [0135] The light absorbing group is a group having absorption in the wavelength range of 150 nm to 300 nm. Examples of the light absorbing group include groups having a light absorbing portion such as a benzene ring, an anthracene ring, and a naphthalene ring. The light absorbing part is interrupted by one or more —O— and —O (CO) —! /, May! /, And the main skeleton Si via an alkylene group having 1 to 20 carbon atoms. It may be bonded to an atom. In addition, one or more light absorbing portions such as a benzene ring, an anthracene ring, and a naphthalene ring may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a hydroxy group. Among these light absorbing groups, a benzene ring is preferable. In addition to the above-described absorbing group, a group having a light absorbing portion having a Si—Si bond can also be used. Further, these light absorbing portions may be included in the main skeleton of the siloxane polymer. Examples of the light absorbing group include phenyl group, naphthyl group, methylphenyl group, ethenylphenyl group, trinole group, chlorophenyl group, bromophenyl group, fluorophenyl group and other aryl groups; benzinole group, phenethyl group, naphthylmethyl group, Examples thereof include aralkyl groups such as diphenylmethyl group, triphenylmethyl group, and 1-methyl-1-phenylethyl group. Of these, a phenyl group is preferable. In particular, in the case of using a phenyl group, the light absorption can be improved and the etching resistance S can be improved with respect to the oxygen-based plasma when used as a hard mask. Furthermore, the (BH) siloxane-based polymer preferably has at least one structural unit represented by the general formula (bh-2).
[0136] [化 32] [0136] [Chemical 32]
L … .， i b — 2 ) L…., I b — 2)
[式中、 R9hは、水素原子、アルキル基、またはカルボニル、エステル、ラタトン、アミド 、エーテル、二トリルから選択される少なくとも 1つの官能基を有する 1価の有機基を 示し、 R1Qhは、水素原子、水酸基、炭素数 1から 6のアルキル基、アルコキシ基を示し 、 sは 0または 1である；前記官能基の炭素数は 1〜6であり、前記一価の有機基の炭 素数は;!〜 6である。 ] [Wherein R 9h represents a hydrogen atom, an alkyl group, or a monovalent organic group having at least one functional group selected from carbonyl, ester, rataton, amide, ether, nitrile, and R 1Qh represents A hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, s is 0 or 1; the functional group has 1 to 6 carbon atoms, and the monovalent organic group has a carbon number of ;! ~ 6. ]
[0137] (BH)シロキサン系共重合体の質量平均分子量の下限値は、 8000であること力 S好 ましぐ 10000であることがより好ましい。 （BH)成分の質量平均分子量を 8000以上 にすることにより、ハードマスクの成膜性を向上させることができる。また、（BH)成分 の質量平均分子量の上限値は、 50000力 S好ましく、 30000力 Sより好ましい。 （BH)成 分の質量平均分子量を 50000以下にすることにより、ハードマスク形成用組成物の 塗布性を向上させることができる。  [0137] The lower limit of the mass average molecular weight of the (BH) siloxane copolymer is 8000, more preferably 10,000. By making the mass average molecular weight of the (BH) component 8000 or more, the film formability of the hard mask can be improved. Further, the upper limit of the mass average molecular weight of the component (BH) is preferably 50000 force S, more preferably 30000 force S. By setting the mass average molecular weight of the (BH) component to 50000 or less, the applicability of the hard mask forming composition can be improved.
[0138] < (BH)シロキサン系重合体の製造方法〉  [0138] <Method for producing (BH) siloxane-based polymer>
(BH)シロキサン系共重合体は、（AH)成分と同様に、それぞれの構造単位を含有 する各モノマーを加水分解して、共重合することにより製造される。  The (BH) siloxane copolymer is produced by hydrolyzing and copolymerizing each monomer containing each structural unit, as in the case of the (AH) component.
[0139] ハードマスク形成用組成物における (AH)成分と（BH)成分との比率は、質量比で 1 : 9から 7 : 3であることが好ましぐ 3 : 7から 6 : 4であることがより好ましぐ 5 : 5であるこ とが最も好ましレ、。 (AH)成分および (BH)成分の比率を上記の範囲にすることによ り、上記組成物から形成されたハードマスク上に形成されるレジストパターンにおける 裾引きを低減することができる。  [0139] The ratio of the (AH) component to the (BH) component in the composition for forming a hard mask is preferably 1: 9 to 7: 3 in terms of a mass ratio of 3: 7 to 6: 4. 5: 5 is the most preferred. By setting the ratio of the (AH) component and the (BH) component in the above range, tailing in the resist pattern formed on the hard mask formed from the composition can be reduced.
さらに、（AH)成分と（BH)成分の含有量を、上記の範囲とすることによって、酸発 生剤を添加しなくても良好な形状のパターンを形成することが可能なハードマスクを 形成することが可能となる。 Furthermore, by setting the content of the (AH) component and the (BH) component in the above range, a hard mask capable of forming a pattern with a good shape without adding an acid generator is provided. It becomes possible to form.
[0140] < (CH)溶剤〉 [0140] <(CH) solvent>
ハードマスク形成用組成物は、（CH)溶剤（以下、（CH)成分ともいう）も含有する。 具体的には、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルァ ノレコーノレ等のー価ァノレコーノレ；エチレングリコーノレ、ジエチレングリコーノレ、プロピレ ングリコーノレ、グリセリン、トリメチローノレプロパン、へキサントリオ一ノレ等のァノレコーノレ 類；エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテノレ 、エチレングリコーノレモノプロピノレエーテノレ、エチレングリコーノレモノブチノレエーテノレ 、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノェチルエーテ ノレ、ジエチレングリコーノレモノプロピノレエーテノレ、ジエチレングリコ一ノレモノブチノレエ 一テル、プロピレングリコールモノメチルエーテル（PGME)、プロピレングリコーノレモ ノエチノレエーテノレ、プロピレングリコーノレモノプロピノレエーテノレ、プロピレングリコーノレ モノブチルエーテル等のアルコールのモノエーテル類；前記モノエーテル類のモノァ セテート、酢酸メチル、酢酸ェチル、酢酸ブチル、乳酸ェチル（EL)等のエステル類； アセトン、メチルェチルケトン、シクロアルキルケトン、メチルイソアミルケトン等のケトン 類；エチレングリコーノレジメチノレエーテノレ、エチレングリコーノレジェチノレエーテノレ、ェ チレングリコーノレジプロピノレエーテノレ、エチレングリコーノレジブチノレエーテノレ、 プロピ レングリコールジメチルエーテル（PGDM)、プロピレングリコールジェチルエーテル 、プロピレングリコーノレジブチノレエーテノレ、ジエチレングリコーノレジメチノレエーテノレ、 ジエチレングリコーノレメチノレエチノレエーテノレ、ジエチレングリコーノレジェチノレエーテ ノレ等のアルコールの水酸基をすベてアルキルエーテル化させたアルコールエーテル 類等が挙げられる。  The composition for forming a hard mask also contains a (CH) solvent (hereinafter also referred to as a (CH) component). Specifically, monovalent vinylols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyranolol; ethylene glycolol, diethyleneglycolanol, propyleneglycolanol, glycerin, trimethylololepropane, hexanetriolanol, etc .; ethylene Glycolic Monomethinoleetenore, Ethylene Glyconole Monopropenoleetenore, Ethylene Glyconole Monopropinoleetenore, Ethylene Glyconole Monobutinoleetenore, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Enotere, Diethylene Glyconore Monopropinoate ethere, diethyleneglycol monoremonobutinoleate, propylene glycol monomethyl ether (PGME), Monoethers of alcohols such as pyreneglycolole noetinoreethenole, propyleneglycololemonopropinoreethenole, propyleneglycolole monobutyl ether; monoacetates of the above monoethers, methyl acetate, ethyl acetate, butyl acetate, lactic acid Esters such as ethyl (EL); Ketones such as acetone, methyl ethyl ketone, cycloalkyl ketone, and methyl isoamyl ketone; Ethylene glycono-resin chineno ethenore, Ethylene glycono lesino ethenore Propino glycolateolene, ethylene glycolenoresbutinoleatenole, propylene glycol dimethyl ether (PGDM), propylene glycol jetyl ether, propylene glycolenoresibutinoate ethere, diethylene glycol Examples include alcohol ethers in which the hydroxyl groups of alcohols are all alkyl etherified such as ricono-resin methinoreatenore, diethyleneglycolenoremethinoleetinoreatenore, and diethyleneglyco-reno-etinoreatenore.
中でも、プロピレングリコールモノメチルエーテルアセテート（PGMEA)、 PGME、 Among them, propylene glycol monomethyl ether acetate (PGMEA), PGME,
ELが好ましい。 EL is preferred.
[0141] これらの有機溶媒は、単独で用いてもよいし、 2種以上を組み合わせて用いてもよ い。  [0141] These organic solvents may be used alone or in combination of two or more.
また、 PGMEAと極性溶剤とを混合した混合溶媒は好ましい。その配合比（質量比 )は、 PGMEAと極性溶剤との相溶性等を考慮して適宜決定すればよいが、好ましく は 1： 9〜9 : 1、より好ましくは 2： 8〜8： 2の範囲内とすることが好まし!/、。 より具体的には、極性溶剤として ELを配合する場合は、 PGMEA : ELの質量比はA mixed solvent in which PGMEA and a polar solvent are mixed is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably Is preferably in the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. More specifically, when EL is used as a polar solvent, the mass ratio of PGMEA: EL is
、好ましくは 1 : 9〜9 : 1、より好ましくは 2 : 8〜8： 2である。また、極性溶剤として PGMThe ratio is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. PGM as a polar solvent
Eを配合する場合は、 PGMEA: PGMEの質量比は、好ましくは 1： 9〜9： 1、より好ま しくは 2： 8〜8： 2、さらに好ましくは 3： 7〜7： 3である。 When E is blended, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7: 3.
この溶剤は、（AH)成分及び（BH)成分の合計質量の、 1から 100倍量であり、 2か ら 20倍量用いられることがより好ましい。この範囲内にすることにより、ハードマスク形 成用組成物の塗布性を向上させることができる。  This solvent is used in an amount of 1 to 100 times, more preferably 2 to 20 times the total mass of the components (AH) and (BH). By making it within this range, the applicability of the hard mask forming composition can be improved.
[0142] < (DH)架橋剤〉 [0142] <(DH) Crosslinking agent>
ハードマスク形成用組成物は、（DH)架橋剤（以下、（DH)成分ともいう）を含有し てもよい。 （DH)架橋剤を添加することにより、ハードマスクの成膜性を向上させること ができる。架橋剤としては、一般的に用いられているものを用いてよい。  The composition for forming a hard mask may contain a (DH) crosslinking agent (hereinafter also referred to as a (DH) component). By adding a (DH) cross-linking agent, the film formability of the hard mask can be improved. As the crosslinking agent, those generally used may be used.
[0143] 具体的には、ビスフエノール A型エポキシ樹脂、ビスフエノール F型エポキシ樹脂、 ビスフエノール S型エポキシ樹脂、フエノールノポラック型エポキシ樹脂、クレゾールノ ポラック型エポキシ樹脂等のエポキシ化合物等が挙げられる。また、ジビュルべンゼ ン、ジビニルスルホン、トリアクリルホルマール、グリオキザールや多価アルコールの アクリル酸エステル又はメタクリル酸エステル等も用いられる。 Specific examples include epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol nopolac type epoxy resin, and cresol nopolac type epoxy resin. . In addition, dibutene benzene, divinyl sulfone, triacryl formal, glyoxal, and polyhydric alcohol acrylate or methacrylate are also used.
