WO2021182182A1 - Treatment liquid and pattern forming method - Google Patents

Treatment liquid and pattern forming method Download PDF

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Publication number
WO2021182182A1
WO2021182182A1 PCT/JP2021/007923 JP2021007923W WO2021182182A1 WO 2021182182 A1 WO2021182182 A1 WO 2021182182A1 JP 2021007923 W JP2021007923 W JP 2021007923W WO 2021182182 A1 WO2021182182 A1 WO 2021182182A1
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group
solvent
carbon atoms
preferable
treatment liquid
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PCT/JP2021/007923
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French (fr)
Japanese (ja)
Inventor
智美 高橋
徹 土橋
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富士フイルム株式会社
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Priority to JP2022505942A priority Critical patent/JPWO2021182182A1/ja
Publication of WO2021182182A1 publication Critical patent/WO2021182182A1/en
Priority to JP2023213680A priority patent/JP2024029021A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a treatment liquid for patterning a resist film and a pattern forming method. More specifically, the present invention is used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit substrates such as liquid crystal and thermal heads, and other photolithography lithography steps.
  • the present invention relates to a treatment liquid and a pattern forming method.
  • Patent Document 1 discloses a developing solution or a rinsing solution containing a predetermined organic solvent.
  • the inner wall of piping used for semiconductor equipment and devices may be coated with a fluororesin typified by a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. If charging occurs when the treatment liquid is passed through the inside of such a pipe, pinholes may occur and problems such as liquid leakage may occur.
  • the present invention has been made in view of the above points, and when used for at least one of development and cleaning (rinsing) of a resist film, it is possible to form a pattern having excellent resolvability, and the present invention is capable of forming a pattern.
  • An object of the present invention is to provide a treatment liquid that is less likely to be charged when it comes into contact with a fluororesin.
  • Another object of the present invention is to provide a pattern forming method for the above-mentioned treatment liquid.
  • a treatment liquid for patterning a resist film which is used for performing at least one of development and cleaning after exposure on a resist film obtained from a sensitive light beam or a radiation-sensitive composition.
  • the organic solvent contains a non-cyclic ester solvent and contains The acyclic ester solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
  • the organic solvent is isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate, amyl acetate, hexyl acetate.
  • the treatment solution according to (8) which comprises at least one selected from the group consisting of methyl n-octanoate and ethyl n-octanoate.
  • the organic solvent contains an acyclic ether solvent, and the organic solvent contains a non-cyclic ether solvent.
  • the acyclic ether solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
  • the treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic ether solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
  • the organic solvent contains a non-cyclic alcohol solvent and contains The acyclic alcohol solvent has 7 or more carbon atoms and has 7 or more carbon atoms.
  • the treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic alcohol solvent and the boiling point of the fluorine solvent is 100 ° C. or higher.
  • the organic solvent is 2,6-dimethyl-4-heptanol, 3-octanol, 2-ethylhexanol, 1-octanol, 2-octanol, 3,5-dimethyl-1-hexin-3-ol, 1-.
  • the organic solvent contains an acyclic ketone solvent, and the organic solvent contains a non-cyclic ketone solvent.
  • the acyclic ketone solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
  • the organic solvent is from diisobutyl ketone, 3-octanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 5-nonanonone, and 2,5-dimethyl-3-hexanone.
  • (16) The treatment liquid according to any one of (1) to (7), wherein the organic solvent contains a hydrocarbon solvent having 7 or more carbon atoms.
  • the processing process is The development process of developing with a developer and Equipped with a rinsing process for cleaning with a rinsing liquid, The pattern forming method, wherein the rinsing liquid is the treatment liquid according to any one of (1) to (18).
  • Ester-based solvents are butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, amyl formate, isoamyl formate, hexyl formate, amyl propionate, isoamyl propionate, isopropyl propionate.
  • the present invention when used for at least one of development and cleaning (rinsing) of a resist film, it is possible to form a pattern having excellent resolution, and when it comes into contact with a fluororesin, it becomes charged. It is possible to provide a treatment liquid that is unlikely to occur. Further, according to the present invention, it is possible to provide a pattern forming method for the above-mentioned treatment liquid.
  • the notation without substitution and non-substitution includes a group having a substituent as well as a group having no substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the "organic group” in the present specification means a group containing at least one carbon atom.
  • active light or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X rays, and electron beams (EUV light: Extreme Ultraviolet), and electron beams (. EB: Electron Beam) and the like.
  • light means active light or radiation.
  • exposure refers to the emission line spectrum of a mercury lamp, exposure to far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, and the like, as well as electron beams and ions. It also includes drawing with particle beams such as beams.
  • the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified.
  • Y when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acrylic represents acrylic and methacryl
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (hereinafter, also referred to as “molecular weight distribution”) (Mw / Mn) of the resin are referred to as GPC (Gel Permeation Chromatography) apparatus ( GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detection Instrument: Defined as a polystyrene-equivalent value by a differential refractive index detector (Refractive Index Detector).
  • GPC Gel Permeation Chromatography
  • the boiling point means the boiling point at 1 atm.
  • organic solvent means an organic compound that is liquid at 25 ° C.
  • the type and content of the organic compound contained in the treatment liquid are measured by, for example, DI-MS (Direct Injection Mass Chromatography).
  • the treatment liquid of the present invention is used to perform at least one of development and cleaning on a resist film obtained from a sensitive light beam or a radiation-sensitive composition (hereinafter, also referred to as “resist composition”).
  • a treatment liquid for patterning a resist film is characterized by a fluorine-based solvent having 3 to 5 carbon atoms (hereinafter, also simply referred to as “fluorine-based solvent”) and an organic solvent other than the fluorine-based solvent having 3 to 5 carbon atoms (hereinafter, simply referred to as “fluorine-based solvent”). , Simply referred to as "second solvent”).
  • the present inventors have found that by using a fluorine-based solvent, charging is prevented when the treatment liquid comes into contact with the fluorine-based resin. On the other hand, when a fluorine-based solvent is used, the resolution is deteriorated. Therefore, it has been found that the resolution is improved while preventing the above-mentioned electrification by using an organic solvent other than the fluorine-based solvent.
  • the fluorine-based solvent having a boiling point lower than that of the second solvent as the fluorine-based solvent.
  • the fluorine-based solvent preferentially volatilizes during drying after treatment with the treatment liquid (for example, rinsing treatment), and the second solvent on the formed pattern. Concentration increases. As a result, the effect of the second solvent is maximized, and the effect of suppressing the pattern collapse in the dense pattern becomes more remarkable.
  • the treatment liquid of the present invention contains a fluorine-based solvent.
  • the fluorine-based solvent has 3 to 5 carbon atoms, and 4 to 5 is preferable, and 5 is even more preferable, because the effect of the present invention is more excellent.
  • the fluorine-based solvent means an organic solvent containing at least one fluorine atom in the molecule.
  • a hydrocarbon having at least one fluorine atom and having 3 to 5 carbon atoms is preferable.
  • the number of fluorine atoms contained in the fluorine-based solvent is preferably twice or more the number of carbon atoms contained in the fluorine-based solvent.
  • the upper limit is not particularly limited, but is preferably 3 times or less, and more preferably 2.5 times or less.
  • the fluorine-based solvent the compound represented by the formula (a) is preferable. More specifically, 2H, 3H-decafluoropentane or 1H-undecafluoropentane is preferable.
  • X 1 to X 6 independently represent a hydrogen atom or a fluorine atom.
  • X 1 to X 6 one or more represents a fluorine atom, three or more preferably represent a fluorine atom, and five or more represent a fluorine atom.
  • Y represents an alkylene group having 1 to 3 carbon atoms, which may have a fluorine atom.
  • the alkylene group which may have a fluorine atom represented by Y may have a linear structure or a branched chain structure. Among them, the alkylene group preferably has a linear structure.
  • the alkylene group represented by Y has 1 to 3 carbon atoms, preferably 2 to 3 and more preferably 3.
  • the alkylene group preferably has a fluorine atom, and the number of fluorine atoms contained in the alkylene group is preferably 2 to 6, more preferably 2 to 4.
  • the boiling point (° C) of the fluorine-based solvent is preferably 40 ° C or higher.
  • the upper limit is not particularly limited, but is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 60 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the fluorine-based solvent may be used alone or in combination of two or more.
  • the content of the fluorosolvent is not particularly limited, and is often 5 to 95% by mass with respect to the total mass of the treatment liquid, and 10 to 80% by mass is preferable because the effect of the present invention is more excellent. It is more preferably from 70% by mass, further preferably from 10 to 50% by mass.
  • the treatment liquid of the present invention contains a second solvent.
  • the second solvent may be a solvent other than the fluorine-based solvent having 3 to 5 carbon atoms, and may be a solvent containing a fluorine atom or a solvent not containing a fluorine atom (non-fluorine-based solvent).
  • the non-fluorine-based solvent means an organic solvent having no fluorine atom in the molecule.
  • the second solvent preferably contains a hydrocarbon which may have a heteroatom.
  • the hetero atom may be an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the second solvent a non-fluorine solvent is preferable.
  • the second solvent include ester-based solvents, ether-based solvents, alcohol-based solvents, ketone-based solvents, and hydrocarbon-based solvents.
  • the second solvent may have a linear structure, a branched chain structure, or a cyclic structure.
  • the second solvent is selected from acyclic ester-based solvent, acyclic ether-based solvent, acyclic alcohol-based solvent, acyclic ketone-based solvent, and hydrocarbon-based solvent. At least one selected from the above group is preferable, and acyclic ester-based solvent, acyclic ether-based solvent, acyclic alcohol-based solvent, or acyclic ketone-based solvent is more preferable.
  • the second solvent may contain an ester solvent.
  • the ester solvent in the present specification also includes a carbonic acid ester solvent.
  • ester solvent examples include isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate, amyl acetate and acetic acid.
  • isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate are the most excellent points of the present invention.
  • the ester solvent may have a linear structure or a branched chain structure. Further, the ester solvent may have a cyclic structure. Among them, the ester solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ester solvent is preferably a non-cyclic ester solvent (ester solvent having no cyclic structure).
  • the ester solvent may have, for example, a linear alkyl group or a branched chain alkyl group. Among them, in that the effect of the present invention is more excellent, the ester solvent is preferably composed of only an ester bond and a linear alkyl group or a branched alkyl group.
  • the carbon number of the ester solvent is not particularly limited, but is preferably 5 or more.
  • the upper limit is not particularly limited, but is preferably 15 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
  • the preferable range of the carbon number of the acyclic ester-based solvent is also the same as the preferable range of the carbon number of the above-mentioned ester-based solvent.
  • the absolute value of the difference between the boiling point (° C.) of the ester solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher.
  • the upper limit is not particularly limited, but is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and even more preferably 120 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the preferable range of the absolute value of the difference between the boiling point of the acyclic ester solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ester solvent and the boiling point of the fluorine solvent. ..
  • the ester solvent may be used alone or in combination of two or more.
  • the second solvent may contain an ether solvent.
  • the ether solvent include diisoamyl ether, amyl ether, diisoamyl ether, amyl ether, and anisole. Among them, diisoamyl ether, amyl ether, diisoamyl ether, or amyl ether is preferable as the ether solvent because the effect of the present invention is more excellent.
  • the ether solvent may have a linear structure or a branched chain structure. Further, the ether solvent may have a cyclic structure. Among them, the ether solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ether solvent is preferably a non-cyclic ether solvent (an ether solvent having no cyclic structure).
  • the ether solvent may have, for example, a linear alkyl group or a branched chain alkyl group. Among them, in that the effect of the present invention is more excellent, the ether solvent is preferably composed of only an ether bond and a linear alkyl group or a branched alkyl group.
  • the number of carbon atoms of the ether solvent is not particularly limited, but 5 or more is preferable, 8 or more is more preferable, and 10 or more is further preferable.
  • the upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
  • the preferable range of the carbon number of the acyclic ether solvent is also the same as the preferable range of the carbon number of the above-mentioned ether solvent.
  • the absolute value of the difference between the boiling point (° C.) of the ether solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher, more preferably 90 ° C. or higher, and even more preferably over 105 ° C.
  • the upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the preferable range of the absolute value of the difference between the boiling point of the acyclic ether solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ether solvent and the boiling point of the fluorine solvent. ..
  • the ether solvent may be used alone or in combination of two or more.
  • the second solvent may contain an alcohol solvent.
  • Examples of the alcohol-based solvent include 2,6-dimethyl-4-heptanol, 3-octanol, 2-ethylhexanol, 1-octanol, 2-octanol, 3,5-dimethyl-1-hexin-3-ol, and 1, -Octin-3-ol, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol-4-methylpentanol, and 1-heptanol Can be mentioned. Among them, 2,6-dimethyl-4-heptanol or 3-octanol is preferable as the alcohol solvent because the effect of the present invention is more excellent.
  • the alcohol solvent may have a linear structure or a branched chain structure. Further, the alcohol solvent may have a cyclic structure. Among them, the alcohol solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the alcohol solvent is preferably a non-cyclic alcohol solvent (alcohol solvent having no cyclic structure).
  • the alcohol solvent may have, for example, a linear alkyl group or a branched chain alkyl group. Further, in that the effect of the present invention is more excellent, the alcohol solvent is preferably composed of only a hydroxyl group and a linear alkyl group or a branched alkyl group.
  • the carbon number of the alcohol solvent is not particularly limited, but is preferably 7 or more, and more preferably 8 or more.
  • the upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
  • the preferable range of the carbon number of the acyclic alcohol solvent is also the same as the preferable range of the carbon number of the alcohol-based solvent described above.
  • the absolute value of the difference between the boiling point (° C.) of the alcohol solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
  • the upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the preferable range of the absolute value of the difference between the boiling point of the acyclic alcohol solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the alcohol solvent and the boiling point of the fluorine solvent. ..
  • the alcohol solvent may be used alone or in combination of two or more.
  • the second solvent may contain a ketone solvent.
  • ketone solvent examples include diisobutyl ketone, 3-octanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 5-nonanonone, and 2,5-dimethyl-3-hexanone. Can be mentioned. Among them, diisobutyl ketone, 3-octanone, or 2,4-dimethyl-3-pentanone is preferable as the ketone solvent because the effect of the present invention is more excellent.
  • the ketone solvent may have a linear structure or a branched chain structure. Further, the ketone solvent may have a cyclic structure. Among them, the ketone solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ketone solvent is preferably a non-cyclic ketone solvent (a ketone solvent having no cyclic structure).
  • the ketone solvent may have, for example, a linear alkyl group or a branched chain alkyl group. Further, from the viewpoint that the effect of the present invention is more excellent, it is preferable that the ketone solvent is composed of only a ketone bond and a linear alkyl group or a branched alkyl group.
  • the carbon number of the ketone solvent is not particularly limited, but is preferably 5 or more, and more preferably 7 or more.
  • the upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
  • the preferable range of the carbon number of the acyclic ketone solvent is also the same as the preferable range of the carbon number of the above-mentioned ketone solvent.
  • the absolute value of the difference between the boiling point (° C.) of the ketone solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher, more preferably 70 ° C. or higher.
  • the upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the preferable range of the absolute value of the difference between the boiling point of the acyclic ketone solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ketone solvent and the boiling point of the fluorine solvent. ..
  • the ketone solvent may be used alone or in combination of two or more.
  • the second solvent may contain a hydrocarbon solvent.
  • aromatic solvent examples include decane, mesitylene, undecane, nonanone, 3-methylnonanone, 4-methylnonanone, and 5-methylnonanone.
  • decane or mesitylene is preferable as the aromatic solvent because the effect of the present invention is more excellent.
  • the hydrocarbon solvent may have a linear structure, a branched chain structure, or a cyclic structure.
  • the hydrocarbon solvent may have, for example, a linear alkyl group, a branched chain alkyl group, an alicyclic group, or an aromatic group.
  • the hydrocarbon solvent preferably has a linear alkyl group or an aromatic group because the effect of the present invention is more excellent.
  • the hydrocarbon-based solvent is preferably composed of only an aromatic ring or a linear alkyl group or a branched alkyl group.
  • the number of carbon atoms in the hydrocarbon solvent is not particularly limited, but 7 or more is preferable, and 8 or more is more preferable.
  • the upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
  • the absolute value of the difference between the boiling point (° C.) of the hydrocarbon solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 100 ° C. or higher, more preferably 105 ° C. or higher.
  • the upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the boiling point is the boiling point at 1 atm.
  • the hydrocarbon solvent may be used alone or in combination of two or more.
  • the content of the second solvent is not particularly limited, and is often 5 to 95% by mass with respect to the total mass of the treatment liquid, and 20 to 90% by mass is preferable in that the effect of the present invention is more excellent. It is more preferably from 90% by mass, still more preferably from 50 to 90% by mass.