[0144] また、メラミン、尿素、ベンゾグアナミン、グリコールゥリルのァミノ基の少なくとも 2つ 力 Sメチロール基又は低級アルコキシメチル基若しくは低級ァシロキシメチル基で置換 された化合物等の 2個以上の反応性基をもつ化合物等が挙げられる。低級アルコキ シメチル基及び低級ァシロキシメチル基の炭素数は 2から 6が好ましい。 [0144] In addition, at least two groups of melamine, urea, benzoguanamine, glycoluril, and two or more reactive groups such as a compound substituted with S methylol group, lower alkoxymethyl group or lower acyloxymethyl group And the like. The lower alkoxymethyl group and the lower acyloxymethyl group preferably have 2 to 6 carbon atoms.
[0145] メラミンのァミノ基の少なくとも 2つがメチロール基又は低級アルコキシメチル基で置 換された化合物としては、へキサメチロールメラミン、へキサメトキシメチルメラミン、へ キサメチロールメラミンの 1個力、ら 6個がメトキシメチル化した化合物及びその混合物； へキサェトキシメチノレメラミン、へキサァシロキシメチノレメラミン、へキサメチローノレメラ ミンのメチロール基の 1個力、ら 5個がァシロキシメチル化した化合物又はその混合物 等が挙げられる。 [0145] The compounds in which at least two of the melamine amino groups are replaced with a methylol group or a lower alkoxymethyl group include hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, and six others. Methoxymethylated compounds and mixtures thereof; hexethoxymethino melamine, hexacyloxy methino melamine, hexamethylone melamine, one of the methylol groups, five of which are acyloxymethylated Or a mixture thereof.
[0146] 尿素のァミノ基の少なくとも 2つがメチロール基又は低級アルコキシメチル基で置換 された化合物としては、テトラメチロールゥレア、テトラメトキシメチルゥレア、テトラエト キシメチルゥレア、テトラメチロールゥレアの 1個力も 4個のメチロール基力 Sメトキシメチ ル基化した化合物又はその混合物等が挙げられる。 [0146] At least two of the urea amino groups are substituted with a methylol group or a lower alkoxymethyl group. Examples of the compound include tetramethylolurea, tetramethoxymethylurea, tetraethoxymethylurea, tetramethylolurea, one compound having four or more methylol group S-methoxymethyl groups, or a mixture thereof.
[0147] ベンゾグアナミンのァミノ基の少なくとも 2つがメチロール基又は低級アルコキシメチ ル基若しくは低級ァシロキシメチル基で置換された化合物としては、テトラメチロール グアナミン、テトラメトキシメチルダアナミン、テトラメチロールグアナミンの 1個から 4個 のメチロール基がメトキシメチル化した化合物及びその混合物；テトラエトキシメチノレ グアナミン、テトラァシロキシグアナミン、テトラメチロールグアナミンの 1個から 4個のメ チロール基がァシロキシメチル化した化合物及びその混合物等が挙げられる。 [0147] Examples of the compound in which at least two of the amino groups of benzoguanamine are substituted with a methylol group, a lower alkoxymethyl group or a lower acyloxymethyl group include tetramethylol guanamine, tetramethoxymethyl dianamine, and tetramethylol guanamine. From 1 to 4 methylol groups methoxymethylated and mixtures thereof; tetraethoxymethylanolamine, tetraacyloxyguanamine, tetramethylolguanamine 1 to 4 methylol groups acyloxymethylated compounds and mixtures thereof Etc.
[0148] グリコールゥリルのァミノ基の少なくとも 2つがメチロール基又は低級アルコキシメチ ル基若しくは低級ァシロキシメチル基で置換された化合物としては、テトラメチロール グリコールゥリル、テトラメトキシグリコールゥリル、テトラメトキシメチルダリコールゥリノレ 、テトラメチロールグリコールゥリルのメチロール基の 1個から 4個がメトキシメチル基化 した化合物又はその混合物；テトラメチロールグリコールゥリルのメチロール基の 1個 力、ら 4個がァシロキシメチル化した化合物又はその混合物が挙げられる。  [0148] Compounds in which at least two of the amino groups of glycoluril are substituted with a methylol group, a lower alkoxymethyl group or a lower acyloxymethyl group include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl. Dalicolurinole, a compound in which one to four of the methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof; one of the methylol groups of tetramethylol glycoluril, four of which are acyloxymethyl Compound or a mixture thereof.
[0149] これらの架橋剤は、単独で用いてもよいし、 2種以上を組み合わせて用いてもよい。  [0149] These crosslinking agents may be used alone or in combination of two or more.
この架橋剤の添加量は、（AH)成分及びシロキサン系重合体を合わせた 100質量部 に対して、 0. 1質量部から 50質量部であり、 0. 5質量部から 40質量部であることがよ り好ましい。  The addition amount of the crosslinking agent is 0.1 to 50 parts by mass and 0.5 to 40 parts by mass with respect to 100 parts by mass of the (AH) component and the siloxane polymer. It is more preferable.
[0150] < (EH)酸発生剤〉  [0150] <(EH) acid generator>
ハードマスク形成用組成物は、（EH)酸発生剤（以下、（EH)成分ともいう）を含有し ていてもよい。  The composition for forming a hard mask may contain (EH) acid generator (hereinafter also referred to as (EH) component).
[0151] 酸発生剤としては、ォニゥム塩、ジァゾメタン誘導体、ダリオキシム誘導体、ビススル ホン誘導体、 β -ケトスルホン誘導体、ジスルホン誘導体、ニトロべンジルスルホネート 誘導体、スルホン酸エステル誘導体、 Ν-ヒドロキシイミド化合物のスルホン酸エステ ノレ誘導体など、公知の酸発生剤を用いることができる。  [0151] Examples of the acid generator include onium salts, diazomethane derivatives, darioxime derivatives, bissulfone derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, and sulfonic acids of ヒ ド ロ キ シ -hydroxyimide compounds. A known acid generator such as an ester derivative can be used.
[0152] ォニゥム塩としては、トリフロォロメタンスルホン酸テトラメチルアンモニゥム、ノナフル ォロブタンスルホン酸テトラメチルアンモニゥム、ノナフルォロブタンスルホン酸テトラ η -ブチルアンモニゥム、ノナフルォロブタンスルホン酸テトラフエ二ルアンモニゥム、 p- トルエンスルホン酸テトラメチルアンモニゥム、トリフルォロメタンスルホン酸ジフエニル ョ一ドニゥム、トリフノレオロメタンスノレホン酸（p - tert -ブトキシフエニノレ）フエニノレョ一 ドニゥム、 p—トルエンスルホン酸ジフエ二ルョードニゥム、 p—トルエンスルホン酸（p — tert—ブトキシフエ二ノレ）フエ二ルョードニゥム、トリフルォロメタンスルホン酸トリフエ ニルスルホニゥム、トリフルォロメタンスルホン酸（p— tert—ブトキシフエ二ノレ）ジフエ ニルスルホニゥム、トリフルォロメタンスルホン酸ビス（p— tert—ブトキシフエ二ノレ）フ ェニルスルホニゥム、トリフルォロメタンスルホン酸トリス（p— tert—ブトキシフエニル） スルホ二ゥム、 p—トノレエンスノレホン酸トリフエニノレスノレホニゥム、 p—トノレエンスノレホン 酸（p— tert—ブトキシフエ二ノレ）ジフエニルスルホニゥム、 p-トノレエンスルホン酸ビス（ p - tert -ブトキシフエ二ノレ）フエニルスルホニゥム、 p-トノレエンスルホン酸トリス（p— t ert—ブトキシフエ二ノレ）スルホ二ゥム、ノナフルォロブタンスルホン酸トリフエニルスル ホニゥム、ブタンスルホン酸トリフエニルスルホニゥム、トリフルォロメタンスルホン酸トリ メチルスルホニゥム、 p—トルエンスルホン酸トリメチルスルホニゥム、トリフルォロメタン スルホン酸シクロへキシルメチル（2—ォキソシクロへキシノレ）スルホ二ゥム、 p—トルェ ンスルホン酸シクロへキシルメチル（2—ォキソシクロへキシル）スルホ二ゥム、トリフノレ ォロメタンスルホン酸ジメチルフエニルスルホニゥム、 p—トルエンスルホン酸ジメチル フェニノレスノレホニゥム、 トリフノレオ口メタンスノレホン酸ジシクロへキシノレフエニノレスノレホ 二ゥム、 p—トルエンスルホン酸ジシクロへキシルフェニルスルホニゥム、トリフルォロメ タンスルホン酸トリナフチルスルホニゥム、トリフルォロメタンスルホン酸シクロへキシル メチル（2—ォキソシクロへキシル）スルホ二ゥム、トリフルォロメタンスルホン酸（2—ノ ノレボニル）メチル（2—ォキソシクロへキシル）スルホ二ゥム、エチレンビス [メチノレ（2— ォキソシクロペンチノレ）スルホニゥムトリフルォロメタンスルホナート]、 1 , 2 '—ナフチ ルカルポニルメチルテトラヒドロチォフエニゥムトリフレート等が挙げられる。 [0152] Examples of onium salts include tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, and tetraηa nonafluorobutanesulfonate. -Butyl ammonium, nonafluorobutanesulfonic acid tetraphenyl ammonium, p-toluenesulfonic acid tetramethyl ammonium, trifluoromethanesulfonic acid diphenyl ammonium, trifanololomethane sulphonic acid (p-tert- Butoxyphenenole) Phenylenolone Donium, p-Toluenesulfonic acid diphenylodium, p-Toluenesulfonic acid (p — tert-Butoxyphenenole) phenylodium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p — Tert-butoxyphenole) diphenyl sulfone, trifluoromethanesulfonic acid bis (p- tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) Ruphonium, p-tonoleensnorephonic acid triphenenolesnorephonium, p-tonoleensenolephonic acid (p-tert-butoxyphenenole) diphenylsulfonium, p-tonoleenesulfonic acid bis (P-tert-butoxyphenyl) phenylsulfonium, p-tonoleenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid Triphenyl sulfone, Trimethyl sulfone trifluoromethanesulfonate, Trimethyl sulfone p-toluenesulfonate, Cyclohexylmethyl trifluoromethylsulfonate (2-oxocyclohexyleno) sulfone, p-Toluene Cyclohexyl methyl (2-oxocyclohexyl) sulfone, Dimethyl phenyl sulfone trifanolosulfonate, dimethyl phenylenolesnorephonium dimethyl p-toluenesulfonate, dicyclohexenorenorenomethane methanesulenoate, p-toluenesulfonate dicyclotoluenesulfonate Xylphenylsulfonium, trifluoromethylsulfonic acid trinaphthylsulfonium, trifluoromethylsulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-non- bornyl) methyl ( 2-oxocyclohexyl) sulfonium, ethylenebis [methinole (2-oxocyclopentinole) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophene triflate, etc. Mentioned It is.
ジァゾメタン誘導体としては、ビス（ベンゼンスルホニル）ジァゾメタン、ビス（p—トル エンスノレホニノレ）ジァゾメタン、ビス（キシレンスノレホニノレ）ジァゾメタン、ビス（シクロへ キシノレスノレホニノレ）ジァゾメタン、ビス（シクロペンチノレスノレホニノレ）ジァゾメタン、ビス（ sec ブチルスルホニノレ）ジァゾメタン、ビス（n—プロピルスルホ二ノレ）ジァゾメタン、 ン、ビス（n アミルスルホニノレ）ジァゾメタン、ビス（イソアミノレスルホ二ノレ）ジァゾメタン 、ビス（sec アミルスルホニノレ）ジァゾメタン、ビス（tert アミルスルホニノレ）ジァゾメ タン、 1—シクロへキシノレスノレホニノレ一 1— (tert ブチノレスノレホニノレ）ジァゾメタン、 1 —シクロへキシノレスノレホニノレ一 1— (tert アミノレスノレホニノレ）ジァゾメタン、 1— tert アミルスルホニルー 1一（tert ブチルスルホニル）ジァゾメタン等が挙げられる。 Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluene senorephoninore) diazomethane, bis (xylene senorephoninore) diazomethane, bis (cyclohexenolesnorenoninore) diazomethane, bis (cyclopentino) Lesnolehoninole) diazomethane, bis ( sec butylsulfonole) diazomethane, bis (n-propylsulfonino) diazomethane, bis (n amylsulfonino) diazomethane, bis (isoaminoresulphoninole) diazomethane, bis (sec amylsulfonino) diazomethane, bis (Tert-amylsulfoninole) diazomethane, 1-cyclohexenolesnorehoninole 1- (tert-butinoresnorehoninole) diazomethane, 1-cyclohexinoresnorehoninore 1- (tert-aminoresnorejo Ninole) diazomethane, 1-tert amylsulfonyl-1-mono (tert butylsulfonyl) diazomethane, and the like.