  • the treatment liquid of the present invention may contain other components other than those described above.
  • the treatment liquid may contain a metal component.
  • the metal component include metal particles and metal ions.
  • the content of the metal component indicates the total content of the metal particles and the metal ions.
  • the treatment liquid may contain either metal particles or metal ions, or may contain both.
  • Examples of the metal atom contained in the metal component include Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na. Examples thereof include metal atoms selected from the group consisting of Ni, Pb, Sn, Sr, Ti, and Zn.
  • the metal component may contain one kind of metal atom or two or more kinds.
  • the metal particles may be simple substances or alloys, and may exist in a form in which the metal is associated with an organic substance.
  • the metal component may be a metal component unavoidably contained in each component (raw material) contained in the treatment liquid, or may be a metal component unavoidably contained during the production, storage, and / or transfer of the treatment liquid. However, it may be added intentionally.
  • the content of the metal component is preferably more than 0 mass ppt and 1 mass ppm or less, more preferably more than 0 mass ppt and 10 mass ppb or less, and 0 mass with respect to the total mass of the treatment liquid. More than 10 mass ppt or less is more preferable.
  • the type and content of the metal component in the treatment liquid can be measured by the ICP-MS method (inductively coupled plasma mass spectrometry).
  • the treatment liquid of the present invention may contain the following ionic liquids.
  • the ionic liquid shall not be contained in the fluorine-based solvent and the second solvent.
  • the ionic liquid include aromatic ions such as pyridinium ion and imidazolium ion, and aliphatic amine ions such as trimethylhexyl ammonium ion as cations.
  • ionic liquids examples include IL-P14 and IL-A2 (manufactured by Koei Chemical Industry Co., Ltd.); quaternary ammonium salt-based ionic liquids such as Elegan SS-100 (manufactured by NOF CORPORATION). Can be mentioned.
  • ionic liquid one type may be used alone, or two or more types may be used in combination.
  • the content of the ionic liquid is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of the treatment liquid. It is more preferably ⁇ 5% by mass.
  • the treatment liquid of the present invention may contain a surfactant.
  • a surfactant When the treatment liquid contains a surfactant, the wettability of the treatment liquid with respect to the resist film is improved, and development and / or rinsing proceeds more effectively.
  • the surfactant the same surfactant as that which can be contained in the resist composition described later can be used.
  • One type of surfactant may be used alone, or two or more types may be used in combination.
  • the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the treatment liquid. , 0.01-0.5% by mass is more preferable.
  • the treatment liquid of the present invention may contain an antioxidant.
  • the antioxidant is preferably an amine-based antioxidant or a phenol-based antioxidant.
  • One type of antioxidant may be used alone, or two or more types may be used in combination.
  • the content of the antioxidant is preferably 0.0001 to 1% by mass, preferably 0.0001 to 0.1% by mass, based on the total mass of the treatment liquid. More preferably, 0.0001 to 0.01% by mass is further preferable.
  • the treatment liquid of the present invention may contain a basic compound.
  • the basic compound include compounds exemplified as acid diffusion control agents that can be contained in the resist composition described later.
  • the basic compound one type may be used alone, or two or more types may be used in combination.
  • the content of the basic compound is preferably 10% by mass or less, more preferably 0.5 to 5% by mass, based on the total mass of the treatment liquid. In the present invention, only one kind of the basic compound may be used, or two or more kinds having different chemical structures may be used in combination.
  • Organic matter with a boiling point of 300 ° C or higher When a treatment liquid containing an organic substance having a boiling point of 300 ° C. or higher is applied to a semiconductor device manufacturing process, the organic substance having a high boiling point may remain without volatilization, which may cause defects in the substrate.
  • the organic substance having a boiling point of 300 ° C. or higher may be, for example, a resin component or a plasticizer contained in a plastic material (for example, an O-ring) used for a member of a manufacturing apparatus, and at any time in the manufacturing process. It is presumed that it was eluted in the liquid.
  • the treatment liquid contains an organic substance having a boiling point of 300 ° C.
  • the content of the organic substance having a boiling point of 300 ° C. or higher is based on the total mass of the treatment liquid from the viewpoint of suppressing defects in the substrate when used in the semiconductor device manufacturing process. Therefore, 0.001 to 50 mass ppm is preferable, 0.001 to 30 mass ppm is more preferable, 0.001 to 15 mass ppm is further preferable, 0.001 to 10 mass ppm is particularly preferable, and 0.001 to 1 mass ppm is particularly preferable. Mass ppm is most preferred.
  • the content of an organic substance having a boiling point of 300 ° C. or higher is 30% by mass or less with respect to the total mass of the treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate. It is preferable in that organic substances are not volatilized and remain on the surface of the substrate to prevent defects from occurring.
  • the content of organic substances having a boiling point of 300 ° C. or higher is 15% by mass or less with respect to the total mass of the treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate, it is baked. It is more preferable from the viewpoint of suppressing the cause of defects (development failure) in order to prevent organic substances having a boiling point of 300 ° C.
  • Organic substances having a boiling point of 300 ° C. or higher that can be contained in the treatment liquid include components such as diisononyl phthalate (DOP, boiling point 385 ° C.) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403 ° C.), and dioctyl adipate.
  • DOP diisononyl phthalate
  • DINP diisononyl phthalate
  • DEP diisononyl phthalate
  • DEP diisononyl phthalate
  • EPDM ethylene propylene rubber
  • Examples of the method for keeping the content of organic substances having a boiling point of 300 ° C. or higher in the treatment liquid within the above range include the methods mentioned in the purification step described later.
  • the present invention also relates to a pattern forming method using the above-mentioned treatment liquid.
  • the pattern forming method is, for example, (I) A resist film forming step of forming a resist film using a resist composition, and (Ii) An exposure step for exposing the resist film and (Iii)
  • the present invention includes a treatment step of treating the exposed resist film with the above-mentioned treatment liquid.
  • the resist film forming step is a step of forming a resist film using a resist composition.
  • a resist composition for example, each component described later is dissolved in a solvent to prepare a resist composition, which is filtered as necessary, and then placed on a support (substrate).
  • a resist composition is applied to form a resist film.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • As the material of the filter polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • the resist composition is applied onto a support (substrate), for example, by an appropriate coating method such as a spinner. Then, the coating film (the coating film of the applied resist composition) is dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, and antireflection film) may be formed under the resist film.
  • the support that forms the resist film is not particularly limited, and is not particularly limited, such as a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal or a thermal head, and other photolithography lithography processes. Commonly used substrates can be used in. Specific examples of the support include an inorganic substrate such as silicon, SiO 2 , and SiN.
  • the substrate also includes a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers.
  • the material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of a group III-V compound such as silicon, silicon germanium, or GaAs, or any combination thereof. ..
  • an interconnect structure such as a metal wire and a dielectric material is exposed and integrated on the above-mentioned semiconductor substrate such as silicon. It may have a circuit structure.
  • Metals and alloys used in the interconnect structure include, but are limited to, aluminum and copper and alloyed aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It is not something that is done.
  • a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on the semiconductor substrate.
  • the heating temperature is preferably 80 to 180 ° C., more preferably 80 to 150 ° C., further preferably 80 to 140 ° C., and particularly preferably 80 to 130 ° C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
  • the film thickness of the resist film is generally 200 nm or less, preferably 100 nm or less.
  • the film thickness of the resist film is preferably 50 nm or less.
  • the film thickness is preferably 15 to 70 nm, more preferably 15 to 65 nm, in that it is more excellent in etching resistance and resolution.
  • a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflection film
  • SOG Spin On Glass
  • SOC Spin On Carbon
  • an antireflection film may be formed between the resist film and the support.
  • a material constituting the resist underlayer film a known organic or inorganic material can be appropriately used.
  • a protective film (top coat) may be formed on the upper layer of the resist film.
  • the protective film a known material can be appropriately used.
  • US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432 The composition for forming a protective film disclosed in US Patent Application Publication No.
  • the composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent. Further, for example, the upper layer film may be formed based on the description in paragraphs [0072] to [2002] of JP-A-2014-059543.
  • the film thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.
  • the exposure method in the (ii) exposure step may be immersion exposure.
  • the pattern forming method preferably includes (iv) preheating (PB: PreBake, hereinafter also referred to as "post-coating bake") step before the (ii) exposure step.
  • the pattern forming method preferably includes (v) post-exposure heating (PEB: Post Exposure Bake, also referred to as post-exposure bake) step after the (ii) exposure step and before the (iii) development step.
  • the pattern forming method may include (ii) exposure steps a plurality of times.
  • the pattern forming method may include (iv) a preheating step a plurality of times.
  • the pattern forming method may include (v) a post-exposure heating step a plurality of times.
  • the (ii) exposure step can be performed by a generally known method.
  • the heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., still more preferably 80 to 130 ° C. in both the (iv) preheating step and the (v) post-exposure heating step.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, still more preferably 60 to 600 seconds in both the (iv) preheating step and the (v) post-exposure heating step.
  • the heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.
  • the wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam.
  • far ultraviolet rays are preferable, and the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, further preferably 1 to 200 nm.
  • KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), and an electron beam or the like
  • KrF excimer laser, ArF excimer laser , EUV, or electron beam is preferable, and EUV or electron beam is more preferable.
  • the step of treating the exposed film usually includes (vi) a developing step of developing with a developing solution (developing step) and (vii) a rinsing step of washing with a rinsing solution (rinsing step).
  • the treatment liquid of the present invention may be used as a developing solution in a developing step, or may be used as a rinsing liquid in a rinsing step. Above all, it is preferable to use it as a rinsing liquid in the rinsing process.
  • the treatment liquid of the present invention is used as a rinsing liquid in the rinsing step, it is preferable to use a treatment liquid other than the treatment liquid of the present invention as the developing liquid in the developing step.
  • the developing step is a step of developing the exposed resist film with a developing solution.
  • Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate.
  • There are methods such as spraying the developer on the surface (spray method) and continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method).
  • spray method spraying the developer on the surface
  • dynamic discharge method dynamic discharge method
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the development time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • the above-mentioned processing solution may be used, or other developing solution may be used.
  • development with an alkaline developer may be performed (so-called double development).
  • the vapor pressure of the organic solvent used in the developing solution is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C.
  • the organic solvent used in the developing solution is not particularly limited, and examples thereof include solvents such as ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
  • the developer preferably contains at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent.
  • ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (acetate).
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, and the like.
  • Examples thereof include phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and ⁇ -butyrolactone.
  • 2-heptanone is preferable.
  • alcohol-based solvent examples include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol
  • Alcohols such as (monohydric alcohol); glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl.
  • Ether triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene.
  • Glycol ether-based solvents containing hydroxyl groups such as glycol monophenyl ether; and the like. Of these, glycol ether solvents are preferable.
  • the ether-based solvent examples include, in addition to the above-mentioned glycol ether-based solvent containing a hydroxyl group, a glycol ether-based solvent containing no hydroxyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; anisole, and , Aromatic ether solvents such as phenetol; examples include dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyl tetrahydrofuran, perfluorotetratetra, 1,4-dioxane, isopropyl ether and the like. Of these, glycol ether solvents or aromatic ether solvents such as anisole are preferable.
  • amide solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. And so on.
  • hydrocarbon solvent examples include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and per.
  • Hydrocarbon solvents such as fluoroheptane; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and Aromatic hydrocarbon-based solvents such as dipropylbenzene; can be mentioned.
  • an unsaturated hydrocarbon-based solvent can also be used, and examples thereof include unsaturated hydrocarbon-based solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene.
  • the number of double bonds or triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position of the hydrocarbon chain.
  • the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.
  • the aliphatic hydrocarbon-based solvent which is a hydrocarbon-based solvent, may be a mixture of compounds having the same number of carbon atoms and different structures.
  • decane when used as an aliphatic hydrocarbon-based solvent, compounds having the same carbon number and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, are aliphatic hydrocarbons. It may be contained in a system solvent. Further, the above-mentioned compounds having the same number of carbon atoms and different structures may contain only one kind, or may contain a plurality of kinds as described above.
  • the developer has 6 or more carbon atoms (preferably 6 to 14, more preferably 6 to 12) in that the swelling of the resist film can be further suppressed when EUV light and an electron beam are used in the above-mentioned exposure step. , 6 to 10 is more preferable), and an ester-based solvent having 2 or less heteroatoms is preferable.
  • the hetero atom may be an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the number of heteroatoms is preferably 2 or less.
  • ester-based solvents having 6 or more carbon atoms and 2 or less heteroatomic atoms include butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and pentyl propionate. It is preferably selected from the group consisting of hexyl propionate, heptyl propionate, butyl butanoate, butyl isobutate, and isobutyl isobutate, and isoamyl acetate or butyl isobutate is more preferable.
  • the above-mentioned carbon number is 6 or more and the heteroatom number is 2 or less in that the suppression of swelling of the ester film is further suppressed.
  • a mixed solvent of an ester solvent and a hydrocarbon solvent, or a mixed solvent of a ketone solvent and a hydrocarbon solvent may be used instead of the ester solvent.
  • the content of the hydrocarbon solvent depends on the solvent solubility of the resist film and is not particularly limited, and the required amount may be determined as appropriate.
  • isoamyl acetate is preferable as the ester solvent.
  • a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc. is preferable because the solubility of the resist film can be easily adjusted.
  • examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-.
  • Heptanone 1-hexanone, 2-hexanone, diisobutylketone, 2,5-dimethyl-4-hexanone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, Examples thereof include acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate, and diisobutyl ketone or 2,5-dimethyl-4-hexanone is preferable.
  • a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
  • octane for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
  • a plurality of the above solvents may be mixed, or a solvent other than the above, or water may be mixed.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total mass of the developer. Mass% is particularly preferred.
  • the developer may contain an appropriate amount of a known surfactant, if necessary.
  • the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution. ..
  • the developer may contain a basic compound.
  • the basic compound include compounds exemplified as acid diffusion control agents that can be contained in the resist composition described later.
  • a solvent represented by the following general formula (S1) or the following general formula (S2) is also preferable.
  • the ester solvent the solvent represented by the general formula (S1) is more preferable, alkyl acetate is more preferable, and butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isoamyl acetate) is particularly preferable.
  • R and R' in the general formula (S1), R and R'independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom.
  • R and R' may combine with each other to form a ring.
  • the alkyl group represented by R and R', the alkoxyl group, and the alkoxycarbonyl group preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
  • the alkyl group represented by R and R', the cycloalkyl group, the alkoxyl group, the alkoxycarbonyl group, and the ring formed by bonding R and R'to each other may have a substituent. ..
  • the substituent is not particularly limited, and examples thereof include a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, an alkoxycarbonyl, etc.), a cyano group, and the like.
  • R and R' preferably a hydrogen atom or an alkyl group.
  • Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate.
  • examples thereof include isopropyl acid acid, methyl 2-hydroxypropionate, and ethyl 2-hydroxypropionate.
  • alkyl acetate is preferable, butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isoamyl acetate) is more preferable, and isoamyl acetate is even more preferable.
  • the developer may further contain one or more other organic solvents (hereinafter, also referred to as “combined solvent”).
  • the combined solvent is not particularly limited as long as it can be mixed with the solvent represented by the general formula (S1) without separation, and is an ester solvent, a ketone solvent, or an alcohol solvent other than the solvent represented by the general formula (S1). , Amid solvent, ether solvent, and solvent selected from the group consisting of hydrocarbon solvent.
  • the combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
  • the mass ratio of the content of the solvent represented by the general formula (S1) to the combined solvent [general formula]
  • the mass of the solvent represented by (S1) / the mass of the combined solvent] is usually 20/80 to 99/1, preferably 50/50 to 97/3, and more preferably 60/40 to 95/5. It is preferable, and 60/40 to 90/10 is more preferable.
  • a solvent represented by the following general formula (S2) is also preferable.
  • R'' and R'''' are independently hydrogen atoms, alkyl groups, cycloalkyl groups, alkoxyl groups, alkoxycarbonyl groups, carboxyl groups, hydroxyl groups, cyano groups, or Represents a halogen atom.
  • R'' and R'''' may be combined with each other to form a ring.
  • a hydrogen atom or an alkyl group is preferable.
  • the alkyl group represented by R'' and R'''', the alkoxyl group, and the alkoxycarbonyl group preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
  • R ′ ′′ represents an alkylene group or a cycloalkylene group, and an alkylene group is preferable.
  • the alkylene group represented by R ′′ ′′ preferably has 1 to 10 carbon atoms
  • the cycloalkylene group represented by R ′′ ′′ preferably has 3 to 10 carbon atoms.
  • the alkylene group represented by R ′′ may have an ether bond in the alkylene chain.
  • the ring formed by bonding R'''' to each other may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, an alkoxycarbonyl, etc.), a cyano group, and the like.
  • Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, and diethylene glycol monomethyl.
  • Ether acetate diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl -3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl Acetate, 3-Methyl-3-methoxybutyl acetate, 3-Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl a
  • propylene glycol monomethyl ether acetate is preferable.
  • R'' and R'''' are unsubstituted alkyl groups
  • R'''' is an unsubstituted alkylene group
  • R'' and R'''' are methyl groups.
  • an ethyl group is more preferable, and R'' and R'''' are even more preferably a methyl group.
  • the developing solution may further contain one or more kinds of combined solvents.
  • the combined solvent is not particularly limited as long as it can be mixed with the solvent represented by the general formula (S2) without being separated, and is an ester solvent, a ketone solvent, or an alcohol solvent other than the solvent represented by the general formula (S2). , Amid solvent, ether solvent, and solvent selected from the group consisting of hydrocarbon solvent.
  • the combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
  • the mass ratio of the content of the solvent represented by the general formula (S2) to the combined solvent [general formula]
  • the mass of the solvent represented by (S2) / the mass of the combined solvent] is usually 20/80 to 99/1, preferably 50/50 to 97/3, and more preferably 60/40 to 95/5. It is preferable, and 60/40 to 90/10 is more preferable.
  • an ether solvent containing one or more aromatic rings is preferable, a solvent represented by the following general formula (S3) is more preferable, and anisole is further preferable.
  • RS represents an alkyl group.
  • the alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
  • a water-based alkaline developer may be used as the developer (other developer).
  • the rinsing step is a step of washing (rinsing) with a rinsing liquid after the above-mentioned developing step.
  • the cleaning treatment method is not particularly limited.
  • a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary discharge method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time.
  • a method (dip method), a method of spraying a rinse liquid on the surface of the substrate (spray method), etc. can be applied.
  • the cleaning treatment is performed by the rotary discharge method, and the substrate is rotated at 2000 to 4000 rpm after cleaning. It is preferable to remove the rinse liquid from the substrate by rotating with.
  • the rinsing time is preferably 10 to 300 seconds, more preferably 10 to 180 seconds, and even more preferably 20 to 120 seconds.
  • the temperature of the rinsing liquid is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • the rinsing liquid As the rinsing liquid, the above-mentioned treatment liquid may be used, or other rinsing liquid may be used. Examples of other rinsing solutions include the above-mentioned other developing solutions and water.
  • a treatment of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid can be performed.
  • a drying treatment may be carried out to remove the solvent remaining in the pattern.
  • the drying temperature is preferably 40 to 160 ° C, more preferably 50 to 150 ° C, and even more preferably 50 to 110 ° C.
  • the drying time is preferably 15 to 300 seconds, more preferably 15 to 180 seconds.
  • the treatment liquid of the present invention is used as at least one of the developing solution and the rinsing solution. Above all, it is preferable that the treatment liquid of the present invention is used as a rinsing liquid.
  • the developing solution and the rinsing solution are supplied to the resist film after exposure. It is preferable to leave an interval of 1 second or more.
  • the developer and the rinse liquid are stored in a common waste liquid tank through a pipe after use.
  • an ester solvent is used as the developing solution in the developing process and the treatment solution of the present invention is used as the rinsing solution in the rinsing process
  • the resist dissolved in the developing solution is precipitated, and the back surface of the substrate and the piping It may adhere to the side surface or the like and stain the device.
  • a method of passing through the pipe As a method of passing through the pipe, a method of cleaning the back surface and side surfaces of the substrate with a solvent that dissolves the resist after cleaning with a rinsing liquid and flowing it, or a method of passing a solvent that dissolves the resist without contacting the resist is passed through the pipe. There is a method of flowing.
  • the solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvent used as the developer described above.
  • propylene glycol monomethyl ether acetate PGMEA
  • propylene glycol monoethyl ether acetate propylene glycol monopropyl ether acetate
  • propylene glycol monobutyl ether acetate propylene glycol monomethyl ether propionate
  • propylene glycol monoethyl ether propionate propylene glycol monoethyl ether propionate
  • the developing solution and the rinsing liquid flowing in the pipe after use are used.
  • examples thereof include a method of adjusting the amount ratio so that the resist does not precipitate, and a method of further mixing a solvent having a high solubility in the resist with the developing solution and the rinsing solution which are passed through the pipe after use.
  • a fluorosolvent contained in the treatment liquid of the present invention and / or an organic solvent having a higher SP value than the second solvent is continuously applied to the back surface of the wafer.
  • a method of suppressing the precipitation / precipitation of the resist in the waste liquid flowing to the waste liquid tank through the pipe after use can be mentioned.
  • the developer and the rinse liquid are stored in separate waste liquid tanks after use.
  • the developer and the rinse liquid are stored in separate waste liquid tanks after use.
  • the developer and the rinse liquid are stored in separate waste liquid tanks after use by switching the piping or by switching the treatment chamber.
  • the inside of the treatment chamber is washed with a solvent having a higher SP value than the fluorine-based solvent contained in the treatment liquid of the present invention after the treatment in order to remove the resist component that may adhere to the inside of the treatment chamber.
  • the resist composition used in combination with the treatment liquid of the present invention may be a so-called chemically amplified resist composition containing, for example, a resin, a photoacid generator, and / or an acid diffusion control agent.
  • a molecular resist composition containing a low-molecular-weight phenol compound instead of the resin may be used, or a metal resist composition containing a metal oxide-based compound may be used. It may be a thing.
  • the resist composition may be a negative type resist composition or a positive type resist composition.
  • a chemically amplified resist composition which is a form of a resist composition that can be used in combination with the treatment liquid of the present invention, will be described in detail. In the following, the chemical amplification type resist composition is referred to, and is also simply referred to as a resist composition.
  • the resist composition contains a resin (hereinafter, also referred to as "acid-decomposable resin” or "resin (A)”) which is decomposed by the action of an acid to increase the polarity. That is, in the pattern forming method, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative type is formed. The pattern is preferably formed.
  • the resin (A) usually contains a group that is decomposed by the action of an acid and whose polarity is increased (hereinafter, also referred to as “acid-degradable group”), and preferably contains a repeating unit having an acid-decomposable group.
  • An acid-degradable group is a group that is decomposed by the action of an acid to form a polar group.
  • the acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, the resin (A) has a repeating unit having a group which is decomposed by the action of an acid to produce a polar group.
  • the polarity of the resin having this repeating unit is increased by the action of the acid, the solubility in the alkaline developer is increased, and the solubility in the organic solvent is decreased.
  • an alkali-soluble group is preferable, and for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene.
  • alkylsulfonyl alkylcarbonyl imide group
  • bis (alkylcarbonyl) methylene group bis (alkylcarbonyl) imide group
  • bis (alkylsulfonyl) methylene group bis (alkylsulfonyl) imide group
  • tris alkylcarbonyl
  • Examples thereof include an acidic group such as a methylene group and a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
  • a carboxyl group a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
  • Rx 1 to Rx 3 are independently an alkyl group (linear or branched chain), a cycloalkyl group (monocyclic or polycyclic), and an alkenyl group (straight chain). (Mole or branched chain) or aryl group (monocyclic or polycyclic).
  • Rx 1 to Rx 3 are alkyl groups (linear or branched chain)
  • Rx 1 to Rx 3 preferably independently represent a linear or branched alkyl group
  • Rx 1 to Rx 3 each independently represent a linear alkyl group. preferable.
  • Rx 1 to Rx 3 may be combined to form a monocyclic ring or a polycyclic ring.
  • alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like.
  • the polycyclic cycloalkyl group of is preferred.
  • the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • a vinyl group is preferable.
  • a cycloalkyl group is preferable as the ring formed by combining two of Rx 1 to Rx 3.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododeca.
  • a polycyclic cycloalkyl group such as an nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group.
  • one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • the group represented by the formula (Y1) or the formula (Y2) is, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group. Is preferable.
  • R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be combined with each other to form a ring.
  • the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R 36 is a hydrogen atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group.
  • R 38 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring.
  • the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
  • L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined).
  • .. M represents a single bond or a divalent linking group.
  • Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, and an aldehyde.
  • the alkyl group and the cycloalkyl group for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.
  • one of L 1 and L 2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
  • L 2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group.
  • the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group
  • examples of the tertiary alkyl group include a tert-butyl group and an adamantane group.
  • Tg glass transition temperature
  • activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may combine with each other to form a non-aromatic ring.
  • Ar is preferably an aryl group.
  • the non-aromatic ring in the non-aromatic ring in the non-aromatic ring. It is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.
  • Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, and 1,1,4.
  • a cyclohexyl group having a substituent (alkyl group, etc.) such as 4-tetramethylcyclohexyl group may be used.
  • repeating unit having an acid-decomposable group As the repeating unit having an acid-decomposable group, the repeating unit represented by the formula (A) is also preferable.
  • L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom
  • R 1 may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, or an iodine atom. It represents an alkyl group or an aryl group which may have a fluorine atom or an iodine atom
  • R 2 represents a desorbing group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
  • at least one of L 1 , R 1 , and R 2 has a fluorine atom or an iodine atom.
  • L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom.
  • the fluorine atom or an iodine atom divalent linking group may have, -CO -, - O -, - S -, - SO -, - SO 2 -, a fluorine atom, or a iodine atom Yes Examples thereof include a hydrocarbon group which may be used (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.), a linking group in which a plurality of these groups are linked, and the like.
  • the L 1, -CO-, or, - arylene - fluorine atom or an alkylene group having iodine atom - are preferred.
  • the arylene group a phenylene group is preferable.
  • the alkylene group may be linear or branched.
  • the number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
  • R 1 represents a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, an alkyl group which may have an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
  • the alkyl group may contain a hetero atom such as an oxygen atom other than the halogen atom.
  • R 2 represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
  • Rx 11 to Rx 13 are alkyl groups (linear or branched), fluorine atoms or iodine atoms which may independently have a fluorine atom or an iodine atom, respectively.
  • a cycloalkyl group (monocyclic or polycyclic) that may have a fluorine atom or an alkenyl group that may have a fluorine atom or an iodine atom (linear or branched chain), or a fluorine atom or an iodine atom.
  • Rx 11 to Rx 13 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 11 to Rx 13 are methyl groups.
  • Rx 11 to Rx 13 are the same as Rx 1 to Rx 3 in (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and are an alkyl group or a cycloalkyl group.
  • Alkyl group, and aryl group are the same as the definition and preferred range.
  • R 136 to R 138 each independently represent a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.
  • R 137 and R 138 may be combined with each other to form a ring.
  • the monovalent organic group which may have a fluorine atom or an iodine atom includes an alkyl group which may have a fluorine atom or an iodine atom, and a cycloalkyl group which may have a fluorine atom or an iodine atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
  • R 138 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring.
  • the group formed by bonding R 138 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
  • L 11 and L 12 each independently may have a hetero atom selected from the group consisting of a hydrogen atom; a fluorine atom, an iodine atom, and an oxygen atom; an alkyl group; a fluorine atom, an iodine.
  • a cycloalkyl group which may have a hetero atom selected from the group consisting of an atom and an oxygen atom; having a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.
  • a combination of an alkyl group and a cycloalkyl group which may have a hetero atom selected from the group consisting of an aryl group; or a group combining these (for example, a fluorine atom, an iodine atom, and an oxygen atom).
  • M 1 represents a single bond or a divalent linking group.
  • Q 1 may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.
  • Cycloalkyl group which may have a heteroatom; aryl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an amino group; an ammonium group; a mercapto group.
  • An alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of a cyano group; an aldehyde group; or a group combining these (for example, a fluorine atom, an iodine atom, and an oxygen atom). Represents a group that combines.
  • Ar 1 represents an aromatic ring group which may have a fluorine atom or an iodine atom.
  • Rn 1 may have an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl which may have a fluorine atom or an iodine atom.
  • Rn 1 and Ar 1 may be combined with each other to form a non-aromatic ring.
  • a repeating unit having an acid-decomposable group a repeating unit represented by the general formula (AI) is also preferable.
  • Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 are independently alkyl groups (linear or branched), cycloalkyl groups (monocyclic or polycyclic), alkenyl groups (linear or branched), or aryl (linear or branched). Represents a monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, etc.).
  • R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, and for example, an alkyl group having 5 or less carbon atoms, which may be substituted by the halogen atom, or a halogen atom is substituted.
  • Examples thereof include an acyl group having 5 or less carbon atoms and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable.
  • Xa 1 a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
  • Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -O-Rt- group and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a -COO-Rt- group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH 2- group,- (CH 2 ) 2- group, or- (CH 2 ) 3- Groups are more preferred.
  • Examples of the alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the polycyclic cycloalkyl group of is preferred.
  • the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • alkenyl group of Rx 1 to Rx 3 a vinyl group is preferable.
  • a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used.
  • Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • Rx 1 is a methyl group or an ethyl group
  • Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
  • the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • the repeating unit represented by the general formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. It is a repeating unit that represents.
  • the content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, more preferably 30 mol% or more, based on all the repeating units in the resin (A). More than mol% is particularly preferable.
  • the upper limit thereof is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol%.
  • Xa 1 represents any of H, CH 3 , CF 3 , and CH 2 OH
  • Rxa and Rxb represent linear or branched-chain alkyl groups having 1 to 5 carbon atoms, respectively. ..
  • the resin (A) may contain a repeating unit other than the repeating unit described above.
  • the resin (A) contains at least one repeating unit selected from the group consisting of the following groups A and / or at least one repeating unit selected from the group consisting of the following groups B. You may. Group A: A group consisting of the following repeating units (20) to (29).
  • Represented repeating unit (29) The repeating unit represented by the formula (E), which will be described later, Group B: A group consisting of the following repeating units (30) to (32).
  • (30) A repeating unit having at least one group selected from a lactone group, a sulton group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, which will be described later.
  • a repeating unit (32) that does not exhibit acid decomposition property which will be described later, is a repeating unit represented by the general formula (III) that does not have either a hydroxyl group or a cyano group.
  • the resin (A) When the resist composition is used for EUV exposure or electron beam exposure, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above group A.
  • the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
  • the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) may have one repeating unit. It may contain two kinds of a repeating unit having a fluorine atom and a repeating unit containing an iodine atom.
  • the resin (A) when the resist composition is used for EUV exposure or electron beam exposure, it is also preferable that the resin (A) has a repeating unit having an aromatic group.
  • the resin (A) preferably has at least one repeating unit selected from the group consisting of group B.
  • the resin (A) preferably contains neither fluorine atoms nor silicon atoms. Further, when the composition is used for ArF applications, the resin (A) preferably has no aromatic group.
  • the resin (A) may have a repeating unit having an acid group.
  • an acid group having a pKa of 13 or less is preferable.
  • the acid group for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, an isopropanol group and the like are preferable.
  • one or more (preferably one or two) fluorine atoms may be substituted with a group other than the fluorine atom (alkoxycarbonyl group or the like).
  • -C (CF 3 ) (OH) -CF 2- thus formed is also preferable as an acid group.
  • one or more of the fluorine atoms may be substituted with a group other than the fluorine atom to form a ring containing ⁇ C (CF 3 ) (OH) ⁇ CF 2-.
  • the repeating unit having an acid group is a repeating unit having a structure in which a polar group is protected by a leaving group desorbed by the action of the above-mentioned acid, and a repeating unit having a lactone group, a sulton group or a carbonate group described later. It is preferably a repeating unit different from the unit.
  • the repeating unit having an acid group may have a fluorine atom or an iodine atom.
  • the repeating unit represented by the formula (B) is preferable.
  • R 3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.
  • the fluorine atom or an organic group may monovalent optionally having iodine atom, a group represented by -L 4 -R 8 are preferred.
  • L 4 represents a single bond or ester group.
  • R 8 is an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, and the like. Alternatively, a group combining these can be mentioned.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.
  • L 2 represents a single bond or an ester group.
  • L 3 represents a (n + m + 1) -valent aromatic hydrocarbon ring group or a (n + m + 1) -valent alicyclic hydrocarbon ring group.
  • the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group.
  • the alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
  • R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).
  • L 3 is preferably an aromatic hydrocarbon ring group having a (n + m + 1) valence.
  • R 7 represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • m represents an integer of 1 or more.
  • n represents an integer of 0 or 1 or more.
  • n is preferably an integer of 1 to 4.
  • (n + m + 1) is preferably an integer of 1 to 5.
  • repeating unit having an acid group a repeating unit represented by the following general formula (I) is also preferable.
  • R 41 , R 42 , and R 43 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • R 42 may be bonded to Ar 4 to form a ring, in which case R 42 represents a single bond or an alkylene group.