[0154] グリオキシム誘導体としては、ビス一 O— (p トルエンスルホニル） α—ジメチル グリオキシム、ビス一 Ο— (ρ トルエンスルホニル） α—ジフエニルダリオキシム、ビ ス一 Ο— (ρ トルエンスルホニル） α—ジシクロへキシルグリオキシム、ビス一 Ο— (ρ トルエンスルホニル） 2, 3 ペンタンジオングリオキシム、ビス一 Ο— (ρ トノレ エンスルホニル）一 2 メチル 3, 4 ペンタンジオングリオキシム、ビス一 Ο— (η— ブタンスルホニル） aージメチルダリオキシム、ビス O—（n—ブタンスルホニル） aージフエニルダリオキシム、ビス O—（n—ブタンスルホニル） α—ジシクロへ キシルグリオキシム、ビス一 Ο— (η ブタンスルホニル） 2, 3 ペンタンジオングリ ォキシム、ビス一 Ο— (η ブタンスルホニル） 2 メチル 3, 4 ペンタンジオング リオキシム、ビス Ο （メタンスノレホニノレ） aージメチノレグリオキシム、ビス O—（ トリフルォロメタンスルホニル） α—ジメチルダリオキシム、ビス一 Ο— ( 1 , 1 , 1—トリ フルォロェタンスルホニル） α—ジメチルダリオキシム、ビス Ο—（tert ブタンス ノレホニル） α—ジメチルダリオキシム、ビス Ο （パーフルォロオクタンスルホニル )一 aージメチルダリオキシム、ビス O （シクロへキサンスルホニル） α ジメチ ノレダリオキシム、ビス Ο （ベンゼンスルホニル） α—ジメチルダリオキシム、ビス - 0 - (ρ フルォロベンゼンスルホニル） α—ジメチルダリオキシム、ビス一 Ο— ( ρ— tert ブチルベンゼンスルホニル） α—ジメチルダリオキシム、ビス Ο （キ シレンスルホニル） α—ジメチルダリオキシム、ビス一 Ο— (カンファースルホニル） aージメチルダリオキシム等が挙げられる。  [0154] The glyoxime derivatives include bis-l-O- (p-toluenesulfonyl) α-dimethyl glyoxime, bis-l-α- (ρ-toluenesulfonyl) α-diphenyldarioxime, bis-l-α- (ρ-toluenesulfonyl) α- Dicyclohexylglyoxime, bis-one Ο— (ρ Toluenesulfonyl) 2, 3 Pentanedione glyoxime, bis-one Ο— (ρ Toleneene sulfonyl) -one 2 Methyl 3, 4 Pentanedione glyoxime, bis-one Ο— (η — Butanesulfonyl) a-dimethyldarioxime, bis O— (n-butanesulfonyl) a-diphenyldarioxime, bis O— (n-butanesulfonyl) α-dicyclohexylglyoxime, bis- 一Sulfonyl) 2, 3 Pentanedione Glyoxime, Bis Ο— (η Butanesulfonyl) 2 Methyl 3, 4 Pentanedione Lioxime, Bis Ο (Methanesulhoninole) a-Dimethylolegrioxime, Bis O— (Trifluoromethanesulfonyl) α-Dimethyldarioxime, Bis Ο— (1, 1, 1-Trifluoroethanesulfonyl) α-dimethyldarioxime, bis Ο- (tert-butanes-norefonyl) α-dimethyldarioxime, bis Ο (perfluorooctanesulfonyl) -a-dimethyldarioxime, bis-O (cyclohexanesulfonyl) α-dimethyl noredarixime, bis Ο (Benzenesulfonyl) α-dimethyldarioxime, bis- 0-(ρ Fluorobenzenesulfonyl) α-dimethyldarioxime, bis- (ρ- tert butylbenzenesulfonyl) α-dimethyldarioxime, bis Ο ( Xylenesulfonyl) α-dimethyldarioxime, bis- 一-(can Asuruhoniru) a chromatography dimethyl Dali oxime, and the like.
[0155] ビススルホン誘導体としては、ビスナフチルスルホニルメタン、ビストリフルォロメチル スノレホニノレメタン、ビスメチノレスノレホニノレメタン、ビスェチノレスノレホニノレメタン、ビスプロ ピノレスノレホニノレメタン、ビスイソプロピノレスノレホニノレメタン、ビス一 p トノレエンスノレホニ ルメタン、ビスベンゼンスルホニルメタン等が挙げられる。 [0155] Examples of the bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethyl sulphononinomethane, bismethinolesnorenoninomethane, biscetenoresnorenoninomethane, bispro Examples thereof include pinoles norehoninoremethane, bisisopropinolesnorehonenomethane, bis-p-to-norenosenorethanolmethane, and bisbenzenesulfonylmethane.
[0156] βーケトスルホン誘導体としては、 2 シクロへキシルカルボ二ルー 2—（ρ トルェ ンスルホニノレ）プロパン、 2—イソプロピルカルボ二ルー 2— (ρ トルエンスルホニル） プロパン等が挙げられる。 [0156] Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl 2- (ρ toluenesulfonole) propane, 2-isopropylcarbonyl 2- (ρtoluenesulfonyl) propane, and the like.
[0157] ジスルホン誘導体としては、ジフエユルジスルホン誘導体、ジシクロへキシルジスル ホン誘導体等のジスルホン誘導体等が挙げられる。  [0157] Examples of the disulfone derivative include disulfone derivatives such as diphenyldisulfone derivatives and dicyclohexyldisulfone derivatives.
[0158] ニトロべンジルスルホネート誘導体としては、 ρ トルエンスルホン酸 2, 6 ジニトロ ベンジル、 ρ トルエンスルホン酸 2, 4 ジニトロべンジル等のニトロべンジルスルホ ネート誘導体等が挙げられる。 [0158] Examples of the nitrobenzyl sulfonate derivative include nitrobenzyl sulfonate derivatives such as ρ toluenesulfonic acid 2,6 dinitrobenzyl and ρ toluenesulfonic acid 2,4 dinitrobenzil.
[0159] スルホン酸エステル誘導体としては、 1 , 2, 3 トリス（メタンスルホニルォキシ）ベン ゼン、 1 , 2, 3—トリス（トリフルォロメタンスルホニルォキシ）ベンゼン、 1 , 2, 3—トリス[0159] Examples of the sulfonic acid ester derivatives include 1, 2, 3 tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris.
(ρ トルエンスルホニルォキシ）ベンゼン等のスルホン酸エステル誘導体等が挙げら れる。 Examples thereof include sulfonic acid ester derivatives such as (ρ toluenesulfonyloxy) benzene.
[0160] Ν ヒドロキシイミド化合物のスルホン酸エステル誘導体としては、 Ν ヒドロキシス クシンイミドメタンスルホン酸エステル、 Ν ヒドロキシスクシンイミドトリフルォロメタンス ノレホン酸エステル、 Ν ヒドロキシスクシンイミドエタンスルホン酸エステル、 Ν ヒドロ キシスクシンイミド 1 プロパンスルホン酸エステル、 Ν ヒドロキシスクシンイミド 2— プロパンスルホン酸エステル、 Ν ヒドロキシスクシンイミド 1 ペンタンスルホン酸ェ ステル、 Ν ヒドロキシスクシンイミド 1—オクタンスルホン酸エステル、 Ν ヒドロキシス クシンイミド ρ—トルエンスルホン酸エステル、 Ν ヒドロキシスクシンイミド ρ メトキシ ベンゼンスルホン酸エステノレ、 Ν ヒドロキシスクシンイミド 2—クロ口エタンスルホン酸 エステル、 Ν ヒドロキシスクシンイミドベンゼンスルホン酸エステル、 Ν ヒドロキシス クシンイミド 2, 4, 6 トリメチルベンゼンスルホン酸エステル、 Ν ヒドロキシスクシン イミド 1—ナフタレンスルホン酸エステル、 Ν ヒドロキシスクシンイミド 2—ナフタレンス ノレホン酸エステル、 Ν ヒドロキシ 2—フエニルスクシンイミドメタンスルホン酸エステ ノレ、 Ν ヒドロキシマレイミドメタンスルホン酸エステル、 Ν ヒドロキシマレイミドエタン スルホン酸エステル、 Ν—ヒドロキシ 2—フエエルマレイミドメタンスルホン酸エステ ノレ、 N ヒドロキシグルタルイミドメタンスルホン酸エステル、 N ヒドロキシグルタルイ ミドベンゼンスルホン酸エステル、 N ヒドロキシフタルイミドメタンスルホン酸エステル 、 N ヒドロキシフタルイミドベンゼンスルホン酸エステル、 N ヒドロキシフタルイミドト リフルォロメタンスルホン酸エステル、 N ヒドロキシフタルイミド p—トルエンスルホン 酸エステル、 N ヒドロキシナフタルイミドメタンスルホン酸エステル、 N ヒドロキシナ フタルイミドベンゼンスルホン酸エステル、 N ヒドロキシ一 5 ノルボルネン一 2, 3- ジカルボキシイミドメタンスルホン酸エステル、 N ヒドロキシ 5 ノルボルネン 2, 3—ジカルボキシイミドトリフルォロメタンスルホン酸エステル、 N ヒドロキシ一 5—ノ ルボルネンー 2, 3 ジカルボキシイミド p トルエンスルホン酸エステル等が挙げられ [0160] ス ル ホ ン Derivatives of hydroxyimide compounds include Ν Hydroxysuccinimide methanesulfonate, Ν Hydroxysuccinimide trifluoromethanesulfonate, Ν Hydroxysuccinimide ethanesulfonate, Ν Hydroxysuccinimide 1 propane Sulfonic acid ester, ヒ ド ロ キ シ Hydroxysuccinimide 2-Propanesulfonic acid ester, ヒ ド ロ キ シ Hydroxysuccinimide 1 Pentanesulfonic acid ester, ヒ ド ロ キ シ Hydroxysuccinimide 1-octane sulfonic acid ester, Ν Hydroxysuccinimide ρ- Toluene sulfonic acid ester, Ν Hydroxysuccinimide ρ Methoxy Benzene sulfonic acid ester, Ν Hydroxysuccinimide 2-chloro ethane sulfonate, ヒ hydride Xylsuccinimide benzene sulfonate, Ν Hydroxy succinimide 2, 4, 6 Trimethylbenzene sulfonate, Ν Hydroxy succinimide 1-Naphthalene sulfonate, Ν Hydroxy succinimide 2-Naphthalene norphonate, ヒ ド ロ キ シ Hydroxy 2-F Nylsuccinimide methanesulfonate ester, Hydroxymaleimide methanesulfonate ester, Ν Hydroxymaleimide ethane sulfonate ester, Ν-hydroxy 2-fuel maleimide methanesulfonate ester Nore, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxy Phthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N-hydroxy-5-norbornene-1, 2, 3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene 2, 3-Dicarboximidotrifluoromethanesulfonate, N-hydroxy-5-norbornene 2, 3 Dicarboximide p Tolu Such as enesulfonic acid esters
[0161] これらの酸発生剤は、単独で用いてもよいし、 2種以上を組み合わせて用いてもよ い。 [0161] These acid generators may be used alone or in combination of two or more.