  • X 4 represents a single bond, -COO-, or -CONR 64-
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 4 represents a single bond or an alkylene group.
  • Ar 4 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with R 42 to form a ring.
  • n represents an integer from 1 to 5.
  • the alkyl groups of R 41 , R 42 , and R 43 in the general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl.
  • Alkyl groups having 20 or less carbon atoms such as groups, octyl groups, and dodecyl groups are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are further preferable.
  • the cycloalkyl groups of R 41 , R 42 , and R 43 in the general formula (I) may be monocyclic or polycyclic. Of these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable.
  • Examples of the halogen atoms of R 41 , R 42 , and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 , and R 43 in the general formula (I) is preferably the same as the alkyl group in R 41 , R 42 , and R 43.
  • Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl group. , Achilloxy group, alkoxycarbonyl group, cyano group, and nitro group.
  • the substituent preferably has 8 or less carbon atoms.
  • Ar 4 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group when n is 1, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a trilene group, a naphthylene group, and an anthracenylene group, or a thiophene ring, a furan ring, or a pyrrole.
  • a divalent aromatic ring group containing a heterocycle such as a ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiazol ring, and a thiazole ring is preferable.
  • the aromatic ring group may have a substituent.
  • (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group can have include R 41 , R 42 , and R 41 in the general formula (I). , R 43 , an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like.
  • R 64 represents a hydrogen atom or an alkyl group
  • the alkyl group for R 64 in, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec Examples thereof include alkyl groups having 20 or less carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
  • X 4 a single bond, -COO-, or -CONH- is preferable, and a single bond, or -COO- is more preferable.
  • the alkylene group for L 4, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and is preferably an alkylene group having 1 to 8 carbon atoms such as octylene group.
  • Ar 4 an aromatic ring group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferable.
  • the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure.
  • Ar 4 is preferably a benzene ring group.
  • the repeating unit represented by the general formula (1) As the repeating unit represented by the general formula (1), the repeating unit represented by the following general formula (1) is preferable.
  • A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
  • R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. If there are, they may be the same or different. When having a plurality of Rs, they may form a ring jointly with each other.
  • a hydrogen atom is preferable as R.
  • a represents an integer of 1 to 3.
  • b represents an integer from 0 to (5-a).
  • the resin contained in the resist composition preferably has a hydroxystyrene-based repeating unit.
  • the hydroxystyrene-based repeating unit include a repeating unit in which A represents a hydrogen atom in the above general formula (1).
  • R represents a hydrogen atom or a methyl group
  • a represents 2 or 3.
  • the content of the repeating unit having an acid group is preferably 5 mol% or more, preferably 10 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is not particularly limited, but is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.
  • the resin (A) may have a repeating unit having a fluorine atom or an iodine atom, in addition to the above-mentioned ⁇ repeating unit having an acid-degradable group >> and ⁇ repeating unit having an acid group >>.
  • the ⁇ repeating unit having a fluorine atom or an iodine atom >> referred to here is ⁇ a repeating unit having a lactone group, a sultone group, or a carbonate group >>, ⁇ a repeating unit having a photoacid generating group >>, etc. It is preferable that the unit is different from other types of repeating units belonging to the group A.
  • the repeating unit represented by the formula (C) is preferable.
  • L 5 represents a single bond or an ester group.
  • R 9 represents an alkyl group which may have a hydrogen atom or a fluorine atom or an iodine atom.
  • R 10 may have an alkyl group which may have a hydrogen atom, a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom.
  • the repeating unit having a fluorine atom or an iodine atom is illustrated below.
  • the content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.
  • the repeating unit having a fluorine atom or the iodine atom does not include ⁇ repeating unit having an acid-degradable group >> and ⁇ repeating unit having an acid group >>, the above-mentioned fluorine atom.
  • the content of the repeating unit having an iodine atom is also intended to be the content of the repeating unit having a fluorine atom or an iodine atom excluding ⁇ repeating unit having an acid-degradable group >> and ⁇ repeating unit having an acid group >>. do.
  • the total content of the repeating units containing at least one of a fluorine atom and an iodine atom is preferably 20 mol% or more, preferably 30 mol%, based on all the repeating units of the resin (A).
  • the above is more preferable, and 40 mol% or more is further preferable.
  • the upper limit is not particularly limited, but is, for example, 100 mol% or less.
  • the repeating unit containing at least one of a fluorine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom or an iodine atom and having an acid-degradable group, a fluorine atom or an iodine atom, and Examples thereof include a repeating unit having an acid group and a repeating unit having a fluorine atom or an iodine atom.
  • the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, collectively, a repeating unit having a lactone group, a sultone group, or a carbonate group). It may also have a "unit"). It is also preferable that the repeating unit having a lactone group, a sultone group, or a carbonate group does not have an acid group such as a hexafluoropropanol group.
  • the lactone group or sultone group may have a lactone structure or a sultone structure.
  • the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
  • a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo structure or a spiro structure or a 5- to 7-membered ring in the form of a bicyclo structure or a spiro structure.
  • a sultone structure in which another ring structure is fused is more preferable.
  • the resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atom of the represented sultone structure. Further, a lactone group or a sultone group may be directly bonded to the main chain. For example, a ring-membered atom of a lactone group or a sultone group may form the main chain of the resin (A).
  • the lactone structure or sultone structure portion may have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like.
  • n2 represents an integer of 0 to 4. When n2 is 2 or more, Rb 2 existing in plural numbers may be different or may be bonded to form a ring Rb 2 between the plurality of.
  • Examples of the repeating unit having the above include a repeating unit represented by the following general formula (AI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab is a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
  • Ab 1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornene group is preferable.
  • V is a group formed by extracting one hydrogen atom from a ring member atom having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or a general formula (SL1-1) to V. It represents a group formed by extracting one hydrogen atom from a ring member atom having a sultone structure represented by any one of (SL1-3).
  • any optical isomer may be used. Further, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
  • a cyclic carbonate group is preferable.
  • a repeating unit having a cyclic carbonate group a repeating unit represented by the following general formula (A-1) is preferable.
  • RA 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • n represents an integer greater than or equal to 0.
  • RA 2 represents a substituent. when n is 2 or more, R A 2 existing in plural, may each be the same or different.
  • A represents a single bond or a divalent linking group.
  • the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof.
  • the valence group is preferred.
  • Z represents an atomic group forming a monocyclic or polycyclic ring with a group represented by —O—CO—O— in the formula.
  • the repeating unit having a lactone group, a sultone group, or a carbonate group is illustrated below.
  • the content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit thereof is not particularly limited, but is preferably 65 mol% or less, more preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 20 mol% or less.
  • the resin (A) may have a repeating unit having a group that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “photoacid generating group”) as a repeating unit other than the above.
  • the repeating unit having this photoacid-generating group corresponds to a compound that generates an acid by irradiation with active light or radiation described later (hereinafter, also referred to as “photoacid generator”).
  • Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
  • R 41 represents a hydrogen atom or a methyl group.
  • L 41 represents a single bond or a divalent linking group.
  • L 42 represents a divalent linking group.
  • R 40 represents a structural site that is decomposed by irradiation with active light or radiation to generate an acid in the side chain.
  • the repeating unit having a photoacid generating group is illustrated below.
  • examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327.
  • the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.
  • the resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
  • the repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.
  • R 6 and R 7 are independently hydrogen atom, hydroxyl group, alkyl group, alkoxy group, asyloxy group, cyano group, nitro group, amino group, halogen atom and ester group (-OCOR or -COOR:
  • R is carbon. It represents an alkyl group of numbers 1 to 6 or a fluorinated alkyl group) or a carboxyl group.
  • As the alkyl group a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable.
  • n 3 represents an integer from 0 to 6.
  • n 4 represents an integer from 0 to 4.
  • X 4 is a methylene group, an oxygen atom, or a sulfur atom.
  • the repeating unit represented by the general formula (V-1) or (V-2) is illustrated below.
  • the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern disintegration during development.
  • Tg is preferably greater than 90 ° C, more preferably greater than 100 ° C, even more preferably greater than 110 ° C, and particularly preferably greater than 125 ° C. Since excessively high Tg causes a decrease in the dissolution rate in the developing solution, Tg is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
  • the glass transition temperature (Tg) of the polymer such as the resin (A) is calculated by the following method.
  • the Tg of a homopolymer composed of only each repeating unit contained in the polymer is calculated by the Bicerano method.
  • the calculated Tg is referred to as "repeating unit Tg".
  • the mass ratio (%) of each repeating unit to all the repeating units in the polymer is calculated.
  • Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) and summed up to obtain the Tg (° C.) of the polymer.
  • the Bicerano method is described in the Precision of policies, Marcel Dekker Inc, New York (1993) and the like.
  • the calculation of Tg by the Bicerano method can be performed using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
  • the motility of the main chain of the resin (A) In order to increase the Tg of the resin (A) (preferably, Tg exceeds 90 ° C.), it is preferable to reduce the motility of the main chain of the resin (A).
  • Examples of the method for reducing the motility of the main chain of the resin (A) include the following methods (a) to (e).
  • (A) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between the resins (A) in the vicinity of the main chain ( d) Main chain formation in a cyclic structure (e) Connection of a cyclic structure to the main chain
  • the resin (A) preferably has a repeating unit in which the Tg of the homopolymer is 130 ° C. or higher.
  • the type of repeating unit having a homopolymer Tg of 130 ° C. or higher is not particularly limited, and any repeating unit having a homopolymer Tg of 130 ° C. or higher calculated by the Bicerano method may be used.
  • the homopolymer corresponds to the repeating unit having a Tg of 130 ° C. or higher.
  • the formula (A) and RA represent a group having a polycyclic structure.
  • R x represents a hydrogen atom, a methyl group, or an ethyl group.
  • the group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed.
  • Specific examples of the repeating unit represented by the formula (A) include the following repeating units.
  • R represents a hydrogen atom, a methyl group, or an ethyl group.
  • Ra is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group (-OCOR'''.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced with a fluorine atom or an iodine atom.
  • R'and R'' are independently alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, asyloxy group, cyano group, nitro group, amino group, halogen atom, respectively.
  • R ′′ ′′ is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by R'and R' may be replaced with a fluorine atom or an iodine atom.
  • L represents a single bond or a divalent linking group.
  • Examples of the divalent linking group include -COO-, -CO- , -O-, -S-, -SO-, -SO 2- , an alkylene group, a cycloalkylene group, an alkaneylene group, and a plurality of these.
  • Examples thereof include a linking group in which is linked.
  • m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are often 2 or less and more often 1 or less.
  • R b1 to R b4 independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
  • the types of other organic groups are not particularly limited.
  • at least two or more organic groups are substituted in which the number of constituent atoms excluding hydrogen atoms is three or more. It is a group.
  • repeating unit represented by the formula (B) include the following repeating units.
  • R independently represents a hydrogen atom or an organic group.
  • the organic group include an organic group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
  • R' is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR'.
  • R'' represents an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
  • m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
  • R c1 to R c4 independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a hydrogen-bonding hydrogen within 3 atoms from the main chain carbon. It is a group having an atom. Among them, in order to induce the interaction between the main chains of the resin (A), it is preferable to have hydrogen-bonding hydrogen atoms within 2 atoms (closer to the main chain).
  • repeating unit represented by the formula (C) include the following repeating units.
  • R represents an organic group.
  • the organic group may have a substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR:
  • R has 1 to 20 carbon atoms.
  • R' represents a hydrogen atom or an organic group.
  • Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like.
  • the hydrogen atom in the organic group may be replaced with a fluorine atom or an iodine atom.
  • cylic represents a group forming a main chain with a cyclic structure.
  • the number of constituent atoms of the ring is not particularly limited.
  • repeating unit represented by the formula (D) include the following repeating units.
  • R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and the like.
  • the ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
  • R' is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group.
  • R ′′ represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
  • m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
  • Re independently represents a hydrogen atom or an organic group.
  • the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like, which may have a substituent.
  • Cylic is a cyclic group containing a carbon atom in the main chain. The number of atoms contained in the cyclic group is not particularly limited.
  • repeating unit represented by the formula (E) include the following repeating units.
  • R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen. It represents an atom, an ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
  • R' is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group.
  • R is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
  • the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
  • m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
  • the two Rs may be bonded to each other to form a ring.
  • the content of the repeating unit represented by the formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.
  • the resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
  • the resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
  • Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating unit described in the above-mentioned ⁇ Repeating unit having a lactone group, sultone group, or carbonate group >>.
  • the preferred content is also as described above in ⁇ Repeating unit having a lactone group, sultone group, or carbonate group >>.
  • the resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.
  • the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
  • the repeating unit having a hydroxyl group or a cyano group preferably has no acid-degradable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIA) to (AIId).
  • R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydrochimethyl group.
  • R 2c to R 4c independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R 2c to R 4c represents a hydroxyl group or a cyano group.
  • one or two are hydroxyl groups and the rest are hydrogen atoms. More preferably, of R 2c to R 4c , two are hydroxyl groups and the rest are hydrogen atoms.
  • the content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.
  • repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
  • the resin (A) may have a repeating unit having an alkali-soluble group.
  • the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol in which the ⁇ -position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group).
  • a carboxyl group is preferred.
  • the repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or a repeating unit in which the alkali-soluble group is directly bonded to the main chain of the resin via a linking group. Repeat units to which an alkali-soluble group is attached can be mentioned.
  • the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
  • a repeating unit made of acrylic acid or methacrylic acid is preferable.
  • the content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, based on all the repeating units in the resin (A).
  • the upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less.
  • Rx represents H, CH 3 , CH 2 OH, or CF 3 .
  • a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group as a repeating unit having at least one kind selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group.
  • a repeating unit having a cyano group and a lactone group is more preferable, and a repeating unit having a structure in which a cyano group is substituted with a lactone structure represented by the general formula (LC1-4) is further preferable.
  • the resin (A) may have an alicyclic hydrocarbon structure and may have a repeating unit that does not exhibit acid decomposition. This makes it possible to reduce the elution of small molecule components from the resist film to the immersion liquid during immersion exposure.
  • Such repeating units include, for example, 1-adamantyl (meth) acrylate-derived repeating units, diamantyl (meth) acrylate-derived repeating units, tricyclodecanyl (meth) acrylate-derived repeating units, and cyclohexyl (meth). Examples include repeating units derived from acrylate.
  • the resin (A) may have a repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group.
  • R 5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
  • Ra represents a hydrogen atom, an alkyl group, or, -CH 2 -O-Ra 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
  • the cyclic structure of R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
  • the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.
  • Examples of the polycyclic hydrocarbon group include a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group.
  • Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring.
  • the crosslinked cyclic hydrocarbon ring also includes a fused ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
  • Examples of the crosslinked cyclic hydrocarbon group, a norbornyl group, an adamantyl group, a bicyclooctanyl group, or, tricyclo [5,2,1,0 2,6] decanyl group are preferred, norbornyl group or more preferably an adamantyl group.
  • the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. ..
  • a halogen atom a bromine atom, a chlorine atom, or a fluorine atom is preferable.
  • the alkyl group a methyl group, an ethyl group, a butyl group, or a t-butyl group is preferable.
  • the alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.
  • Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
  • the alkyl group an alkyl group having 1 to 4 carbon atoms is preferable.
  • the substituted methyl group a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, or a 2-methoxyethoxymethyl group is preferable.
  • a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group is preferable.
  • the acyl group an aliphatic acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a pivaloyl group is preferable.
  • an alkoxycarbonyl group an alkoxycarbonyl group having 1 to 4 carbon atoms is preferable.
  • the content of the repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group, is preferably 0 to 40 mol%, preferably 0 to 20 mol%, based on all the repeating units in the resin (A). More preferably mol%.
  • Specific examples of the repeating unit represented by the general formula (III) are given below, but the present invention is not limited thereto.
  • Ra represents H, CH 3 , CH 2 OH, or CF 3 .
  • the resin (A) may have a repeating unit other than the repeating unit described above.
  • the resin (A) is a repeating unit selected from the group consisting of a repeating unit having an oxazolone ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may have. Such repeating units are illustrated below.
  • the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. You may have.
  • all of the repeating units are composed of (meth) acrylate-based repeating units.
  • all of the repeating units are methacrylate-based repeating units
  • all of the repeating units are acrylate-based repeating units
  • all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. It can be used, and the acrylate-based repeating unit is preferably 50 mol% or less of all the repeating units.
  • the resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight of the resin (A) is preferably 1000 to 200,000, more preferably 3000 to 20000, and even more preferably 5000 to 15000.
  • the dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern.
  • the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.
  • the solid content is intended to be a component of the composition excluding the solvent, and any component other than the solvent is regarded as a solid content even if it is a liquid component.
  • the resin (A) may be used alone or in combination of two or more.
  • the chemically amplified resist composition preferably contains a compound that generates an acid by active light or radiation (hereinafter, also referred to as "photoacid generator (PAG)").
  • the photoacid generator may be in the form of a small molecule compound or may be incorporated into a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
  • the photoacid generator is in the form of a small molecule compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the photoacid generator When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A).
  • the photoacid generator is preferably in the form of a small molecule compound.
  • the photoacid generator is not particularly limited as long as it is known, but organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and bis (alkylsulfonyl) imide can be obtained by irradiation with active light or radiation, preferably electron beam or extreme ultraviolet light.
  • a compound that produces at least one of tris (alkylsulfonyl) methides is preferred. More preferably, the compound represented by the following general formula (ZI), the compound represented by (ZII), and the compound represented by (ZIII) can be mentioned.
  • R 201 , R 202, and R 203 each independently represent an organic group.
  • the carbon number of the organic group as R 201 , R 202 , and R 203 is preferably 1 to 30, and more preferably 1 to 20.
  • two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (for example, a butylene group and a pentylene group).
  • Z - represents a non-nucleophilic anion (anion with a significantly lower ability to undergo a nucleophilic reaction).
  • non-nucleophilic anion examples include a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, and camphor sulfonic acid anion, etc.) and a carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion). , And aralkyl carboxylic acid anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
  • the aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and a linear or branched alkyl having 1 to 30 carbon atoms is preferable. Examples thereof include a group and a cycloalkyl group having 3 to 30 carbon atoms.
  • an aryl group having 6 to 14 carbon atoms is preferable.
  • a phenyl group, a tolyl group, a naphthyl group and the like can be mentioned.
  • the alkyl group, cycloalkyl group, and aryl group may have a substituent.
  • substituents include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably 1 to 15 carbon atoms), and cycloalkyl groups (preferably 3 to 15 carbon atoms).
  • Aryl group preferably 6 to 14 carbon atoms
  • alkoxycarbonyl group preferably 2 to 7 carbon atoms
  • acyl group preferably 2 to 12 carbon atoms
  • alkoxycarbonyloxy group preferably 2 to 7 carbon atoms.
  • Alkoxythio group (preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), aryloxysulfonyl group (preferably having 1 to 15 carbon atoms). 6 to 20), alkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably 10 to 20 carbon atoms), alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms) , And a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms) and the like.
  • an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.
  • an aralkyl group having 7 to 12 carbon atoms is preferable.
  • a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like can be mentioned.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion or the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group and the like.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
  • the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions e.g., fluorinated phosphorus (e.g., PF 6 -), fluorinated boron (e.g., BF 4 -), and, fluorinated antimony (e.g., SbF 6 -) and the like is ..
  • fluorinated phosphorus e.g., PF 6 -
  • fluorinated boron e.g., BF 4 -
  • fluorinated antimony e.g., SbF 6 -
  • non-nucleophilic anion examples include an aliphatic sulfonic acid anion in which at least the ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the fluorine atom or a group having a fluorine atom is substituted, and an alkyl group is a fluorine atom.
  • Bis (alkylsulfonyl) imide anions substituted with, and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred.
  • non-nucleophilic anion a perfluoroaliphatic sulfonic acid anion (preferably 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom is more preferable, and a nonafluorobutane sulfonic acid anion and a perfluorooctane sulfonic acid are used.
  • Anions, pentafluorobenzene sulfonic acid anions, or 3,5-bis (trifluoromethyl) benzene sulfonic acid anions are more preferred.
  • the pKa of the generated acid is preferably -1 or less.
  • an anion represented by the following general formula (AN1) is also mentioned as a preferable embodiment.
  • Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R 1 and R 2 may be the same or different, respectively.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the general formula (AN1) will be described in more detail.
  • the number of carbon atoms of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4.
  • the alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferable.
  • Specific examples of Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH.
  • the alkyl groups of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably have 1 to 4 carbon atoms. Among them, the alkyl groups of R 1 and R 2 are preferably perfluoroalkyl groups having 1 to 4 carbon atoms. Specific examples of alkyl groups having substituents on R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 and C 7 F 15.
  • C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 and CH 2 CH 2 C 4 F 9 can be mentioned.
  • CF 3 is preferable.
  • R 1 and R 2 a fluorine atom or CF 3 is preferable.
  • x is preferably 1 to 10, more preferably 1 to 5.
  • y is preferably 0 to 4, more preferably 0.
  • z is preferably 0 to 5, more preferably 0 to 3.
  • the divalent linking group of L is not particularly limited, and is: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene group, cycloalkylene group, Examples thereof include an alkaneylene group and a linking group in which a plurality of these groups are linked. Of these, a linking group having a total carbon number of 12 or less is preferable. Further, -COO-, -OCO-, -CO-, or -O- is preferable, and -COO- or -OCO- is more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and has an alicyclic group, an aryl group, and a heterocyclic group (not only those having aromaticity but also aromaticity). (Including those that do not), etc.
  • the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, or a norbornyl group, a tricyclodecanyl group, or a tetracyclodecanyl group.
  • Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
  • alicyclic groups having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are used in the post-exposure heating step. It is preferable from the viewpoint of improving MEEF (maskeror enhancement factor) because it can suppress the diffusivity in the membrane.
  • MEEF mask enhancement factor
  • Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
  • Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring, or a pyridine ring are preferable.
  • examples of the cyclic organic group include a lactone structure, and specific examples thereof include lactone structures represented by the following general formulas (LC1-1) to (LC1-17).
  • the cyclic organic group may have a substituent, and the substituent may be any of an alkyl group (linear, branched, or cyclic, and has 1 to 12 carbon atoms.
  • substituent may be any of an alkyl group (linear, branched, or cyclic, and has 1 to 12 carbon atoms.
  • cycloalkyl group which may be monocyclic, polycyclic, or spiro ring, preferably 3 to 20 carbon atoms
  • aryl group preferably 6 to 14 carbon atoms
  • hydroxy group examples thereof include an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • the substituent corresponds to Rb 2 in the general formulas (LC1-1) to (LC1-17).
  • n2 represents an integer of 0 to 4.
  • Rb 2 existing in plural numbers may be the same or different or may be bonded to form a ring Rb 2 between the plurality of.
  • examples of the organic group of R 201 , R 202 , and R 203 include an aryl group, an alkyl group, a cycloalkyl group, and the like.
  • R 201 , R 202 , and R 203 it is preferable that at least one is an aryl group, and it is more preferable that all three are aryl groups.
  • the aryl group in addition to a phenyl group, a naphthyl group and the like, a heteroaryl group such as an indole residue and a pyrrole residue can also be used.
  • alkyl group and cycloalkyl group of R 201 to R 203 a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms is preferable.
  • alkyl group a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like are preferable.
  • cycloalkyl group a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like are preferable.
  • These groups may further have a substituent.
  • a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms) and a cycloalkyl group (preferably having 1 to 15 carbon atoms). 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), and an alkoxycarbonyloxy.
  • Groups (preferably 2 to 7 carbon atoms) and the like can be mentioned, but the group is not limited thereto.
  • R 204 to R 207 independently represent an aryl group, an alkyl group, or a cycloalkyl group, respectively.
  • aryl group of R 204 to R 207 a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group in R 204 to R 207 include a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group). , Or a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group) is preferable.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). ⁇ 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.
  • Z ⁇ represents a non-nucleophilic anion. Specifically, it is the same as that described as Z ⁇ in the general formula (ZI), and the preferred form is also the same.
  • the photoacid generator has a volume of 130 ⁇ 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution.
  • (more preferably sulfonic acid) in the size of the acid is a compound which generates, more preferably (more preferably sulfonic acid) acid volume 190 ⁇ 3 or more in size is a compound that generates a volume 270 ⁇ 3 It is more preferably a compound that generates an acid having a size of the above size (more preferably a sulfonic acid), and particularly preferably a compound that generates an acid (more preferably a sulfonic acid) having a volume of 400 ⁇ 3 or more.
  • the volume is more preferably preferably 2000 ⁇ 3 or less, is 1500 ⁇ 3 or less.
  • the above volume value was determined using "WinMOPAC" manufactured by Fujitsu Limited.
  • the chemical structure of the acid according to each example is input, then the most stable conformation of each acid is determined by the molecular mechanics field calculation using the MM3 method with this structure as the initial structure, and then the most stable conformation of each acid is determined.
  • the "accessible volume" of each acid can be calculated by calculating the molecular orbital of the stable conformation using the PM3 method.
  • 1 ⁇ means 0.1 nm.
  • a photoacid generator that generates the acids exemplified below by irradiation with active light or radiation is preferable.
  • the calculated value of the volume is added to a part of the example (unit: ⁇ 3 ).
  • the calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion portion.
  • Examples of the photoacid generator include paragraphs [0368] to [0377] of JP2014-41328, and paragraphs [0240] to [0262] of JP2013-228681 (corresponding US Patent Application Publication No. 2015 / Paragraph [0339]) of Gazette No. 004533 can be incorporated, the contents of which are incorporated herein by reference.
  • the following compounds can be mentioned as preferable specific examples, but the present invention is not limited thereto.
  • the photoacid generator may be used alone or in combination of two or more.
  • the content of the photoacid generator in the resist composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and further 8 to 40% by mass, based on the total solid content of the composition. preferable.
  • the content of the photoacid generator is high in order to achieve both high sensitivity and high resolution when exposed to electron beams or extreme ultraviolet rays. From the above viewpoint, 10 to 40% by mass is preferable, and 10 to 35% by mass is more preferable.
  • a solvent can be used when preparing the resist composition by dissolving each of the above-mentioned components.
  • the solvent that can be used include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and a ring having 4 to 10 carbon atoms.
  • organic solvents such as monoketone compounds, alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvate which may be used.
  • alkylene glycol monoalkyl ether carboxylate examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl.
  • examples thereof include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
  • alkylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
  • lactate alkyl ester examples include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.
  • alkyl alkoxypropionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
  • Examples of the cyclic lactone having 4 to 10 carbon atoms include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -.
  • Caprolactone, ⁇ -octanoic lactone, and ⁇ -hydroxy- ⁇ -butyrolactone can be mentioned.
  • Examples of the monoketone compound having 4 to 10 carbon atoms and which may contain a ring include 2-butanone, 3-methylbutanone, pinacone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone and 4-.
  • alkylene carbonate examples include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
  • alkoxyalkyl acetate examples include -2-methoxyethyl acetate, -2-ethoxyethyl acetate, -2- (2-ethoxyethoxy) ethyl acetate, -3-methoxy-3-methylbutyl acetate, and -1-acetic acid. Examples include methoxy-2-propyl.
  • alkyl pyruvate examples include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
  • a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure is preferable.
  • cyclopentanone, ⁇ -butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, ethyl acetate-2-ethoxyethyl, acetate -2- (2-ethoxyethoxy) ethyl and propylene carbonate can be mentioned.
  • the above solvent may be used alone or in combination of two or more.
  • the organic solvent a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used may be used.
  • the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Of these, propylene glycol monomethyl ether or ethyl lactate is preferable.
  • solvent containing no hydroxyl group examples include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, and dimethyl.
  • solvent containing no hydroxyl group examples include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, and dimethyl.
  • examples thereof include sulfoxide.
  • propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, or butyl acetate is preferable
  • propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, or 2-heptanone is preferable.
  • the mass ratio of the content of the solvent containing hydroxyl groups to the solvent containing no hydroxyl groups [mass content of solvent containing hydroxyl groups / mass content of solvent not containing hydroxyl groups] is preferably 1/99 to 99/1, and is preferably 10/90. ⁇ 90/10 is more preferable, and 20/80 to 60/40 is even more preferable.
  • the mass of the solvent containing no hydroxyl group in the mixed solvent is preferably 50% by mass or more.
  • the solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate, and more preferably a combination of ⁇ -butyl lactone and butyl acetate.
  • the solvent for example, the solvents described in paragraphs [0013] to [0029] of JP2014-219664A can also be used.
  • the resist composition preferably contains an acid diffusion control agent in order to reduce the change in performance with time from exposure to heating.
  • Examples of the acid diffusion control agent include basic compounds.
  • Examples of the basic compound include compounds having a structure represented by the following formulas (A1) to (E1).
  • R 200 , R 201 , and R 202 in the general formulas (A1) and (E1) may be the same or different, and may be the same or different, and are a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), and a cycloalkyl group (preferably 1 to 20 carbon atoms). Represents 3 to 20 carbon atoms) or an aryl group (preferably 6 to 20 carbon atoms).
  • R 201 and R 202 may be combined with each other to form a ring.
  • R 203 , R 204 , R 205 , and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (A1) and (E1) are preferably unsubstituted.
  • Compounds having structures represented by the general formulas (A1) to (E1) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin, piperidine, imidazole structure, diazabicyclo structure, and onium hydroxide. Examples thereof include compounds having a structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
  • Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [5, 4,0] Undeca-7-en and the like.
  • Examples of the compound having an onium hydroxide structure include a triarylsulfonium hydroxide, a phenacylsulfonium hydroxide, and a sulfonium hydroxide having a 2-oxoalkyl group.
  • triphenylsulfonium hydroxide tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium. Hydroxyldo and the like can be mentioned.
  • Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Can be mentioned.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
  • Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like.
  • Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
  • examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
  • amine compound primary, secondary and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom.
  • the group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
  • the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • the oxyalkylene group includes an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-).
  • an oxyethylene group is more preferred.
  • ammonium salt compound a primary, secondary, tertiary or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the ammonium salt compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or a cycloalkyl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom.
  • the aryl group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
  • the ammonium salt compound preferably has an oxygen atom in the alkyl chain and has an oxyalkylene group formed therein.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • the oxyalkylene group a group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or CH 2 CH 2 CH 2 O-) is preferable, and oxy Ethylene groups are more preferred.
  • the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate.
  • a halogen atom or a sulfonate is preferable. Chloride, bromide, and iodide are preferable as the halogen atom.
  • an organic sulfonate having 1 to 20 carbon atoms is preferable.
  • alkyl sulfonate having 1 to 20 carbon atoms and aryl sulfonate are preferable.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy group, acyl group, aryl group and the like.
  • alkyl sulphonate examples include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate.
  • aryl group of the aryl sulfonate examples include a benzene ring, a naphthalene ring, and an anthracene ring.
  • the benzene ring, naphthalene ring, and anthracene ring may have a substituent, and the substituent may be a linear or branched alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. Cycloalkyl groups are preferred. As linear or branched alkyl group and cycloalkyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n. -Hexyl group, cyclohexyl group and the like can be mentioned. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group and the like.
  • the amine compound having a phenoxy group or the ammonium salt compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound.
  • the phenoxy group may have a substituent.
  • the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryl.
  • the substituent of the substituent may be any of 2 to 6 positions. The number of substituents may be in the range of 1 to 5.
  • the oxyalkylene group includes an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-).
  • an oxyethylene group is more preferred.
  • the amine compound having a phenoxy group is prepared by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, and then using a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium. After adding the aqueous solution, it is obtained by extraction with an organic solvent such as ethyl acetate and chloroform.
  • a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal are heated and reacted, and then an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium is added. Then, it is obtained by extraction with an organic solvent such as ethyl acetate and chloroform.
  • composition according to the present invention has a proton-accepting functional group as an acid diffusion control agent, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have a proton acceptor property.
  • PA acidic
  • the proton-accepting functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or ⁇ . It means a functional group having a nitrogen atom having an unshared electron pair that does not contribute to conjugation.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.
  • Compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic.
  • the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group.
  • it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
  • Specific examples of the compound (PA) include the following compounds. Further, specific examples of the compound (PA) include, for example, paragraphs [0421] to [0428] of JP-A-2014-014328 and paragraphs [0108]-[0116] of JP-A-2014-134686. The ones described may be incorporated and these contents are incorporated herein by reference.
  • the acid diffusion control agent may be used alone or in combination of two or more.
  • the content of the acid diffusion control agent is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, based on the total solid content of the resist composition.
  • the molar ratio is preferably 2.5 or more, and preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time from exposure to heat treatment.
  • the photoacid generator / acid diffusion control agent (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.
  • Examples of the acid diffusion control agent include the compounds described in paragraphs [0140] to [0144] of JP2013-011833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). Can be used.
  • the resist composition may contain a hydrophobic resin in addition to the resin (A).
  • Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule and polar / non-polar substances are uniformly mixed. It does not have to contribute to.
  • the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgas, and the like.
  • the hydrophobic resin preferably has one or more of fluorine atoms, silicon atoms, and a CH 3-part structure contained in the side chain portion of the resin. It is more preferable to have the above. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.
  • the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.
  • the partial structure having a fluorine atom is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
  • the alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Further, it may have a substituent other than a fluorine atom.