この酸発生剤の添加量は、（AH)成分および (BH)成分を合わせた 100質量部に 対して、 0. 1質量部から 50質量部であり、 0. 5質量部から 40質量部であることがより 好ましい。  The amount of the acid generator added is from 0.1 to 50 parts by mass and from 0.5 to 40 parts by mass with respect to 100 parts by mass of the (AH) component and the (BH) component. More preferably.
[0162] 本発明のハードマスク形成用組成物は、上記の（AH)成分から（EH)成分の必要 な成分を混合することにより得られる。なお、得られたレジスト下層膜組成物は、フィ ルターで濾過することが好ましレ、。  [0162] The composition for forming a hard mask of the present invention is obtained by mixing the necessary components (EH) to (AH). The resulting resist underlayer film composition is preferably filtered with a filter.
[0163] <ハードマスク形成方法〉  [0163] <Hard mask formation method>
上記の好ましいハードマスク形成用組成物を用いてハードマスクを形成するには、 被カロェ膜上 (場合によっては、被加工膜上に形成されたボトムレイヤー）にスピンコー ター、スリットノズルコーター等を用いて塗布し、乾燥後、加熱すればよい。加熱は、 一段階の加熱または多段加熱法を用いることができる。多段加熱法を用いる場合に は、例えば、まず 100°Cから 120°Cにおいて、 60秒間から 120秒間、次いで 200°C 力も 250°Cにおいて、 60秒間から 120秒間加熱することが好ましい。  In order to form a hard mask using the above preferred hard mask forming composition, a spin coater, a slit nozzle coater or the like is used on the film to be processed (in some cases, the bottom layer formed on the film to be processed). It is sufficient to apply, dry and heat. For the heating, a single-stage heating or a multi-stage heating method can be used. In the case of using the multi-stage heating method, for example, it is preferable to first heat at 100 ° C. to 120 ° C. for 60 seconds to 120 seconds, and then at 200 ° C. force at 250 ° C. for 60 seconds to 120 seconds.
[0164] このようにして形成されたハードマスクの厚さは、 20nmから 150nmであることが好 ましい。その後このハードマスクの上にレジスト膜用組成物を例えば lOOnmから 200 nmの厚さで設けてレジスト膜を製造する。 [0165] 《支持体》 [0164] The thickness of the hard mask thus formed is preferably 20 nm to 150 nm. Thereafter, a resist film composition is provided on the hard mask in a thickness of, for example, lOOnm to 200 nm to produce a resist film. [0165] [Support]
支持体としては、特に限定されず、従来公知のものを用いることができる。例えば、 電子部品用の基板や、これに所定の配線パターンが形成されたもの等を例示するこ と力できる。より具体的には、シリコンゥエーノ、、銅、クロム、鉄、アルミニウム等の金属 製の基板や、ガラス基板等が挙げられる。配線パターンの材料としては、例えば銅、 アルミニウム、ニッケル、金等が使用可能である。  The support is not particularly limited, and a conventionally known support can be used. For example, it is possible to exemplify a substrate for an electronic component or a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
[0166] 《下層膜》 [0166] << Underlayer >>
下層膜としては従来公知のものを用いることができ、無機系、有機系の膜のいずれ でもよいが、ドライエッチング可能な有機系の膜が好ましぐ例えば、通常の多層レジ スト法等で用いる有機膜を用いることができる。  As the lower layer film, a conventionally known film can be used. Either an inorganic film or an organic film may be used, but an organic film that can be dry-etched is preferred. For example, it is used in a normal multilayer resist method or the like. An organic film can be used.
中でも酸素プラズマエッチング等のエッチングが可能な有機膜を形成できる材料で あることが好ましい。  In particular, a material capable of forming an organic film capable of etching such as oxygen plasma etching is preferable.
このような有機膜形成用材料としては、従来、有機反射防止膜 (有機 BARC)など の有機膜を形成するために用いられている材料であってよい。例えば、ブリューヮサ ィエンス社製の ARCシリーズ、ロームアンドハース社製の ARシリーズ、東京応化工 業社製の SWKシリーズなどが挙げられる。  Such a material for forming an organic film may be a material conventionally used for forming an organic film such as an organic antireflection film (organic BARC). Examples include the ARC series manufactured by Brew Sciences, the AR series manufactured by Rohm and Haas, and the SWK series manufactured by Tokyo Ohka Kogyo.
中でも、上述した様に、エッチング工程において酸素プラズマエッチングを用いる 場合、有機膜を、酸素プラズマエッチングによりエッチングしゃすぐかつハロゲンガ ス、具体的には CFガス又は CHFガス等のフッ化炭素系ガスに対して耐性が比較  In particular, as described above, when oxygen plasma etching is used in the etching process, the organic film is etched by oxygen plasma etching and is applied to halogen gas, specifically, a fluorocarbon gas such as CF gas or CHF gas. Compare resistance
4 3  4 3
的高レヽ材料から構成するのが好ましレ、。  It is preferable to make it from high-quality materials.
これらの材料は、酸素プラズマエッチング等のエッチングを行いやすいと同時に、フ ッ化炭素系ガスに対する耐性が強ぐ本発明において好適である。すなわち一般に、 基板等のエッチングはフッ化炭素系ガス等のハロゲンガスを用いて行われるので、こ の様な材料から有機膜を構成することにより、有機膜パターンを形成する際に酸素プ ラズマエッチングを用いて加工性を向上させるとともに、基板等をエッチングするフッ 化炭素系ガス等のハロゲンガスを用いた後工程においては、耐エッチング性を向上 させること力 sでさる。  These materials are suitable for the present invention because they are easy to perform etching such as oxygen plasma etching and at the same time have high resistance to carbon fluoride gas. That is, generally, etching of a substrate or the like is performed using a halogen gas such as a fluorocarbon-based gas. Therefore, by forming an organic film from such a material, oxygen plasma etching is performed when forming an organic film pattern. In the subsequent process using a halogen gas such as a fluorocarbon gas for etching the substrate or the like, the etching resistance can be improved with a force s.
これらの樹脂成分は 1種を単独で用いてもよぐ 2種以上を混合して用いてもよい。 [0167] 有機膜形成用材料には、さらに所望により混和性のある添加剤、例えば有機膜の 性能を改良するための付加的樹脂、塗布性を向上させるための界面活性剤、溶解 抑制剤、可塑剤、安定剤、着色剤、ハレーション防止剤などを適宜含有させることが できる。 These resin components may be used alone or as a mixture of two or more. [0167] The organic film-forming material further contains, if desired, miscible additives such as an additional resin for improving the performance of the organic film, a surfactant for improving the coating property, a dissolution inhibitor, Plasticizers, stabilizers, colorants, antihalation agents and the like can be appropriately contained.
有機膜形成用材料は、上述した樹脂成分等の材料を有機溶剤に溶解させて製造 すること力 Sできる。有機溶剤としては、上述した化学増幅型ポジ型シリコン系レジスト 組成物の（S)成分として例示したものと同様のものを用いることができる。  The organic film forming material can be manufactured by dissolving the above-described resin components and the like in an organic solvent. As the organic solvent, the same organic solvents as those exemplified as the component (S) of the chemically amplified positive silicon resist composition described above can be used.
[0168] 《化学増幅型ネガ型レジスト組成物》 [0168] << Chemically Amplified Negative Resist Composition >>
化学増幅型ネガ型レジスト組成物としては従来公知のものを用いることができ、特 に限定されない。例えば、アルカリ可溶性樹脂、露光により酸を発生する酸発生剤、 架橋剤が配合され、レジストパターン形成時に、露光により酸が発生すると、露光部 は、前記酸が作用してアルカリ可溶性樹脂と架橋剤との間で架橋が起こり、アルカリ 不溶性へ変化するものが挙げられる。アルカリ可溶性樹脂としては、 a （ヒドロキシ アルキル）アクリル酸、または α （ヒドロキシアルキル）アクリル酸の低級アルキルェ ステルから選ばれる少なくとも一つから誘導される単位を有する樹脂、フッ素化アル コールを有する樹脂などが、膨潤の少ない良好なレジストパターンが形成でき、好ま しい。なお、 α （ヒドロキシアルキル）アクリル酸は、カルボキシ基が結合する α位の 炭素原子に水素原子が結合しているアクリル酸と、この α位の炭素原子にヒドロキシ アルキル基（好ましくは炭素数 1〜 5のヒドロキシアルキル基）が結合している α—ヒド ロキシアルキルアクリル酸の一方または両方を示す。  Conventionally known chemical amplification negative resist compositions can be used and are not particularly limited. For example, an alkali-soluble resin, an acid generator that generates an acid upon exposure, and a crosslinking agent are blended, and when an acid is generated by exposure at the time of resist pattern formation, the exposed portion acts to react with the alkali-soluble resin and the crosslinking agent. Cross-linking occurs between the two and alkali-insoluble. Examples of the alkali-soluble resin include a resin having a unit derived from at least one selected from a lower alkyl ester of a (hydroxyalkyl) acrylic acid or α (hydroxyalkyl) acrylic acid, and a resin having a fluorinated alcohol. It is preferable because a good resist pattern with less swelling can be formed. In addition, α (hydroxyalkyl) acrylic acid is composed of acrylic acid in which a hydrogen atom is bonded to the α-position carbon atom to which the carboxy group is bonded, and a hydroxyalkyl group (preferably having a carbon number of 1 to One or both α-hydroxyalkylacrylic acids to which 5 hydroxyalkyl groups) are bonded.
架橋剤としては、例えば、通常は、メチロール基またはアルコキシメチル基を有する グリコールゥリルなどのアミノ系架橋剤を用いると、膨潤の少ない良好なレジストバタ ーンが形成でき、好ましい。架橋剤の配合量は、アルカリ可溶性樹脂 100質量部に 対し、；!〜 50質量部であることが好ましい。  As the crosslinking agent, for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group because a good resist pattern with less swelling can be formed. The compounding amount of the crosslinking agent is preferably from! To 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
[0169] 次に、本発明のパターン形成方法について説明する。 [0169] Next, the pattern forming method of the present invention will be described.
《パターン形成方法》  <Pattern formation method>
本発明のパターン形成方法は、支持体上に、下層膜形成材料を用いて下層膜を 形成する工程と、前記下層膜上にシリコン系ハードマスク形成材料を用いてハードマ スクを形成する工程と、前記ハードマスク上に化学増幅型ネガ型レジスト組成物を塗 布して第一のレジスト膜を形成する工程と、前記第一のレジスト膜を、第一のマスクパ ターンを介して選択的に露光し、現像して第一のレジストパターンを形成する工程と 、前記第一のレジストパターンをマスクとして、ハードマスクをエッチングして第一のパ ターンを形成する工程 (ここまでを以下、パターユング工程（1 )という）と、前記第一の パターン上に化学増幅型ポジ型シリコン系レジスト組成物を塗布して第二のレジスト 膜を形成する工程と、前記第二のレジスト膜を、第二のマスクパターンを介して選択 的に露光し、現像して第二のレジストパターンを形成する工程と、前記第二のレジスト ノ ターンをマスクとして、下層膜をエッチングして第二のパターンを形成する工程 (パ ターニング工程（1)の後からここまでを以下、パターユング工程（2)とレ、う）とを含む。 以下、図面を用いて説明する。 The pattern forming method of the present invention includes a step of forming a lower layer film on a support using a lower layer film forming material, and a hard mask using a silicon-based hard mask forming material on the lower layer film. Forming a first resist film by applying a chemically amplified negative resist composition on the hard mask, and forming a first mask pattern on the hard mask. A step of selectively exposing and developing the first resist pattern, and a step of forming a first pattern by etching the hard mask using the first resist pattern as a mask (until now). Hereinafter referred to as a patterning step (1)), a step of applying a chemically amplified positive silicon resist composition on the first pattern to form a second resist film, and the second resist The film is selectively exposed through a second mask pattern and developed to form a second resist pattern, and the lower layer film is etched using the second resist pattern as a mask. Forming a second pattern by (from after patterning step (1) Up to this point below, putter Jung steps (2) Les, U) and a. Hereinafter, it demonstrates using drawing.