  • the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.
  • the aryl group having a fluorine atom include a phenyl group and a group in which at least one hydrogen atom of an aryl group such as a naphthyl group is substituted with a fluorine atom, and further has a substituent other than the fluorine atom. May be good.
  • Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph [0519] of US2012 / 0251948A1.
  • the hydrophobic resin may also preferably comprise a CH 3 partial structure side chain moiety.
  • the CH 3 partial structure contained in the side chain portion of the hydrophobic resin an ethyl group, and is intended to encompass CH 3 partial structure a propyl group has.
  • the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the ⁇ -methyl group of the repeating unit having a methacrylic acid structure) contributes to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. small order, and it shall not be included in the CH 3 partial structures in the present invention.
  • the resins described in JP-A-2011-24801, JP-A-2010-175859, and / or JP-A-2012-032544 can also be preferably used.
  • the resist composition may further contain a surfactant.
  • a surfactant makes it possible to form a pattern with less adhesion and less development defects with good sensitivity and resolution when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less. ..
  • As the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
  • Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or
  • fluoroaliphatic compounds produced by the telomerization method also called the telomer method
  • the oligomerization method also called the oligomer method
  • a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant.
  • This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991.
  • surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • the surfactant may be used alone or in combination of two or more.
  • the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and 0.0005 to 1 with respect to the total solid content of the composition. Mass% is more preferred.
  • the chemically amplified resist composition is a dissolution-inhibiting compound, a dye, a plasticizing agent, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1000 or less, or a compound. , An alicyclic or aliphatic compound containing a carboxyl group) may be further contained.
  • the resist composition may further contain a dissolution inhibitory compound.
  • a dissolution inhibitory compound is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
  • the treatment liquid of the present invention preferably carries out the following purification steps in order to keep the content of metal components and organic substances having a boiling point of 300 ° C. or higher within a desired range.
  • the purification step may be carried out at any timing.
  • Examples of the purification step include the following purification treatments I to IV. That is, the purification treatment I is a treatment for purifying the raw material used for the production of the organic solvent before the production of the organic solvent contained in the treatment liquid. Further, the purification treatment II is a treatment for purifying the organic solvent contained in the treatment liquid at the time of production and / or after production. Further, the purification treatment III is a treatment in which each component is purified before mixing two or more kinds of organic solvents at the time of producing the treatment liquid. Further, the purification treatment IV is a treatment for purifying the mixture after mixing two or more kinds of organic solvents at the time of producing the treatment liquid.
  • purification may be performed after purifying the individual organic solvents, or may be performed after mixing the respective organic solvents.
  • a method of blending a purified organic solvent is preferable in that the blend ratio of the organic solvent can be produced to be constant.
  • Each of the purification treatments I to IV may be carried out only once or twice or more.
  • the organic solvent to be used high-purity grade products (particularly those having a small content of the above-mentioned organic impurities, metal impurities, water, etc.) are purchased, and further, the purification treatment described later is performed on them. Can be used.
  • the purification target in the purification step is simply collectively referred to as "the liquid to be purified".
  • the purification step for example, a first ion exchange treatment for performing an ion exchange treatment of the liquid to be purified, a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and a distillation for distilling the liquid to be purified after the dehydration treatment.
  • a first ion exchange treatment for performing an ion exchange treatment of the liquid to be purified for example, a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and a distillation for distilling the liquid to be purified after the dehydration treatment.
  • the second ion exchange treatment for performing the ion exchange treatment of the liquid to be purified after the treatment and the distillation treatment and the organic impurity removal treatment for removing the organic impurities of the liquid to be purified after the second ion exchange treatment are carried out in this order.
  • the purification method for preparing the treatment liquid of the present invention is not limited thereto.
  • a dehydration treatment for dehydrating the liquid to be purified is performed, a distillation treatment for distilling the liquid to be purified after the dehydration treatment, a first ion exchange treatment for ion exchange treatment of the liquid to be purified, and a second.
  • the organic impurity removing treatment for removing the organic impurities in the liquid to be purified after the ion exchange treatment may be carried out in this order.
  • an ionic component for example, a metal component
  • a first ion exchange means such as an ion exchange resin is used.
  • the ion exchange resin a cation exchange resin or an anion exchange resin is provided on a single bed, a cation exchange resin and an anion exchange resin are provided on a double bed, and a cation exchange resin and an anion exchange resin are mixed. It may be any of those provided in.
  • the ion exchange resin it is preferable to use a dry resin containing as little water as possible in order to reduce the elution of water from the ion exchange resin.
  • a dry resin a commercially available product can be used, and 15JS-HG / DRY (trade name, dry cation exchange resin, moisture content of 2% or less) manufactured by Organo Corporation and MSPS2-1 / DRY (trade name, mixed).
  • Floor resin moisture content of 10% or less and the like.
  • the dehydration treatment water in the liquid to be purified can be removed. Further, when zeolite described later (particularly, molecular sieve (trade name) manufactured by Union Showa Co., Ltd.) is used in the dehydration treatment, olefins can also be removed.
  • the dehydrating means used for the dehydration treatment include a dehydration film, a water adsorbent insoluble in the liquid to be purified, an aeration replacement device using a dry inert gas, and a heating or vacuum heating device. When a dehydrated membrane is used, membrane dehydration is performed by osmotic vaporization (PV) or vapor permeation (VP).
  • the dehydrated membrane is configured as, for example, a permeable membrane module.
  • a film made of a polymer-based material such as polyimide-based, cellulosic-based, or polyvinyl alcohol-based, or an inorganic-based material such as zeolite can be used.
  • the water adsorbent is used by adding it to the liquid to be purified. Examples of the water adsorbent include zeolite, diphosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, anhydrous zinc chloride, fuming sulfuric acid, soda lime and the like.
  • the distillation means is composed of, for example, a single-stage distillation apparatus. Impurities are concentrated in a distillation apparatus or the like by the distillation treatment, but in order to prevent a part of the concentrated impurities from flowing out, a part of the liquid in which the impurities are concentrated is periodically used in the distillation means. Alternatively, it is preferable to provide means for constantly discharging to the outside.
  • the second ion exchange treatment when impurities accumulated in the distillation apparatus flow out, they can be removed.
  • eluate from pipes such as stainless steel (SUS) used as a liquid feeding line can be removed.
  • the second ion exchange means include a column-shaped container filled with an ion exchange resin and an ion adsorption membrane.
  • an ion adsorption membrane is preferable from the viewpoint of being able to process at a high flow velocity.
  • the ion adsorption membrane include Neocepta (trade name, manufactured by Astom Co., Ltd.).
  • each of the above-mentioned treatments is carried out in a hermetically sealed state and in an atmosphere of an inert gas in which water is unlikely to be mixed in the liquid to be purified.
  • each treatment is preferably performed in an inert gas atmosphere having a dew point temperature of ⁇ 70 ° C. or lower in order to suppress the mixing of water as much as possible. This is because in an inert gas atmosphere of ⁇ 70 ° C. or lower, the water concentration in the gas phase is 2 mass ppm or less, so that the possibility of water being mixed in the liquid to be purified is reduced.
  • Examples of the purification step include, in addition to the above treatment, an adsorption purification treatment of a metal component using silicon carbide, which is described in International Publication No. WO2012 / 043496.
  • the organic impurity removing treatment high boiling point organic impurities and the like (including organic substances having a boiling point of 300 ° C. or higher) that are contained in the liquid to be purified after the distillation treatment and are difficult to remove by the distillation treatment can be removed.
  • the organic impurity removing means for example, it can be carried out by an organic impurity adsorbing member provided with an organic impurity adsorbing filter capable of adsorbing organic impurities.
  • the organic impurity adsorption member is usually configured to include the organic impurity adsorption filter and a base material for fixing the impurity adsorption filter.
  • the organic impurity adsorption filter has an organic substance skeleton capable of interacting with organic impurities on the surface from the viewpoint of improving the adsorption performance of organic impurities (in other words, the surface is modified by the organic substance skeleton capable of interacting with organic impurities. It is preferable.
  • having an organic substance skeleton capable of interacting with organic impurities on the surface means that the surface of the base material constituting the organic impurity adsorption filter described later is provided with the organic substance skeleton capable of interacting with the organic impurities. Take as an example.
  • Examples of the organic substance skeleton capable of interacting with organic impurities include a chemical structure capable of reacting with organic impurities and capturing the organic impurities in an organic impurity adsorption filter. More specifically, when the organic impurity contains dioctyl phthalate, diisononyl phthalate, dioctyl adipate, or dibutyl phthalate, the organic skeleton includes a benzene ring skeleton. When ethylene propylene rubber is contained as the organic impurity, the organic skeleton includes an alkylene skeleton.
  • the organic skeleton includes an alkyl group.
  • the base material (material) constituting the organic impurity adsorption filter include cellulose carrying activated carbon, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.
  • the organic impurity removing filter a filter in which activated carbon described in JP-A-2002-273123 and JP-A-2013-150979 is fixed to a non-woven fabric can also be used.
  • the organic impurity removing treatment is not limited to the mode using the organic impurity adsorption filter capable of adsorbing the organic impurities as described above, and may be, for example, a mode of physically supplementing the organic impurities.
  • Organic impurities having a relatively high boiling point of 250 ° C. or higher are often coarse (for example, compounds having 8 or more carbon atoms), and therefore can be physically supplemented by using a filter having a pore size of about 1 nm. Is.
  • an organic impurity removing filter having a pore diameter of 1 nm dioctyl phthalate cannot pass through the pores of the filter. That is, dioctyl phthalate is physically trapped by the filter and is therefore removed from the liquid to be purified.
  • the removal of organic impurities can be achieved not only by chemical interaction but also by applying a physical removal method.
  • a filter having a pore diameter of 3 nm or more is used as a “filter member” described later, and a filter having a pore diameter of less than 3 nm is used as an “organic impurity removing filter”.
  • the purification step may further include, for example, a purification process V and a purification process VI described later.
  • the purification treatment V and the purification treatment VI may be carried out at any timing, and examples thereof include after the purification treatment IV is carried out.
  • the purification process V is a filtering process using a metal ion adsorbing member for the purpose of removing metal ions.
  • the purification treatment VI is a filtration treatment for removing coarse particles.
  • the purification treatment V and the purification treatment VI will be described.
  • the metal ion adsorption member has a configuration including at least one metal ion adsorption filter, and may have a configuration in which a plurality of metal ion adsorption filters are stacked according to a target purification level.
  • the metal ion adsorption member is usually configured to include the metal ion adsorption filter and a base material for fixing the metal ion adsorption filter.
  • the metal ion adsorption filter has a function of adsorbing metal ions in the liquid to be purified.
  • the metal ion adsorption filter is preferably a filter capable of ion exchange.
  • the metal ion to be adsorbed is not particularly limited, but Fe, Cr, Ni, and Pb are preferable from the viewpoint of easily causing defects in the semiconductor device.
  • the metal ion adsorption filter preferably has an acid group on its surface from the viewpoint of improving the adsorption performance of metal ions. Examples of the acid group include a sulfo group and a carboxyl group.
  • the base material (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.
  • An example of the purification treatment VI is an embodiment in which a filtration member provided with a filter having a particle size removal diameter of 20 nm or less is used as the filtration means.
  • the liquid to be purified can remove particulate impurities from the liquid to be purified.
  • the "particulate impurities” include particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw materials used in the production of the liquid to be purified, and the liquid to be purified. Examples include particles of dust, dust, organic solids, and inorganic solids that are brought in as contaminants during purification, and those that finally exist as particles without being dissolved in the liquid to be purified fall under this category.
  • the "particulate impurities” also include colloidal impurities containing metal atoms.
  • the metal atom is not particularly limited, but Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, and Pb (preferably Fe, Cr, Ni, and Pb). ), When the content of at least one metal atom selected from the group is particularly low (for example, when the content of the metal atoms in the liquid to be purified is 1000 mass ppt or less, respectively), these metal atoms are used. Impurities contained are likely to colloid. With the metal ion adsorption member, it tends to be difficult to remove colloidal impurities.
  • a filter having a particle size removal diameter of 20 nm or less for example, a microfiltration membrane having a pore size of 20 nm or less
  • colloidal impurities can be effectively removed.
  • the particulate impurities have a size that can be removed by a filter having a particle size removal diameter of 20 nm or less, and specifically, particles having a diameter of 20 nm or more.
  • particulate impurities may be referred to as "coarse particles".
  • the particle size of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm.
  • the particle size removal means the minimum size of particles that can be removed by the filter.
  • the removal particle diameter of the filter is 20 nm
  • particles having a diameter of 20 nm or more can be removed.
  • the material of the filter include 6-nylon, 6,6-nylon, polyethylene, polypropylene, polystyrene, fluororesin and the like.
  • the filtration member may further include a filter having a particle size removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles having a pore size of 50 nm or more).
  • a filter having a particle removal diameter of 20 nm or less for example, pore size.
  • Filtering of the liquid to be purified using a filter with a particle removal diameter of 50 nm or more for example, a precision filtration film for removing fine particles with a pore size of 50 nm or more
  • a precision filtration membrane with a particle size of 20 nm or less By carrying out the above, the filtration efficiency of a filter having a particle removal diameter of 20 nm or less (for example, a precision filtration film having a pore size of 20 nm or less) is improved, and the removal performance of coarse particles is further improved.
  • the liquid to be purified obtained by obtaining each of these treatments can be used for preparing the treatment liquid of the present invention, or can be used as the treatment liquid itself of the present invention.
  • the above-mentioned purification step the case where all the treatments are performed is shown, but the present invention is not limited to this, and each of the above treatments may be performed alone or in combination of a plurality of the above treatments. .. Further, each of the above processes may be performed once or a plurality of times.
  • the raw material of the organic solvent constituting the treatment liquid or the treatment It is also possible to store the liquid itself in a container in which impurities are less likely to elute. Further, there is also a method of lining the inner wall of the pipe with a fluororesin so that the metal component does not elute from the “pipe” or the like during the production of the treatment liquid.
  • the treatment liquid of the present invention can be filled in an arbitrary container, stored, transported, and used as long as corrosiveness does not become a problem.
  • the container it is preferable that the container has a high degree of cleanliness and less elution of impurities for semiconductor applications.
  • Specific examples of the containers that can be used include, but are not limited to, the "clean bottle” series manufactured by Aicello Chemical Co., Ltd. and the "pure bottle” manufactured by Kodama Resin Industry.
  • the inner wall of the container (the wetted portion in contact with the solution in the container) is preferably formed of a non-metallic material.
  • Non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, ethylene tetrafluoride resin (PTFE), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (PFA), ethylene tetrafluoride-hexfluoride.
  • Propropylene copolymer resin (FEP) ethylene tetrafluoride-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride copolymer
  • FEP Propropylene copolymer resin
  • EFE ethylene tetrafluoride-ethylene copolymer resin
  • ECTFE ethylene trifluoride-ethylene copolymer resin
  • PVDF vinylidene fluoride resin
  • quartz or a metal material (more preferably, an electropolished metal material, in other words, an electropolished metal material) is preferably used for the inner wall of the container.
  • the metal material (particularly, the metal material used for producing the electropolished metal material) preferably contains chromium in an amount of more than 25% by mass with respect to the total mass of the metal material, and examples thereof include stainless steel.
  • the chromium content in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material.
  • the upper limit is not particularly limited, but is generally preferably 90% by mass or less.
  • the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
  • austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.
  • the method for electrolytically polishing a metal material is not particularly limited, and a known method can be used.
  • a known method can be used.
  • the methods described in paragraphs [0011] to [0014] of JP2015-227501 and paragraphs [0036] to [0042] of JP2008-264929 can be used.
  • the metal material is preferably buffed.
  • the method of buffing is not particularly limited, and a known method can be used.
  • the size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
  • the buffing is preferably performed before the electrolytic polishing. Further, even if the metal material is processed by combining one or two or more of a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of the abrasive grains. good.
  • a container having the above-mentioned container and the above-mentioned treatment liquid contained in the container is also referred to as a solution container.
  • the treatment liquid of the present invention may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.
  • the gallon bottle may or may not be made of glass material.
  • the inside of the container may be replaced with an inert gas (chisso, argon, etc.) having a purity of 99.99995% by volume or more for the purpose of preventing changes in the components in the treatment liquid during storage.
  • an inert gas chisso, argon, etc.
  • a gas having a low water content is preferable.
  • the temperature may be at room temperature, but in order to prevent deterioration, the temperature may be controlled in the range of ⁇ 20 ° C. to 20 ° C.
  • the clean room preferably meets the ISO 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and satisfy ISO class 1. Is even more preferable.
  • ISO International Organization for Standardization
  • the treatment liquid of the present invention or the organic solvent contained in the treatment liquid may further have a static elimination step in the preparation and purification.