[0170] <パターユング工程（1)〉 [0170] <Patterning process (1)>
図 1Aから図 1Eは、本発明のパターン形成方法の好ましい実施態様のうち、パター ユング工程（1)を例示する概略工程図である。  1A to 1E are schematic process diagrams illustrating a patterning process (1) in a preferred embodiment of the pattern forming method of the present invention.
本実施態様においては、まず、図 1Aに示すように、支持体 1上に、前記下層膜形 成材料を用いて下層膜 2を形成し、前記下層膜 2上に前記シリコン系ハードマスク形 成材料を用いてハードマスク 3を形成し、前記ハードマスク 3上に化学増幅型ネガ型 レジスト組成物を塗布して第一のレジスト膜 4を形成する。下層膜 2、ハードマスク 3お よび第一のレジスト膜 4を形成する工程は従来公知の方法を適用すればよい。  In this embodiment, first, as shown in FIG. 1A, a lower layer film 2 is formed on a support 1 using the lower layer film forming material, and the silicon hard mask is formed on the lower layer film 2. A hard mask 3 is formed using a material, and a chemically amplified negative resist composition is applied on the hard mask 3 to form a first resist film 4. A conventionally known method may be applied to the step of forming the lower layer film 2, the hard mask 3, and the first resist film 4.
[0171] 例えば、支持体 1上に下層膜形成材料を塗布する方法としては、特に限定されるも のではなく、当該下層膜形成材料に応じて、例えば、スプレー法、ロールコート法、 回転塗布法等を適宜選択することができる。 [0171] For example, the method of applying the lower layer film-forming material on the support 1 is not particularly limited, and, for example, according to the lower layer film-forming material, for example, a spray method, a roll coating method, a spin coating method. Laws and the like can be selected as appropriate.
下層膜 2の厚さは、 目的とするアスペクト比と下層膜 2のドライエッチングに要する時 間を考慮したスループットのバランスから適宜選択することができ、好ましくは 150nm 以上 500nm以下、より好ましくは 200nm以上 350nm以下、更に好ましくは 200nm 以上 300nm以下である。下層膜 2の厚さをこの範囲内とすることにより、高アスペクト 比のレジストパターンが形成できる。  The thickness of the lower layer film 2 can be appropriately selected from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the lower layer film 2, and is preferably 150 nm or more and 500 nm or less, more preferably 200 nm or more 350 nm or less, more preferably 200 nm or more and 300 nm or less. By setting the thickness of the lower layer film 2 within this range, a resist pattern having a high aspect ratio can be formed.
ここでいうアスペクト比とは、レジストパターンのパターン幅 Xに対する、支持体上に 形成されたパターンの高さ yの比（y/χ)である。尚、レジストパターンのパターン幅 X は、下層膜に転写した後のパターン幅と同じである。 The aspect ratio here refers to the resist pattern width X on the support. The ratio of the height y of the formed pattern (y / χ). The pattern width X of the resist pattern is the same as the pattern width after transfer to the lower layer film.
パターン幅とは、レジストパターンがラインアンドスペースパターン、孤立ラインパタ ーン等のライン状パターンである場合には、凸条 (ライン）の幅をいう。レジストパター ンがホールパターンである場合には、パターン幅は、形成された孔（ホール）の内径 をいう。また、レジストパターンが円柱状ドットパターンである場合には、その直径をい 5。  The pattern width means the width of a ridge (line) when the resist pattern is a line pattern such as a line and space pattern or an isolated line pattern. When the resist pattern is a hole pattern, the pattern width refers to the inner diameter of the formed hole (hole). If the resist pattern is a cylindrical dot pattern, enter the diameter.
なお、これらのパターン幅は、いずれもパターン下方（支持体側）の幅である。  In addition, all of these pattern widths are widths below the pattern (support side).
[0172] また、例えば、下層膜 2上に前記シリコン系ハードマスク形成材料を塗布する方法と しては、特に限定されるものではなぐ上記の好ましいハードマスク形成用組成物を 用いてハードマスクを形成する方法と同様である。 [0172] Further, for example, the method for applying the silicon-based hard mask forming material onto the lower layer film 2 is not particularly limited, and the hard mask is formed using the preferable hard mask forming composition described above. It is the same as the method of forming.
ハードマスク 3の厚さは、 20nm以上 150nm以下であること力 S好ましく、 30nm以上 50nm以下であることがさらに好ましい。  The thickness of the hard mask 3 is preferably 20 nm or more and 150 nm or less, more preferably 30 nm or more and 50 nm or less.
前記シリコン系ハードマスク形成材料のシリコン含有量は、高アスペクト比のパター ンを良好に形成できることから、 20%以上であることが好ましぐ 30%以上であること 力 Sさらに好ましい。  The silicon content of the silicon-based hard mask forming material is preferably 20% or more, more preferably 30% or more because the high aspect ratio pattern can be satisfactorily formed.
[0173] また、例えば、化学増幅型ネガ型レジスト組成物は、スピンナーなどでハードマスク  [0173] Further, for example, a chemically amplified negative resist composition is hard masked with a spinner or the like.
3上に塗布し、形成された塗膜をベータ処理 (プレベータ）して、第一のレジスト膜 4を 成膜すればよい。  The first resist film 4 may be formed by applying a beta treatment (pre-beta) on the coating film formed on the substrate 3.
第一のレジスト膜 4の厚さは、 目的とするアスペクト比とハードマスク 3のドライエッチ ングに要する時間を考慮したスループットのバランスから適宜選択することができ、好 ましくは 50nm以上 200nm以下、より好ましくは lOOnm以上 200nm以下である。厚 さを 200nm以下とすることにより、レジストパターンを高解像度で形成でき、また、 50 nm以上とすることにより、ドライエッチングに対する十分な耐性が得られる等の効果 を有する。  The thickness of the first resist film 4 can be appropriately selected from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the hard mask 3, and is preferably 50 nm to 200 nm. More preferably, it is lOOnm or more and 200nm or less. By setting the thickness to 200 nm or less, the resist pattern can be formed with high resolution, and by setting the thickness to 50 nm or more, there are effects such as sufficient resistance to dry etching.
[0174] 続いて、図 1Bに示すように、前記第一のレジスト膜 4を、第一のマスクパターン 5を 介して選択的に露光し、任意に、前記レジスト膜 4をさらにベータ処理 (ポストエタスポ 一ジャーベータ（PEB) )し、前記レジスト膜 4を、現像して第一のレジストパターン 4 ' を形成する。選択的露光および現像は従来公知の方法を適用すればよい。ここで用 いる第一のマスクパターン 5は、所望のパターンを考慮して適宜選択すればよい。こ こでは、スペース幅 d、ピッチ 2dのものを例示している力 これに限定されない。 Subsequently, as shown in FIG. 1B, the first resist film 4 is selectively exposed through the first mask pattern 5 and, optionally, the resist film 4 is further subjected to a beta treatment (post-etaspot). 1 jar beta (PEB)), the resist film 4 is developed, and the first resist pattern 4 ' Form. For the selective exposure and development, a conventionally known method may be applied. The first mask pattern 5 used here may be appropriately selected in consideration of a desired pattern. Here, the force exemplified for the space width d and the pitch 2d is not limited to this.
[0175] 選択的露光条件は、特に限定されるものではない。露光に用いる光源及び方法に 応じて、露光領域、露光時間、露光強度等を適宜選択することが可能である。 [0175] The selective exposure conditions are not particularly limited. Depending on the light source and method used for exposure, the exposure region, exposure time, exposure intensity, and the like can be appropriately selected.
露光光源は、特に限定されず、 ArFエキシマレーザー、 KrFエキシマレーザー、 F  The exposure light source is not particularly limited. ArF excimer laser, KrF excimer laser, F
2 エキシマレーザー、 EUV (極紫外線）、 VUV (真空紫外線）、 EB (電子線）、 X線、軟 X線等の放射線を用いて行うことができる。  2 Excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. can be used.
[0176] 現像に用いられるアルカリ現像液は、特に限定されるものではない。例えば、 0. 05 質量％以上 10質量％以下、好ましくは 0. 05質量％以上 3質量％以下のテトラメチ ルアンモニゥムヒドロキシド水溶液を用いることができる。  [0176] The alkali developer used for development is not particularly limited. For example, an aqueous tetramethylammonium hydroxide solution having a concentration of 0.05% by mass to 10% by mass, preferably 0.05% by mass to 3% by mass can be used.
化学増幅型ネガ型レジスト組成物として、アルカリ可溶性樹脂、酸発生剤、架橋剤 が配合されたものを用いれば、選択的露光により露光部において酸が発生し、前記 酸が作用してアルカリ可溶性樹脂と架橋剤との間で架橋が起こり、露光部はアルカリ 不溶性へ変化する。したがって、アルカリ現像液を用いてウエット現像することで、未 露光部が現像液に溶解し、第一のレジストパターン 4'が形成される。第一のレジスト パターン 4，は、図 1Cに示すように、ライン幅 d/2、スペース幅 3d/2でピッチ 2dのラ インアンドスペースのレジストパターン（以下、 L/Sパターンと言う）となる。  If a chemically amplified negative resist composition containing an alkali-soluble resin, an acid generator, and a crosslinking agent is used, an acid is generated in the exposed area by selective exposure, and the acid acts to react with the alkali-soluble resin. Cross-linking occurs between the resin and the cross-linking agent, and the exposed area changes to alkali-insoluble. Therefore, by performing wet development using an alkaline developer, the unexposed portion is dissolved in the developer, and the first resist pattern 4 ′ is formed. As shown in FIG. 1C, the first resist pattern 4 is a line-and-space resist pattern (hereinafter referred to as an L / S pattern) having a line width d / 2, a space width 3d / 2, and a pitch 2d. .
[0177] 前記ベータ処理条件は、特に限定されるものではない。例えば、 70°C以上 130°C 以下の温度条件で、 40秒から 180秒の時間、好ましくは 60秒から 90秒の時間、カロ 熱することが望ましい。  [0177] The beta treatment conditions are not particularly limited. For example, it is desirable to heat the calorie under the temperature condition of 70 ° C or higher and 130 ° C or lower for 40 seconds to 180 seconds, preferably 60 seconds to 90 seconds.
[0178] 次いで、前記第一のレジストパターン 4，をマスクとして、ハードマスク 3をエッチング して第一のパターンを形成する。すなわち、ハードマスク 3に第一のレジストパターン 4'が転写される。  Next, the hard mask 3 is etched using the first resist pattern 4 as a mask to form a first pattern. That is, the first resist pattern 4 ′ is transferred to the hard mask 3.
エッチングは従来公知の方法を適用できる。例えば、プラズマ及び/又は反応性ィ オンを照射することにより行うことができる。エッチング条件は、使用するガスの種類 等に応じて適宜選択することができる。  A conventionally known method can be applied to the etching. For example, it can be performed by irradiation with plasma and / or reactive ions. Etching conditions can be appropriately selected according to the type of gas used.
エッチングに使用されるプラズマ及び/又は反応性イオンのガスは、ドライエツチン グ分野で通常用いられているガスであれば、特に限定されるものではない。例えば、 酸素、ハロゲン、二酸化硫黄等を挙げることができる力 CF、 CHF等のハロゲンを The plasma and / or reactive ion gas used for etching is dry ethyne. The gas is not particularly limited as long as it is a gas usually used in the field of gas. For example, the force that can mention oxygen, halogen, sulfur dioxide, etc. Halogen such as CF, CHF, etc.