  • the static elimination step is a step of reducing the charging potential of a purified product or the like by removing static electricity from at least one selected from the group consisting of a raw material, a reactant, and a purified product (hereinafter referred to as "refined product or the like").
  • the static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the static elimination method include a method in which the purified liquid or the like is brought into contact with the conductive material.
  • the contact time for bringing the purified liquid or the like into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 seconds.
  • the conductive material include stainless steel, gold, platinum, diamond, glassy carbon and the like.
  • the method of bringing the purified liquid or the like into contact with the conductive material include a method of arranging a grounded mesh made of the conductive material inside the conduit and passing the purified liquid or the like through the grounded mesh.
  • the static elimination step may be carried out at any time from the supply of the raw material to the filling of the purified product.
  • the group consisting of the raw material supply step, the reaction step, the liquid preparation step, the purification step, the filtration step, and the filling step It is preferable that it is contained before at least one step selected from the above steps, and it is more preferable to carry out a static elimination step before injecting the purified product or the like into the container used in each of the above steps. This makes it possible to prevent impurities derived from the container or the like from being mixed into the purified product or the like.
  • the reaction solution (contents of the above flask) was cooled to room temperature and then added dropwise to hexane (3 L) to obtain a mixed solution in which the polymer was precipitated.
  • the above mixed solution was filtered to obtain a solid (filter).
  • the obtained solid (filter) was dissolved in acetone (500 ml) and added dropwise to hexane (3 L) again to obtain a solid (filter) again in the same manner as described above.
  • the obtained solid was dried under reduced pressure to obtain 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1a) (160 g).
  • the copolymer (A-1a) (10 g), methanol (40 ml), 1-methoxy-2-propanol (200 ml), and concentrated hydrochloric acid (1.5 ml) obtained above are emptied in the reaction vessel.
  • the reaction solution (contents of the above flask) was heated to 80 ° C. and stirred for 5 hours.
  • the reaction solution was allowed to cool to room temperature and then added dropwise to distilled water (3 L) to obtain a mixed solution.
  • the above mixed solution was filtered to obtain a solid (filter).
  • the obtained solid (filter) was dissolved in acetone (200 ml) and added dropwise to distilled water (3 L) again to obtain a solid (filter) again in the same manner as described above.
  • the obtained solid was dried under reduced pressure to obtain a resin (A-1) (8.5 g).
  • the weight average molecular weight of the resin (A-1) was 10800, and the molecular weight dispersion (Mw / Mn) was 1.5
  • Synthesis Example 2 Synthesis of Resin (A-2) A resin (A-2) was further synthesized by the same method as in Synthesis Example 1 above, except that the monomer used was changed. The composition ratio (molar ratio) of each repeating unit in the resin was calculated by 1 H-NMR (Nuclear Magnetic Resonance) measurement.
  • composition ratio (molar ratio) indicates the content (composition ratio (molar ratio)) of each repeating unit constituting each resin.
  • the content of each repeating unit shown in the "Structure” column corresponds to the value shown in the "Composition ratio (molar ratio)” column in order from the left.
  • Photoacid generator The following components were used as the photoacid generator.
  • Base compound (acid diffusion control agent)> The following components were used as the basic compound.
  • a composition for forming an organic film (product name: AL412, manufactured by Brewer Science) was applied onto a 6-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an organic film having a film thickness of 20 nm.
  • the resist composition 1 shown in Table 2 was applied onto the resist composition 1 and baked at a temperature of 120 ° C. for 60 seconds to form a resist film having a film thickness of 60 nm.
  • the wafer was taken out from the electron beam irradiator and immediately heated (baked after exposure) on a hot plate at a temperature of 110 ° C. for 60 seconds.
  • FIG. 1 shows micrographs of patterns formed by exposure with exposure amounts of shot numbers 3 to 10 in Example A-1 and Comparative Example A-1.
  • Comparative Example A-1 it was determined that the resolution was not a problem only when the exposure was performed with the exposure amount of shot number 4. That is, in Comparative Example A-1, the number of shots (number of resolution frames) that could be resolved without any problem was 1.
  • Example 1 it was determined that the resolution was not a problem when the exposure was performed with the exposure amounts of shot numbers 4 to 8.
  • Example A-1 the number of shots (number of resolution frames) that could be resolved without any problem was 5. Based on the same criteria, the number of resolution frames was calculated for other examples and comparative examples. It was evaluated according to the following evaluation criteria. A: 5 or more B: 4 C: 3 D: 2 E: 1 or less
  • the "boiling point difference between the two solvents” means the value obtained by the following formula (Bp).
  • Formula (Bp) "Boiling point difference between two solvents (° C)”
  • the boiling point is the boiling point at 1 atm.
  • the "skeleton" column indicates whether or not the second solvent has a linear structure, a branched chain structure, or a cyclic structure.
  • the description of "cyclic” means that the second solvent has a cyclic structure.
  • the description of "branched” means that the second solvent has a branched chain alkyl group and does not have a cyclic structure.
  • the description of "straight chain” means that the second solvent has a linear alkyl group and does not have a cyclic structure or a branched chain alkyl group.
  • the content of the fluorine-based solvent is 10 to 80% by mass with respect to the total mass of the treatment liquid. In that case, it was confirmed that the effect was superior. Also from the comparison of Examples B-1 to B-5, the comparison of Examples C-1 to C-5, the comparison of Examples D-1 to D-5, and the comparison of Examples E-1 to E-5. The above effect can be seen.
  • Example F-1 When a pattern was formed by carrying out the same procedure as in Example A-1 except that the resist composition 2 was used instead of the resist composition 1, the resolution was evaluated as C, and the exposed film was reduced. The evaluation was B, the evaluation of bridge defects was A, and the evaluation of chargeability was A. From the above results, it was confirmed that when the resin has a hydroxystyrene-based repeating unit, a more excellent effect can be obtained.
  • the treatment liquid of the present invention can be used not only as a rinse liquid described above but also as a developing liquid to obtain a desired effect.
  • the developer was changed to a mixed solution of butyl acetate and 2H, 3H-decafluoropentane in a volume ratio of 3: 2 (butyl acetate: 2H, 3H-decafluoropentane). A pattern was obtained in the same manner even when the development was carried out.

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Abstract

The present invention provides: a treatment liquid from which a pattern having excellent resolution can be formed when used for at least one among the development and cleaning (rinsing) of a resist film, and electrification is less likely to occur when in contact with a fluorine-based resin; and a pattern forming method pertaining to said treatment liquid. A treatment liquid according to the present invention is a treatment liquid which is for patterning a resist film, and used for performing at least one among development and cleaning after exposure on a resist film obtained from an actinic ray-sensitive or radiation-sensitive composition, and contains a fluorine-based solvent having 3 to 5 carbon atoms, and an organic solvent other than the fluorine-based solvent having 3 to 5 carbon atoms.

Description

処理液、パターン形成方法Treatment liquid, pattern formation method
　本発明は、レジスト膜パターニング用の処理液及びパターン形成方法に関する。
　より詳細には、本発明は、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ、集積回路）等の半導体製造工程、液晶及びサーマルヘッド等の回路基板の製造、更にはその他のフォトファブリケーションのリソグラフィー工程等に使用される、処理液、及び、パターン形成方法に関する。 The present invention relates to a treatment liquid for patterning a resist film and a pattern forming method.
More specifically, the present invention is used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit substrates such as liquid crystal and thermal heads, and other photolithography lithography steps. The present invention relates to a treatment liquid and a pattern forming method.
　従来、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ、集積回路）及びＬＳＩ（Ｌａｒｇｅ　Ｓｃａｌｅ　Ｉｎｔｅｇｒａｔｅｄ　ｉｒｃｕｉｔ、大規模集積回路）等の半導体デバイスの製造プロセスにおいては、フォトレジスト組成物を用いたリソグラフィーによる微細加工が行われている。近年、集積回路の高集積化に伴い、サブミクロン領域及びクオーターミクロン領域の超微細パターン形成が要求されるようになってきている。それに伴い、露光波長もｇ線からｉ線に、更にＫｒＦエキシマレーザー光に、というように短波長化の傾向が見られる。更には、現在では、エキシマレーザー光以外にも、電子線、Ｘ線、又は、ＥＵＶ光（Ｅｘｔｒｅｍｅ　Ｕｌｔｒａ　Ｖｉｏｌｅｔ、極紫外線）を用いたリソグラフィーも開発が進んでいる。
　このようなリソグラフィーにおいては、感活性光線又は感放射線性組成物（レジスト組成物とも呼ばれる）により膜（レジスト膜）を形成した後、得られた膜を現像液により現像したり、現像後の膜をリンス液で洗浄したりする処理が行われている。
　例えば、特許文献１には、所定の有機溶剤を含む現像液又はリンス液が開示されている。 Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits, integrated circuits) and LSIs (Large Scale Integrated Circuits, large-scale integrated circuits), fine processing by lithography using a photoresist composition has been performed. In recent years, with the increasing integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quartermicron region has been required. Along with this, there is a tendency for the exposure wavelength to be shortened from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beam, X-ray, or EUV light (Extreme Ultra Violet) is also being developed.
In such lithography, a film (resist film) is formed by a sensitive light beam or a radiation-sensitive composition (also called a resist composition), and then the obtained film is developed with a developing solution, or the developed film is developed. Is being washed with a rinse solution.
For example, Patent Document 1 discloses a developing solution or a rinsing solution containing a predetermined organic solvent.
特開２０１３－２５７３７９号公報Japanese Unexamined Patent Publication No. 2013-257379
　近年、集積回路の高集積化に伴って、レジスト組成物を用いた微細パターン（高解像なパターン）の形成が求められている。このような微細パターンの形成においては、微細化に伴いパターン同士の距離が狭まることで、大きな毛管力が発生し、良質なパターンを形成しにくくなるといった問題がある。
　本発明者らは、特許文献１に具体的に開示されている処理液（炭素数６～１０のフッ素系溶剤）を用いた場合、所望の効果が得られないことを知見した。 In recent years, with the increasing integration of integrated circuits, the formation of fine patterns (high-resolution patterns) using resist compositions has been required. In the formation of such a fine pattern, there is a problem that a large capillary force is generated due to the narrowing of the distance between the patterns as the miniaturization occurs, and it becomes difficult to form a high-quality pattern.
The present inventors have found that the desired effect cannot be obtained when the treatment liquid (fluorine-based solvent having 6 to 10 carbon atoms) specifically disclosed in Patent Document 1 is used.
　また、半導体設備及び装置に使用される配管の内壁は、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体に代表されるフッ素系樹脂で被覆される場合がある。このような配管内部に処理液を通した際に、帯電が生じると、ピンホールが発生し、漏液等の問題が生じるおそれがある。 In addition, the inner wall of piping used for semiconductor equipment and devices may be coated with a fluororesin typified by a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. If charging occurs when the treatment liquid is passed through the inside of such a pipe, pinholes may occur and problems such as liquid leakage may occur.
　本発明は、以上の点を鑑みてなされたものであり、レジスト膜に対する現像及び洗浄（リンス）の少なくとも一方に使用された場合に、解像性に優れたパターン形成が可能であり、かつ、フッ素系樹脂と接触した際に帯電が生じにくい処理液を提供することを課題とする。
　また、本発明は、上記処理液に関するパターン形成方法を提供することを課題とする。 The present invention has been made in view of the above points, and when used for at least one of development and cleaning (rinsing) of a resist film, it is possible to form a pattern having excellent resolvability, and the present invention is capable of forming a pattern. An object of the present invention is to provide a treatment liquid that is less likely to be charged when it comes into contact with a fluororesin.
Another object of the present invention is to provide a pattern forming method for the above-mentioned treatment liquid.
　本発明者らは、上記課題について鋭意検討した結果、下記構成により上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.
（１）　感活性光線又は感放射線性組成物から得られるレジスト膜に対して、露光後の現像及び洗浄の少なくとも一方を行うために使用される、レジスト膜パターニング用の処理液であって、
　炭素数３～５のフッ素系溶剤と、炭素数３～５のフッ素系溶剤以外の有機溶剤とを含む、処理液。
（２）　有機溶剤が、ヘテロ原子を有していてもよい炭化水素を含む、（１）に記載の処理液。
（３）　処理液がリンス液である、（１）又は（２）に記載の処理液。
（４）　フッ素系溶剤に含まれるフッ素原子数が、フッ素系溶剤に含まれる炭素数に対して、２倍以上である、（１）～（３）のいずれかに記載の処理液。
（５）　フッ素系溶剤の含有量が、処理液の全質量に対して、１０～８０質量％である、（１）～（４）のいずれかに記載の処理液。
（６）　フッ素系溶剤が、２Ｈ，３Ｈ－デカフルオロペンタン、及び、１Ｈ－ウンデカフルオロペンタンからなる群から選ばれる少なくとも１種を含む、（１）～（５）のいずれかに記載の処理液。
（７）　有機溶剤が、エステル系溶剤、エーテル系溶剤、アルコール系溶剤、ケトン系溶剤、及び、炭化水素系溶剤からなる群から選ばれる少なくとも１種を含む、（１）～（６）のいずれかに記載の処理液。
（８）　有機溶剤が非環状エステル系溶剤を含み、
　非環状エステル系溶剤の炭素数が炭素数５以上であり、
　非環状エステル系溶剤の沸点と、フッ素系溶剤の沸点との差の絶対値が５０℃以上である、（１）～（７）のいずれかに記載の処理液。
（９）　有機溶剤が、プロピオン酸イソプロピル、酢酸ｓｅｃ－ブチル、ギ酸イソアミル、酢酸ブチル、炭酸ジエチル、酪酸ブチル、酪酸アミル、酪酸イソブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸イソアミル、酢酸アミル、酢酸ヘキシル、酢酸－２－エチルブチル、ギ酸アミル、ギ酸ヘキシル、ギ酸イソヘキシル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸プロピル、プロピオン酸ヘキシル、酪酸エチル、イソ酪酸エチル、酪酸ヘキシル、イソ酪酸イソブチル、ヘキサン酸エチル、ｎ－オクタン酸メチル、及び、ｎ－オクタン酸エチルからなる群から選ばれる少なくとも１種を含む、（８）に記載の処理液。
（１０）　有機溶剤が非環状エーテル系溶剤を含み、
　非環状エーテル系溶剤の炭素数５以上であり、
　非環状エーテル系溶剤の沸点と、フッ素系溶剤の沸点との差の絶対値が５０℃以上である、（１）～（７）のいずれかに記載の処理液。
（１１）　有機溶剤が、ジイソアミルエーテル、アミルエーテル、ジイソアミルエーテル、及び、アミルエーテルからなる群から選ばれる少なくとも１種を含む、（１０）に記載の処理液。
（１２）　有機溶剤が非環状アルコール系溶剤を含み、
　非環状アルコール系溶剤の炭素数７以上であり、
　非環状アルコール系溶剤の沸点と、フッ素系溶剤の沸点との差の絶対値が１００℃以上である、（１）～（７）のいずれかに記載の処理液。
（１３）　有機溶剤が、２，６－ジメチル－４－ヘプタノール、３－オクタノール、２－エチルヘキサノール、１－オクタノール、２－オクタノール、３，５－ジメチル－１－ヘキシン－３－オール、１－オクチン－３－オール、３，７－ジメチル－３－オクタノール、３，５，５－トリメチル－１－ヘキサノール、３－エチル－３－ペンタノール－４－メチルペンタノール、及び、１－ヘプタノールからなる群から選ばれる少なくとも１種を含む、（１２）に記載の処理液。
（１４）　有機溶剤が非環状ケトン系溶剤を含み、
　非環状ケトン系溶剤の炭素数５以上であり、
　非環状ケトン系溶剤の沸点と、フッ素系溶剤の沸点との差の絶対値が５０℃以上である、（１）～（７）のいずれかに記載の処理液。
（１５）　有機溶剤が、ジイソブチルケトン、３－オクタノン、２，４－ジメチル－３－ペンタノン、２，６－ジメチル－４－ヘプタノン、５－ノナノン、及び、２，５－ジメチル－３－ヘキサノンからなる群から選ばれる少なくとも１種を含む、（１４）に記載の処理液。
（１６）　有機溶剤が炭素数７以上の炭化水素系溶剤を含む、（１）～（７）のいずれかに記載の処理液。
（１７）　有機溶剤が、デカン、メシチレン、ウンデカン、ノナノン、３－メチルノナノン、４－メチルノナノン、及び、５－メチルノナンからなる群から選ばれる少なくとも１種を含む、（１６）に記載の処理液。
（１８）　感活性光線又は感放射線性組成物が、ヒドロキシスチレン系繰り返し単位を有する樹脂を含む、（１）～（１７）のいずれかに記載の処理液。
（１９）　感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
　レジスト膜を露光する露光工程と、
　露光されたレジスト膜を（１）～（１８）のいずれかに記載の処理液によって処理する処理工程とを備える、パターン形成方法。
（２０）　感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
　レジスト膜を露光する露光工程と、
　露光されたレジスト膜を処理する処理工程とを備える、パターン形成方法であって、
　処理工程は、
　現像液によって現像する現像工程と、
　リンス液によって洗浄するリンス工程とを備え、
　リンス液が（１）～（１８）のいずれかに記載の処理液である、パターン形成方法。
（２１）　現像液が、エステル系溶剤を含む、（２０）に記載のパターン形成方法。
（２２）　エステル系溶剤が、酢酸ブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸ｓｅｃ－ブチル、酢酸アミル、酢酸イソアミル、ギ酸アミル、ギ酸イソアミル、ギ酸ヘキシル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸イソプロピル、プロピオン酸プロピル、酪酸エチル、イソ酪酸エチル、炭酸ジエチル、炭酸ジブチル、ブタン酸ブチル、イソ酪酸イソブチル、イソ吉草酸エチル、イソ吉草酸ブチル、ヘプタン酸プロピル、ヘプタン酸エチル、ヘキサン酸ブチル、ヘキサン酸プロピル、及び、３－メチル吉草酸エチルからなる群から選ばれる少なくとも１種を含む、（２１）に記載のパターン形成方法。 (1) A treatment liquid for patterning a resist film, which is used for performing at least one of development and cleaning after exposure on a resist film obtained from a sensitive light beam or a radiation-sensitive composition.