4 3  4 3
含むプラズマ及び/又は反応性イオンを用いることが好まし!/、。  It is preferred to use plasma and / or reactive ions!
エッチングの方法としては、特に限定されるものではない。例えば、ダウンフローェ ツチングゃケミカルドライエッチング等の化学的エッチング;スパッタエッチングゃィォ ンビームエッチング等の物理的エッチング; RIE (反応性イオンエッチング）等の化学 的 ·物理的エッチングなどの公知の方法を用いることができる。  The etching method is not particularly limited. For example, chemical etching such as down-flow etching or chemical dry etching; physical etching such as sputter etching ion beam etching; or chemical / physical etching such as RIE (reactive ion etching). Can be used.
最も一般的なドライエッチングとしては、平行平板型 RIEが挙げられる。この方法で は、先ず、 RIE装置のチャンバ一にレジストパターンが形成された積層体を入れ、必 要なエッチングガスを導入する。チャンバ一内において、上部電極と平行に置かれた レジスト積層体のホルダーに高周波電圧を加えると、ガスがプラズマ化される。プラズ マ中には、正 ·負のイオンや電子などの電荷粒子、中性活性種などがエッチング種と して存在している。これらのエッチング種が下部有機層に吸着すると、化学反応が生 じ、反応生成物が表面から離脱して外部へ排気され、エッチングが進行する。  The most common dry etching is parallel plate RIE. In this method, first, a laminated body on which a resist pattern is formed is placed in a chamber of an RIE apparatus, and a necessary etching gas is introduced. In the chamber, when a high frequency voltage is applied to the resist stack holder placed in parallel with the upper electrode, the gas is turned into plasma. In the plasma, charged particles such as positive and negative ions and electrons, and neutral active species exist as etching species. When these etching species are adsorbed on the lower organic layer, a chemical reaction occurs, the reaction product is detached from the surface and exhausted to the outside, and etching proceeds.
[0179] ハードマスク 3のエッチング後は、図 1Eに示すように、第一のレジストパターン 4'を 除去して、下層膜 2上のハードマスクのパターン 3'を第一のパターンとしてもよいし、 図 1Dに示すように、第一のレジストパターン 4，を残して、第一のレジストパターン 4， およびハードマスクのパターン 3，を第一のパターンとしてもよい。  [0179] After the etching of the hard mask 3, as shown in FIG. 1E, the first resist pattern 4 'may be removed, and the hard mask pattern 3' on the lower layer film 2 may be used as the first pattern. As shown in FIG. 1D, the first resist pattern 4 may be left, and the first resist pattern 4 and the hard mask pattern 3 may be used as the first pattern.
[0180] <パターユング工程（2)〉  [0180] <Patterning process (2)>
前記パターユング工程（1)に次いで、第二のパターンを形成する。図 2Aから図 2D は、本発明のパターン形成方法の好ましい実施態様のうち、パターユング工程（2)を 例示する概略工程図である。なお図 2Aから図 2Dにおいては、第一のレジストパター ン 4'を除去して、ハードマスクのパターン 3'を第一のパターンとして用いる場合を例 示しているが、第一のレジストパターン 4'を残して第一のパターンとする場合も、同様 の手順で第二のパターンを形成することができる。なお、第一のレジストパターンを除 去する方法としては、剥離液を用いる方法等の公知の手法を用いてパターンを剥離 すればよい。  Following the patterning step (1), a second pattern is formed. 2A to 2D are schematic process diagrams illustrating the patterning process (2) in a preferred embodiment of the pattern forming method of the present invention. 2A to 2D show an example in which the first resist pattern 4 'is removed and the hard mask pattern 3' is used as the first pattern. However, the first resist pattern 4 ' Even when the first pattern is left, the second pattern can be formed by the same procedure. As a method for removing the first resist pattern, the pattern may be peeled off using a known method such as a method using a stripping solution.
図 2Aに示すように上記のように形成された第一のパターン及び下層膜 2の上に、 前記化学増幅型ポジ型シリコン系レジスト組成物を塗布して第二のレジスト膜 6を形 成する。第二のレジスト膜 6は、第一のレジスト膜 4と同様、従来公知の方法で形成す れば'よい。 On the first pattern and the lower layer film 2 formed as described above as shown in FIG. A second resist film 6 is formed by applying the chemically amplified positive silicon resist composition. Similar to the first resist film 4, the second resist film 6 may be formed by a conventionally known method.
[0181] 第二のレジスト膜 6の厚さは、 目的とするアスペクト比と下層膜 2のドライエッチング に要する時間を考慮したスループットのバランスから適宜選択することができ、好まし くは lOOnm以上 200nm以下である。厚さを 200nm以下とすることにより、レジス卜ノ ターンを高解像度で形成でき、また、 lOOnm以上とすることにより、ドライエッチング に対する十分な耐性が得られる等の効果を有する。  [0181] The thickness of the second resist film 6 can be selected as appropriate from the balance of throughput in consideration of the target aspect ratio and the time required for dry etching of the lower layer film 2, and is preferably lOOnm or more and 200 nm. It is as follows. By setting the thickness to 200 nm or less, the resist pattern can be formed with high resolution, and by setting it to lOO nm or more, there is an effect that sufficient resistance to dry etching can be obtained.
また、前記化学増幅型ポジ型シリコン系レジスト組成物のシリコン含有量は、高ァス ぺクト比のパターンを良好に形成できることから、 10%以上であることが好ましぐ 20 %以上であることがさらに好ましい。  In addition, the silicon content of the chemical amplification type positive silicon resist composition is preferably 10% or more, preferably 20% or more, because a pattern with a high aspect ratio can be formed satisfactorily. Is more preferable.
[0182] 続いて、図 2Bに示すように、前記第二のレジスト膜 6を、第二のマスクパターン 7を 介して選択的に露光し、現像して第二のレジストパターン 6 'を形成する。選択的露光 および現像は、第一のレジストパターン 4'形成時と同様に、従来公知の方法を適用 すればよい。ここで用いる第二のマスクパターン 7も、前記第一のマスクパターン 5同 様、所望のパターンを考慮して適宜選択すればよい。ここでは、第二のレジストバタ ーン 6 'として、第一のレジストパターン 4'と同様のものを形成する場合を例示してお り、第二のマスクパターン 7は、第一のマスクパターン 5同様、スペース幅 d、ピッチ 2d である。すなわち本具体例においては、第二のレジストパターン 6 '形成時に、第二の マスクパターン 7として第一のマスクパターン 5を用いて、前記マスクパターンを、第一 のレジスト膜 4の選択的露光時とは異なる位置に設けて、第二のレジスト膜 6を選択 的に露光することができる。  Subsequently, as shown in FIG. 2B, the second resist film 6 is selectively exposed through the second mask pattern 7 and developed to form a second resist pattern 6 ′. . For the selective exposure and development, a conventionally known method may be applied as in the case of forming the first resist pattern 4 ′. The second mask pattern 7 used here may be appropriately selected in consideration of a desired pattern like the first mask pattern 5. Here, the case where the same pattern as the first resist pattern 4 ′ is formed as the second resist pattern 6 ′ is illustrated, and the second mask pattern 7 is the same as the first mask pattern 5. , Space width d, pitch 2d. That is, in this specific example, when the second resist pattern 6 ′ is formed, the first mask pattern 5 is used as the second mask pattern 7, and the mask pattern is used during the selective exposure of the first resist film 4. The second resist film 6 can be selectively exposed at a position different from the above.
[0183] 化学増幅型ポジ型シリコン系レジスト組成物として、上記のものを用いれば、選択的 露光により露光部において酸が発生し、前記酸が作用して露光部の樹脂はアルカリ 可溶性へ変化する。したがって、アルカリ現像液を用いてウエット現像することで、露 光部が現像液に溶解し、第二のレジストパターン 6 'が形成される。第二のレジストパ ターン 6，は、図 2Cに示すように、ライン幅 d/2、スペース幅 3d/2でピッチ 2dの L/ Sパターンとなる。そして、第一のパターンであるハードマスクのパターン 3'とは、スぺ ース幅 d/2で隣接する。 [0183] If the above-described chemical amplification type positive silicon resist composition is used, an acid is generated in the exposed area by selective exposure, and the acid acts to change the resin in the exposed area to alkali-soluble. . Therefore, by performing wet development using an alkaline developer, the exposed portion is dissolved in the developer and a second resist pattern 6 ′ is formed. As shown in FIG. 2C, the second resist pattern 6 is an L / S pattern having a line width d / 2, a space width 3d / 2, and a pitch 2d. The hard mask pattern 3 ', which is the first pattern, is Adjacent with a source width of d / 2.
[0184] 次いで、図 2Dに示すように、前記第一のパターン 3'及び第二のレジストパターン 6 ，をマスクとして、下層膜 2をエッチングし、下層膜 2に第一のパターン 3'及び第二の レジストパターン 6 'を転写する。そして、得られた下層膜 2のパターン 2'を第二のパ ターンとする。下層膜 2をエッチングする方法は、ハードマスク 3をエッチングする方法 と同様に従来公知の方法を適用できる。エッチングに使用されるプラズマ及び/又 は反応性イオンのガスも特に限定されず、例えば、酸素、ハロゲン、二酸化硫黄等を 挙げること力 Sできる。得られるパターンの解像度が高いこと、汎用的に用いられている ことから、酸素を含むプラズマ及び/又は反応性イオンを用いることが好ましい。  Next, as shown in FIG. 2D, the lower layer film 2 is etched using the first pattern 3 ′ and the second resist pattern 6 as a mask, and the first pattern 3 ′ and the second pattern 2 are etched on the lower layer film 2. Transfer the second resist pattern 6 '. Then, the obtained pattern 2 ′ of the lower layer film 2 is used as a second pattern. A conventionally known method can be applied to the method of etching the lower layer film 2 in the same manner as the method of etching the hard mask 3. The plasma and / or reactive ion gas used for etching is not particularly limited, and can include, for example, oxygen, halogen, sulfur dioxide and the like. It is preferable to use oxygen-containing plasma and / or reactive ions because the resulting pattern has high resolution and is used for general purposes.
[0185] 前記第二のパターンでは、ライン幅は d/2、スペース幅は d/2、ピッチは dの L/S パターンとなる。ここで例えば、 dが 180nmとすると、本発明により、ライン幅およびス ペース幅が 90nmの高精細なパターンを形成することが可能である。なお、ここで得 られる第二のパターンにおいて、ライン幅およびスペース幅は、各工程の条件により 多少前後することがある。  In the second pattern, the L / S pattern has a line width of d / 2, a space width of d / 2, and a pitch of d. Here, for example, when d is 180 nm, a high-definition pattern having a line width and a space width of 90 nm can be formed according to the present invention. In the second pattern obtained here, the line width and space width may slightly vary depending on the conditions of each step.
このように本発明において基板上に形成されるパターンは、高アスペクト比であり、 ノ ターン倒れもなぐ形状も、垂直性の高い良好なものである。一方、単層のレジスト パターユングを経て得られる従来のパターンでは、このような高精細かつ高アスペクト 比のものは得られない。また、従来提案されているダブルパターユング法でも、バタ ーンの精度が悪ぐパターン倒れや垂直性が高くない形状のものが混在して、高精 細なものが得られない。  As described above, the pattern formed on the substrate in the present invention has a high aspect ratio, and the shape that does not collapse is also excellent in high perpendicularity. On the other hand, conventional patterns obtained through single-layer resist patterning cannot achieve such high definition and high aspect ratio. In addition, the double patterning method that has been proposed in the past cannot be obtained with high precision because of the mixed pattern with poor pattern accuracy and patterns with low verticality.
実施例  Example
[0186] 以下、具体的実施例により、本発明についてさらに詳しく説明する。ただし、本発明 は以下に示す実施例に何ら限定されるものではない。  [0186] Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
[0187] <ハードマスク形成材料の調製〉  [0187] <Preparation of hard mask forming material>
国際公開第 2006/065321号パンフレットに記載の合成方法に従って下記化学 式（1)で表されるシロキサン系共重合体を合成した。即ち、 120gの PGMEA、 5. 29 g (0. 025モノレ）のフエ二ノレトリクロロシラン、 6· 77g(0. 050モノレ）のトリクロロシラン、 22. 43g (0. 150モノレ）のメチノレ卜リクロロシラン及び 5. 54g (0. 025モノレ）の 2—力ノレ ボメトキシェチルトリクロロシランの混合物を窒素雰囲気下で反応器へ入れた。 200g の PGMEA溶液と 10g (0. 555モル）の水を前記トリクロロシラン溶液に 1時間以上に わたって加えた。 20°Cで 1時間攪拌して反応させた。その後、 40°Cでロータリーエバ ポレーターによってレジン溶液を約 10wt%に濃縮した。約 40gのエタノールをレジン 溶液に加えた。溶液をもう一度ストリツビングして 20wt%とした。再びフラスコを除去 し、 PGMEAを加えて溶液を 10wt%に希釈し、 0. 20ミクロンの PTFEフィルターでろ 過した。この方法に従って合成した下記化学式（1)で表される、質量平均分子量 (M w) 24000、分散度（Mw/Mn) 3. 17のシロキサン系共重合体 100質量部、下記化 学式（2)で表される酸発生剤 7質量部、およびへキサデシルトリメチルアンモニゥムク ロリド 3質量部を、これらの固形分濃度が 2質量0 /0となるように、 PGMEA/EL = 6/ 4 (質量比）の混合溶媒に溶解して、ハードマスク形成材料を得た。 A siloxane copolymer represented by the following chemical formula (1) was synthesized according to the synthesis method described in WO 2006/065321 pamphlet. 120 g of PGMEA, 5.29 g (0.025 monole) of phenolinotrichlorosilane, 6.77 g (0.050 monole) of trichlorosilane, 22.43 g (0.150 monole) of methylolene chlorosilane and 5. 54g (0. 025 mono) 2-force force A mixture of bomethoxyethyl chlorosilane was placed in the reactor under a nitrogen atmosphere. 200 g of PGMEA solution and 10 g (0.555 mol) of water were added to the trichlorosilane solution over 1 hour. The reaction was stirred for 1 hour at 20 ° C. Thereafter, the resin solution was concentrated to about 10 wt% by a rotary evaporator at 40 ° C. About 40 g of ethanol was added to the resin solution. The solution was stripped again to 20 wt%. The flask was again removed, PGMEA was added to dilute the solution to 10 wt%, and filtered through a 0.20 micron PTFE filter. 100 parts by mass of a siloxane copolymer having a mass average molecular weight (Mw) of 24000 and a dispersity (Mw / Mn) of 3.17 and represented by the following chemical formula (1) synthesized according to this method, acid generator 7 parts represented by), and to the hexadecyl trimethyl ammonium Niu solid Rorido 3 parts by mass, as those solid concentration of 2 mass 0/0, PGMEA / EL = 6/4 ( (Mass ratio) was dissolved in a mixed solvent to obtain a hard mask forming material.
[0188] [化 33] [0188] [Chemical 33]
Figure imgf000067_0001
Figure imgf000067_0001
■ ' · ■ ( 2 )  ■ '· ■ (2)
[0189] (化学増幅型ネガ型レジスト組成物の調製） [0189] (Preparation of chemically amplified negative resist composition)
質量平均分子量 4400、分散度 1. 7の下記化学式 (A1)— 1で表される樹脂 100 トキシメチル化グリコールゥリル MX270 (三和ケミカル社製） 5. 0質量部、及びトリイソ プロパノールァミン 0· 4質量部を、 PGMEA/PGME = 6/4 (質量比）の混合溶剤 1550質量部に溶解してネガ型レジスト組成物を調製した。 Resin represented by the following chemical formula (A1) —1 having a mass average molecular weight of 4400 and a dispersity of 1. Toximethylated glycoluril MX270 (manufactured by Sanwa Chemical Co., Ltd.) 5.0 parts by weight and triisopropanolamine 0.4 part by weight are dissolved in 1550 parts by weight of a mixed solvent of PGMEA / PGME = 6/4 (mass ratio) Thus, a negative resist composition was prepared.
[0190] [化 34] [0190] [Chemical 34]
Figure imgf000068_0001
Figure imgf000068_0001
[0191] <化学増幅型ポジ型シリコン系レジスト組成物の調製〉 [0191] <Preparation of chemically amplified positive silicon resist composition>
(水素シルセスキォキサン樹脂の調製）  (Preparation of hydrogen silsesquioxane resin)
濃 H SOおよび SOガスを用いてトルエンをスルホン化することによって調製したト Tone prepared by sulfonation of toluene using concentrated H 2 SO and SO gas
2 4 3 2 4 3
ルエンスルホン酸一水和物（TSAM)溶液 100gを、コンデンサー、温度計、マグネ チックステアバーおよび窒素バブラ一を備えた 500mLフラスコに投入した。次いで、 前記フラスコ内に、トリクロロシラン（10g、 0. 075モノレ）を 50gのトルエンに溶解した 溶液を、強く撹拌しながら徐々に滴下して混合物を得た。得られた混合物を、脱ィォ ン水で少なくとも 3回洗浄し、その後、有機相を抽出した。抽出した有機相の溶媒を、 減圧下にてロータリーエバポレータで除去し、固形分量 5〜25質量％の範囲の水素 シルセスキォキサン樹脂（HSQ)溶液を得た。  100 g of ruene sulfonic acid monohydrate (TSAM) solution was placed in a 500 mL flask equipped with a condenser, thermometer, magnetic stir bar and nitrogen bubbler. Next, a solution in which trichlorosilane (10 g, 0.075 monole) was dissolved in 50 g of toluene was gradually dropped into the flask while vigorously stirring to obtain a mixture. The resulting mixture was washed with deionized water at least three times, after which the organic phase was extracted. The solvent of the extracted organic phase was removed by a rotary evaporator under reduced pressure to obtain a hydrogen silsesquioxane resin (HSQ) solution having a solid content in the range of 5 to 25% by mass.
[0192] (酸分解性基の導入） [0192] (Introduction of acid-decomposable group)
約 0. 1モルのビシクロ [2, 2, 1]ヘプトー 5—ェンー2— t—ブチルカルボキシレート と無水トルエン（50： 50)とを混合してォレフィン溶液を調製した。得られたォレフィン 溶液に、 200ppmの 1 , 3—ジエテュノレ一 1 , 1 , 3, 3—テトラメチルジシロキサン錯体 (白金、濃縮）を加えた。引き続き、このォレフィン溶液を、コンデンサー、温度計、マ グネチックステアバーおよび窒素バブラ一を備えたフラスコに投入し、窒素パージし た。窒素パージ後、ォレフィン溶液中に、上記で調製した HSQ溶液をゆっくりと添カロ した。添加後、この系を緩やかに撹拌しながら 8時間の還流を行った。 ifi— NMRを 用いて系内の反応（ヒドロシリル化反応）をモニターし、ォレフィンピークが完全になく なった時点で反応を終了した。これにより、 HSQに下記式 (I) 1で表される酸分解 性基が導入されたシロキサン系共重合体を得た。ゲルパーミエーシヨンクロマトグラフ ィー（GPC)によるポリスチレン換算基準で、質量平均分子量 6300、分散度 2. 1であ つた。また、シロキサン系共重合体中、 HSQと、 HSQに下記式で表される酸分解性 基が導入された構成単位との組成比は、 57： 43 (モル比）であった。 About 0.1 mol of bicyclo [2,2,1] hepto-5-ene-2-t-butylcarboxylate and anhydrous toluene (50:50) were mixed to prepare an olefin solution. To the resulting olefin fin solution, 200 ppm of 1,3-diethylenol 1,1,3,3-tetramethyldisiloxane complex (platinum, concentrated) was added. Subsequently, this olefin solution was put into a flask equipped with a condenser, a thermometer, a magnetic stir bar and a nitrogen bubbler, and purged with nitrogen. After purging with nitrogen, slowly add the HSQ solution prepared above into the olefin solution. did. After the addition, the system was refluxed for 8 hours with gentle stirring. The reaction in the system (hydrosilylation reaction) was monitored using ifi-NMR, and the reaction was terminated when the olefin fin peak disappeared completely. As a result, a siloxane copolymer in which an acid-decomposable group represented by the following formula (I) 1 was introduced into HSQ was obtained. Based on polystyrene standards by gel permeation chromatography (GPC), the mass average molecular weight was 6300, and the degree of dispersion was 2.1. In the siloxane copolymer, the composition ratio between HSQ and the structural unit in which an acid-decomposable group represented by the following formula was introduced into HSQ was 57:43 (molar ratio).
[0193] [化 35]  [0193] [Chemical 35]
Figure imgf000069_0001
Figure imgf000069_0001
[0194] 得られた樹脂溶液について、 PGMEA/PGME = 8/2 (質量比）の混合溶剤で 溶剤置換を行うことにより、固形分濃度 5質量％の上記シロキサン系共重合体の PG MEA/PGME溶液を得た。 [0194] The obtained resin solution was subjected to solvent substitution with a mixed solvent of PGMEA / PGME = 8/2 (mass ratio), so that PG MEA / PGME of the above siloxane copolymer having a solid content concentration of 5 mass% was obtained. A solution was obtained.
[0195] 上記シロキサン系共重合体の PGMEA/PGME溶液（固形分換算で 100質量部 のシロキサン系共重合体を含有）と、下記表 1に示す種類と配合量の（B)成分、化合 物（C)、（D)成分、（E)成分および (F)成分と、下記表 1に示す配合量の γ プチ口 ラタトンとを混合、溶解してレジスト組成物を調製した。  [0195] PGMEA / PGME solution of the above siloxane-based copolymer (containing 100 parts by mass of siloxane-based copolymer in terms of solid content), component (B) of the types and blending amounts shown in Table 1 below, and compounds Components (C), (D), (E), and (F) were mixed and dissolved in the blending amounts shown in Table 1 below to prepare a resist composition.
[0196] [表 1]
Figure imgf000070_0001
[0196] [Table 1]
Figure imgf000070_0001
[0197] 表 1中、 [ ]内の数値は配合量（質量部）を示す。また、各略号はそれぞれ以下の [0197] In Table 1, the values in [] indicate the blending amount (parts by mass). Each abbreviation is as follows:
(B)— 1:下記式 (B) 1で表される化合物。 (B) —1: Compound represented by the following formula (B) 1.
(B)— 2:下記式 (B) 2で表される化合物。  (B) — 2: Compound represented by the following formula (B) 2.
(C) 1:下記式 (C) 1で表される化合物。  (C) 1: Compound represented by the following formula (C) 1.
(D)— 1:下記式 (D) -1で表される化合物。  (D) —1: A compound represented by the following formula (D) -1.
(E)— 1:下記式 (E) 1で表される化合物。  (E) —1: A compound represented by the following formula (E) 1.
(F)— 1:マロン酸。  (F) — 1: Malonic acid.
[0198] [化 36] [0198] [Chemical 36]
Figure imgf000071_0001
Figure imgf000071_0001
[0199] <パターン形成〉 [0199] <Pattern formation>
以下の手順で、図 1Aから図 1Eおよび図 2Aから図 2Dに示したのと同様の工程で、 ノ ターンを形成した。  In the following procedure, a pattern was formed in the same process as shown in FIGS. 1A to 1E and FIGS. 2A to 2D.
8インチシリコンゥエーハ上に、下層膜形成材料として BLC730 (商品名：東京応化 工業株式会社製）を塗布して、 250°Cで 90秒間ベータ処理することにより、膜厚 250 nmの下層膜を形成した。  BLC730 (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on an 8-inch silicon wafer as a lower layer film forming material, and beta treatment is performed at 250 ° C for 90 seconds to form a lower layer film with a thickness of 250 nm. Formed.
[0200] 前記ハードマスク形成材料を前記下層膜上に塗布して、 250°Cで 90秒間べーク処 理することにより、膜厚 45nmのハードマスクを形成した。  [0200] The hard mask forming material was applied onto the lower layer film, and baked at 250 ° C for 90 seconds to form a hard mask with a film thickness of 45 nm.
[0201] 次いで、前記ハードマスク上に、前記ネガ型レジスト組成物をスピンコート塗布し、 8 0°C、 60秒の条件でプレベータ（PAB)を行うことにより、膜厚 160nmの第一のレジス ト膜を形成した。 [0201] Next, the negative resist composition was spin-coated on the hard mask, and 8 A first resist film having a thickness of 160 nm was formed by performing pre-beta (PAB) at 0 ° C. for 60 seconds.
次いで、この第一のレジスト膜を、 ArFエキシマレーザ露光機 NSR—S302 (Niko n社製、 NA=0. 6、 σ =0. 75)を用いて、マスクを介して選択的に露光した。  Next, this first resist film was selectively exposed through a mask using an ArF excimer laser exposure machine NSR-S302 (manufactured by Nikon, NA = 0.6, σ = 0.75).
次いで、 100°C、 60秒の条件で露光後加熱（PEB)を行った後、 2. 38質量％テト ラメチルアンモユウムヒドロキシド水溶液を用いて、 23°Cで 30秒間現像した。引き続 き、純水にて 30秒間のリンス処理を行い、第一のレジストパターンを形成した。  Next, post-exposure heating (PEB) was performed at 100 ° C. for 60 seconds, and then development was performed at 23 ° C. for 30 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. Subsequently, a first resist pattern was formed by rinsing with pure water for 30 seconds.
次いで、前記第一のレジストパターンをマスクとし、エッチング装置「TCE— 7811」 (商品名：東京応化工業株式会社製)を用いて、テーブル温度を 25/20°Cとし、 CF /CHF /He (sccm) = 60/20/160のエッチングガスを出力 300W、圧力 300 Next, using the first resist pattern as a mask, using an etching apparatus “TCE-7811” (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.), the table temperature was set to 25/20 ° C., and CF / CHF / He ( sccm) = 60/20/160 etching gas output 300W, pressure 300
4 3 4 3
mTorrで、 26秒間導入して、ハードマスクをエッチング処理した。その結果、第一の レジストパターンがハードマスクに転写され、第一のパターンが形成された。このし/ Sパターンの断面形状を SEM (走査型電子顕微鏡）により観察したところ、ライン幅 9 0nm、スペース幅 270nmであることが確認された。次に、テトラメチルアンモニゥムヒ Introduced with mTorr for 26 seconds, the hard mask was etched. As a result, the first resist pattern was transferred to the hard mask, and the first pattern was formed. When the cross-sectional shape of the S / S pattern was observed with a scanning electron microscope (SEM), it was confirmed that the line width was 90 nm and the space width was 270 nm. Next, tetramethylammonumhi
)の剥離液に 40°Cで 6分間浸漬させることで、レジスト膜を剥離した。 The resist film was peeled off by immersing it in a stripping solution at 40 ° C for 6 minutes.
前記第一のパターン上に、前記化学増幅型ポジ型シリコン系レジスト組成物をスピ ンコート塗布し、 85°C、 60秒の条件でプレベータ（PAB)を行うことにより、膜厚 130η mの第二のレジスト膜を形成した。  The chemically amplified positive silicon resist composition is spin-coated on the first pattern, and pre-beta (PAB) is performed at 85 ° C. for 60 seconds to obtain a second film having a thickness of 130 ηm. The resist film was formed.
次いで、前記マスクを、第一のレジスト膜露光時の位置から、 90nmずらして設置し 、前記マスクを介して、 ArFエキシマレーザ露光機 NSR— S302 (Nikon社製、 NA =0. 6、 σ =0. 75)を用いて、前記第二のレジスト膜を選択的に露光した。  Next, the mask was placed 90 nm away from the position at which the first resist film was exposed, and the ArF excimer laser exposure machine NSR-S302 (Nikon, NA = 0.6, σ = The second resist film was selectively exposed using 0.75).
次いで、 95°C、 60秒の条件で露光後加熱（PEB)を行った後、 2. 38質量％テトラ メチルアンモニゥムヒドロキシド水溶液を用いて、 23°Cで 30秒間現像した。引き続き、 純水にて 30秒間のリンス処理を行い、第二のレジストパターンを形成した。この時の L/Sパターンの断面形状を SEM (走査型電子顕微鏡）により観察したところ、ライン 幅はハードマスクが 93nm、第二のレジスト膜が 90nm、スペース幅は 88nmであるこ とが確認された。 次いで、前記第一のパターン及び第二のレジストパターンをマスクとし、エッチング 装置「GP— 12」（商品名：東京応化工業株式会社製)を用いて、テーブル温度を 25 /20°Cとし、 O /N (sccm) = 60/40のエッチングガスを出力 1600W/バイアス Next, post-exposure heating (PEB) was performed at 95 ° C. for 60 seconds, and then development was performed at 23 ° C. for 30 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Subsequently, a rinsing process for 30 seconds was performed with pure water to form a second resist pattern. When the cross-sectional shape of the L / S pattern at this time was observed by SEM (scanning electron microscope), it was confirmed that the line width was 93 nm for the hard mask, 90 nm for the second resist film, and the space width was 88 nm. . Next, using the first pattern and the second resist pattern as a mask, using an etching apparatus “GP-12” (trade name: manufactured by Tokyo Ohka Kogyo Co., Ltd.), the table temperature is set to 25/20 ° C., and O / N (sccm) = 60/40 etching gas output 1600W / bias
2 2  twenty two
100W、圧力 3mTorrで、 4分間導入して、下層膜をエッチング処理し、第二のパタ ーンを形成した。この L/Sパターンの断面形状を SEM (走査型電子顕微鏡）により 観察した。その結果、ライン幅はハードマスクでマスクされた部位が 90nm、第二のレ ジスト膜でマスクされた部位が 89nm、スペース幅は 92nmであることが確認された。 一方、第二のパターン形成後のアスペクト比を算出すると約 3· 2となり、高アスペクト 比のパターンが得られたことが確認された。  Introduced for 4 minutes at 100 W and a pressure of 3 mTorr, the lower layer film was etched to form a second pattern. The cross-sectional shape of this L / S pattern was observed by SEM (scanning electron microscope). As a result, it was confirmed that the line width was 90 nm at the portion masked with the hard mask, the portion masked with the second resist film was 89 nm, and the space width was 92 nm. On the other hand, when the aspect ratio after the second pattern was formed was about 3.2, it was confirmed that a pattern with a high aspect ratio was obtained.
産業上の利用可能性 Industrial applicability
本発明によれば、支持体上に高精細かつ高アスペクト比のパターンが形成できる ノ ターン形成方法を提供できるから、産業上極めて有効である。  According to the present invention, since a pattern forming method capable of forming a high-definition and high-aspect-ratio pattern on a support can be provided, it is extremely effective industrially.

Claims

請求の範囲 The scope of the claims
[1] 化学増幅型レジスト組成物を用いてパターンを形成するパターン形成方法であつ て、  [1] A pattern forming method for forming a pattern using a chemically amplified resist composition,
支持体上に、下層膜形成材料を用いて下層膜を形成する工程と、前記下層膜上に シリコン系ハードマスク形成材料を用いてハードマスクを形成する工程と、前記ハード マスク上に化学増幅型ネガ型レジスト組成物を塗布して第一のレジスト膜を形成する 工程と、前記第一のレジスト膜を、第一のマスクパターンを介して選択的に露光し、 現像して第一のレジストパターンを形成する工程と、前記第一のレジストパターンをマ スクとして、ハードマスクをエッチングして第一のパターンを形成する工程と、  Forming a lower layer film on the support using a lower layer film forming material; forming a hard mask on the lower layer film using a silicon hard mask forming material; and chemically amplifying on the hard mask. A step of applying a negative resist composition to form a first resist film; and selectively exposing the first resist film through a first mask pattern; developing the first resist pattern; Forming a first pattern by etching the hard mask using the first resist pattern as a mask, and
前記第一のパターン及び下層膜の上に化学増幅型ポジ型シリコン系レジスト組成 物を塗布して第二のレジスト膜を形成する工程と、前記第二のレジスト膜を、第二の マスクパターンを介して選択的に露光し、現像して第二のレジストパターンを形成す る工程と、前記第一のパターン及び第二のレジストパターンをマスクとして、下層膜を エッチングして第二のパターンを形成する工程とを含むことを特徴とするパターン形 成方法。  A step of applying a chemically amplified positive silicon-based resist composition on the first pattern and the lower layer film to form a second resist film; and the second resist film with a second mask pattern. A second resist pattern is formed by selectively exposing and developing through a lower layer film by using the first pattern and the second resist pattern as a mask to form a second pattern. The pattern formation method characterized by including the process to perform.
[2] 前記化学増幅型ポジ型シリコン系レジスト組成物は、  [2] The chemically amplified positive silicon resist composition includes:
酸の作用によりアルカリ溶解性が増大する樹脂成分 (A)および露光により酸を発生 する酸発生剤成分 (B)を含有するレジスト組成物であって、  A resist composition comprising a resin component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon exposure,
前記樹脂成分 (A)が、下記一般式 (al)で表される構成単位 (al)と、下記一般式（ a2)で表される構成単位 (a2)とを有する樹脂 (A1)を  The resin component (A) comprises a resin (A1) having a structural unit (al) represented by the following general formula (al) and a structural unit (a2) represented by the following general formula (a2):
含有する請求項 1に記載のパターン形成方法。  The pattern forming method according to claim 1, which is contained.
[化 1コ
Figure imgf000074_0001
[Chemical 1
Figure imgf000074_0001
[式 (a2)中、 R1は下記一般式 (I)で表される酸分解性基である。 ] [In the formula (a2), R 1 is an acid-decomposable group represented by the following general formula (I). ]
[化 2] (R^)gj L— -{R3}^— ~~Z , , , . ) [Chemical 2] (R ^) gj L—-{R 3 } ^ — ~~ Z,,,.)
[式 (I)中、 R2〜R3はそれぞれ独立に連結基であり； Lは炭素数 1〜； 10の直鎖状また は分岐鎖状アルキレン基、炭素数 2〜20の直鎖状または分岐鎖状フルォロアルキレ ン基、置換または無置換のァリーレン基、置換または無置換の環状アルキレン基、お よび置換または無置換のアルカリ一レン基からなる群から選択される基であり； Zは酸 解離性基であり； gは 0または 1であり； hは 0または 1である。 ] [In the formula (I), R 2 to R 3 are each independently a linking group; L is a C 1 -C; linear or branched alkylene group having 10 carbons, and a linear chain having 2 to 20 carbons. Or a group selected from the group consisting of a branched fluoralkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted cyclic alkylene group, and a substituted or unsubstituted alkali monoylene group; A dissociable group; g is 0 or 1; h is 0 or 1. ]
前記第二のマスクパターンとして前記第一のマスクパターンを用い、第一のレジスト 膜の選択的露光時とは異なる位置に前記第一のマスクパターンを設けて、第二のレ ジスト膜を選択的に露光する請求項 1または 2に記載のパターン形成方法。  The first mask pattern is used as the second mask pattern, the first mask pattern is provided at a position different from that during selective exposure of the first resist film, and the second resist film is selectively used. The pattern forming method according to claim 1, wherein the pattern is exposed to light.
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