A treatment liquid containing a fluorinated solvent having 3 to 5 carbon atoms and an organic solvent other than the fluorinated solvent having 3 to 5 carbon atoms.
(2) The treatment liquid according to (1), wherein the organic solvent contains a hydrocarbon which may have a hetero atom.
(3) The treatment liquid according to (1) or (2), wherein the treatment liquid is a rinse liquid.
(4) The treatment solution according to any one of (1) to (3), wherein the number of fluorine atoms contained in the fluorine-based solvent is twice or more the number of carbon atoms contained in the fluorine-based solvent.
(5) The treatment liquid according to any one of (1) to (4), wherein the content of the fluorine-based solvent is 10 to 80% by mass with respect to the total mass of the treatment liquid.
(6) The treatment according to any one of (1) to (5), wherein the fluorine-based solvent contains at least one selected from the group consisting of 2H, 3H-decafluoropentane, and 1H-undecafluoropentane. liquid.
(7) Any of (1) to (6), wherein the organic solvent contains at least one selected from the group consisting of an ester solvent, an ether solvent, an alcohol solvent, a ketone solvent, and a hydrocarbon solvent. The treatment liquid described in the solvent.
(8) The organic solvent contains a non-cyclic ester solvent and contains
The acyclic ester solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
The treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic ester solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
(9) The organic solvent is isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate, amyl acetate, hexyl acetate. , 2-ethylbutyl acetate, amyl formate, hexyl formate, isohexyl formate, butyl propionate, isobutyl propionate, propyl propionate, hexyl propionate, ethyl butyrate, ethyl isobutyrate, hexyl butyrate, isobutyl isobutyrate, ethyl hexanoate, The treatment solution according to (8), which comprises at least one selected from the group consisting of methyl n-octanoate and ethyl n-octanoate.
(10) The organic solvent contains an acyclic ether solvent, and the organic solvent contains a non-cyclic ether solvent.
The acyclic ether solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
The treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic ether solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
(11) The treatment liquid according to (10), wherein the organic solvent contains at least one selected from the group consisting of diisoamyl ether, amyl ether, diisoamyl ether, and amyl ether.
(12) The organic solvent contains a non-cyclic alcohol solvent and contains
The acyclic alcohol solvent has 7 or more carbon atoms and has 7 or more carbon atoms.
The treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic alcohol solvent and the boiling point of the fluorine solvent is 100 ° C. or higher.
(13) The organic solvent is 2,6-dimethyl-4-heptanol, 3-octanol, 2-ethylhexanol, 1-octanol, 2-octanol, 3,5-dimethyl-1-hexin-3-ol, 1-. Consists of octin-3-ol, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol-4-methylpentanol, and 1-heptanol The treatment solution according to (12), which comprises at least one selected from the group.
(14) The organic solvent contains an acyclic ketone solvent, and the organic solvent contains a non-cyclic ketone solvent.
The acyclic ketone solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
The treatment liquid according to any one of (1) to (7), wherein the absolute value of the difference between the boiling point of the acyclic ketone solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
(15) The organic solvent is from diisobutyl ketone, 3-octanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 5-nonanonone, and 2,5-dimethyl-3-hexanone. The treatment liquid according to (14), which comprises at least one selected from the group.
(16) The treatment liquid according to any one of (1) to (7), wherein the organic solvent contains a hydrocarbon solvent having 7 or more carbon atoms.
(17) The treatment liquid according to (16), wherein the organic solvent contains at least one selected from the group consisting of decane, mesitylene, undecane, nonanone, 3-methylnonanone, 4-methylnonanone, and 5-methylnonanone.
(18) The treatment solution according to any one of (1) to (17), wherein the active ray or radiation-sensitive composition contains a resin having a hydroxystyrene-based repeating unit.
(19) A resist film forming step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
The exposure process for exposing the resist film and
A pattern forming method comprising a treatment step of treating an exposed resist film with the treatment liquid according to any one of (1) to (18).
(20) A resist film forming step of forming a resist film using a sensitive light beam or a radiation-sensitive composition, and
The exposure process for exposing the resist film and
A pattern forming method comprising a processing step of processing an exposed resist film.
The processing process is
The development process of developing with a developer and
Equipped with a rinsing process for cleaning with a rinsing liquid,
The pattern forming method, wherein the rinsing liquid is the treatment liquid according to any one of (1) to (18).
(21) The pattern forming method according to (20), wherein the developer contains an ester solvent.
(22) Ester-based solvents are butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, amyl formate, isoamyl formate, hexyl formate, amyl propionate, isoamyl propionate, isopropyl propionate. , Propyl propionate, ethyl butyrate, ethyl isobutyrate, diethyl carbonate, dibutyl carbonate, butyl butanoate, isobutyl isobutyrate, ethyl isovalerate, butyl isoamyl acetate, propyl heptate, ethyl heptate, butyl hexanoate, hexanoic acid The pattern forming method according to (21), which comprises at least one selected from the group consisting of propyl and ethyl 3-methylvalerate.
　本発明によれば、レジスト膜に対する現像及び洗浄（リンス）の少なくとも一方に使用された場合に、解像性に優れたパターン形成が可能であり、かつ、フッ素系樹脂と接触した際に帯電が生じにくい処理液を提供できる。
　また、本発明によれば、上記処理液に関するパターン形成方法を提供できる。 According to the present invention, when used for at least one of development and cleaning (rinsing) of a resist film, it is possible to form a pattern having excellent resolution, and when it comes into contact with a fluororesin, it becomes charged. It is possible to provide a treatment liquid that is unlikely to occur.
Further, according to the present invention, it is possible to provide a pattern forming method for the above-mentioned treatment liquid.
実施例及び比較例で作製されたパターンの一例を示す顕微鏡写真図である。It is a micrograph which shows an example of the pattern produced in Example and Comparative Example.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に限定されない。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
　本明細書中における基（原子団）の表記について、本発明の趣旨に反しない限り、置換及び無置換を記していない表記は、置換基を有さない基と共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。また、本明細書中における「有機基」とは、少なくとも１個の炭素原子を含む基をいう。 Regarding the notation of a group (atomic group) in the present specification, unless it is contrary to the gist of the present invention, the notation without substitution and non-substitution includes a group having a substituent as well as a group having no substituent. do. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.
　本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光：　Ｅｘｔｒｅｍｅ　Ｕｌｔｒａｖｉｏｌｅｔ）、Ｘ線、及び、電子線（ＥＢ：Ｅｌｅｃｔｒｏｎ　Ｂｅａｍ）等を意味する。本明細書中における「光」とは、活性光線又は放射線を意味する。 As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X rays, and electron beams (EUV light: Extreme Ultraviolet), and electron beams (. EB: Electron Beam) and the like. As used herein, the term "light" means active light or radiation.
　本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、Ｘ線、及び、ＥＵＶ光等による露光、並びに、電子線及びイオンビーム等の粒子線による描画も含む。 Unless otherwise specified, the term "exposure" as used herein refers to the emission line spectrum of a mercury lamp, exposure to far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, and the like, as well as electron beams and ions. It also includes drawing with particle beams such as beams.
　本明細書において、「～」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。 In this specification, "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
　本明細書において表記される２価の基の結合方向は、特に断らない限り制限されない。例えば、「Ｘ－Ｙ－Ｚ」なる一般式で表される化合物中の、Ｙが－ＣＯＯ－である場合、Ｙは、－ＣＯ－Ｏ－であってもよく、－Ｏ－ＣＯ－であってもよい。また、上記化合物は「Ｘ－ＣＯ－Ｏ－Ｚ」であってもよく「Ｘ－Ｏ－ＣＯ－Ｚ」であってもよい。 The bonding direction of the divalent group described in the present specification is not limited unless otherwise specified. For example, when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
　本明細書において、（メタ）アクリレートはアクリレート及びメタクリレートを表し、（メタ）アクリルはアクリル及びメタクリルを表す。 In the present specification, (meth) acrylate represents acrylate and methacrylate, and (meth) acrylic represents acrylic and methacryl.
　本明細書において、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられる。 In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　本明細書において、樹脂の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、及び分散度（以下、「分子量分布」ともいう。）（Ｍｗ／Ｍｎ）は、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）装置（東ソー製ＨＬＣ－８１２０ＧＰＣ）によるＧＰＣ測定（溶剤：テトラヒドロフラン、流量（サンプル注入量）：１０μＬ、カラム：東ソー社製ＴＳＫ　ｇｅｌ　Ｍｕｌｔｉｐｏｒｅ　ＨＸＬ－Ｍ、カラム温度：４０℃、流速：１．０ｍＬ／分、検出器：示差屈折率検出器（Ｒｅｆｒａｃｔｉｖｅ　Ｉｎｄｅｘ　Ｄｅｔｅｃｔｏｒ））によるポリスチレン換算値として定義される。 In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (hereinafter, also referred to as “molecular weight distribution”) (Mw / Mn) of the resin are referred to as GPC (Gel Permeation Chromatography) apparatus ( GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detection Instrument: Defined as a polystyrene-equivalent value by a differential refractive index detector (Refractive Index Detector).
　本明細書において、沸点とは、１気圧における沸点を意味する。 In the present specification, the boiling point means the boiling point at 1 atm.
　本明細書において、有機溶剤とは、２５℃において液状である有機化合物を意味する。
　処理液中に含まれる有機化合物の種類及び含有量等は、例えば、ＤＩ－ＭＳ（ダイレクトインジェクションマスクロマトグラフィー）で測定される。 As used herein, the term "organic solvent" means an organic compound that is liquid at 25 ° C.
The type and content of the organic compound contained in the treatment liquid are measured by, for example, DI-MS (Direct Injection Mass Chromatography).
［処理液］
　本発明の処理液は、感活性光線又は感放射線性組成物（以下、「レジスト組成物」ともいう。）から得られるレジスト膜に対して現像及び洗浄の少なくとも一方を行うために使用される、レジスト膜パターニング用の処理液である。本発明の処理液の特徴点としては、炭素数３～５のフッ素系溶剤（以下、単に「フッ素系溶剤」ともいう。）と、炭素数３～５のフッ素系溶剤以外の有機溶剤（以下、単に「第二溶剤」ともいう。）とを含むことが挙げられる。
　本発明者らはフッ素系溶剤を使用することにより、処理液がフッ素系樹脂と接触した際に帯電が防止されることを知見している。一方で、フッ素系溶剤を使用すると、解像性が悪化してしまう。そこで、フッ素系溶剤以外の有機溶剤を用いることにより、上記帯電を防止しつつ、解像性が向上することを知見した。 [Treatment liquid]
The treatment liquid of the present invention is used to perform at least one of development and cleaning on a resist film obtained from a sensitive light beam or a radiation-sensitive composition (hereinafter, also referred to as "resist composition"). A treatment liquid for patterning a resist film. The treatment liquid of the present invention is characterized by a fluorine-based solvent having 3 to 5 carbon atoms (hereinafter, also simply referred to as “fluorine-based solvent”) and an organic solvent other than the fluorine-based solvent having 3 to 5 carbon atoms (hereinafter, simply referred to as “fluorine-based solvent”). , Simply referred to as "second solvent").
The present inventors have found that by using a fluorine-based solvent, charging is prevented when the treatment liquid comes into contact with the fluorine-based resin. On the other hand, when a fluorine-based solvent is used, the resolution is deteriorated. Therefore, it has been found that the resolution is improved while preventing the above-mentioned electrification by using an organic solvent other than the fluorine-based solvent.
　また、上記処理液において、フッ素系溶剤としては、第二溶剤よりも沸点が低いフッ素系溶剤を選択することが好ましい。
　フッ素系溶剤の沸点が第二溶剤の沸点よりも低い場合、処理液による処理（例えば、リンス処理）後の乾燥時に、フッ素系溶剤が優先的に揮発し、形成されたパターン上における第二溶剤の濃度が高まる。その結果、第二溶剤による効果が最大限発揮され、特に密集パターンでのパターン倒れの抑制効果がより顕著となる。 Further, in the above-mentioned treatment liquid, it is preferable to select a fluorine-based solvent having a boiling point lower than that of the second solvent as the fluorine-based solvent.
When the boiling point of the fluorine-based solvent is lower than the boiling point of the second solvent, the fluorine-based solvent preferentially volatilizes during drying after treatment with the treatment liquid (for example, rinsing treatment), and the second solvent on the formed pattern. Concentration increases. As a result, the effect of the second solvent is maximized, and the effect of suppressing the pattern collapse in the dense pattern becomes more remarkable.
　本発明の処理液に含まれるフッ素系溶剤及び第二溶剤について、以下に詳述する。 The fluorine-based solvent and the second solvent contained in the treatment liquid of the present invention will be described in detail below.
〔炭素数３～５のフッ素系溶剤（フッ素系溶剤）〕
　本発明の処理液は、フッ素系溶剤を含む。
　フッ素系溶剤の炭素数は、３～５であり、本発明の効果がより優れる点で、４～５が好ましく、５が更に好ましい。
　フッ素系溶剤とは、分子内に少なくとも１つのフッ素原子を含む有機溶剤をいう。フッ素系溶剤としては、少なくとも１つのフッ素原子を有する、炭素数３～５の炭化水素が好ましい。 [Fluorine-based solvent with 3 to 5 carbon atoms (fluorine-based solvent)]
The treatment liquid of the present invention contains a fluorine-based solvent.
The fluorine-based solvent has 3 to 5 carbon atoms, and 4 to 5 is preferable, and 5 is even more preferable, because the effect of the present invention is more excellent.
The fluorine-based solvent means an organic solvent containing at least one fluorine atom in the molecule. As the fluorine-based solvent, a hydrocarbon having at least one fluorine atom and having 3 to 5 carbon atoms is preferable.
　フッ素系溶剤に含まれるフッ素原子数は、フッ素系溶剤に含まれる炭素数に対して、２倍以上であることが好ましい。上限は特に制限されないが、３倍以下が好ましく、２．５倍以下がより好ましい。 The number of fluorine atoms contained in the fluorine-based solvent is preferably twice or more the number of carbon atoms contained in the fluorine-based solvent. The upper limit is not particularly limited, but is preferably 3 times or less, and more preferably 2.5 times or less.
　フッ素系溶剤としては、式（ａ）で表される化合物が好ましい。より具体的には、２Ｈ，３Ｈ－デカフルオロペンタン、又は、１Ｈ－ウンデカフルオロペンタンが好ましい。 As the fluorine-based solvent, the compound represented by the formula (a) is preferable. More specifically, 2H, 3H-decafluoropentane or 1H-undecafluoropentane is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ａ）中、Ｘ１～Ｘ６は、それぞれ独立に、水素原子又はフッ素原子を表す。
　Ｘ１～Ｘ６のうち、１つ以上がフッ素原子を表し、３つ以上がフッ素原子を表すことが好ましく、５つ以上がフッ素原子を表すことがより好ましい。 In formula (a), X 1 to X 6 independently represent a hydrogen atom or a fluorine atom.
Of X 1 to X 6 , one or more represents a fluorine atom, three or more preferably represent a fluorine atom, and five or more represent a fluorine atom.
　Ｙは、フッ素原子を有していてもよい、炭素数１～３のアルキレン基を表す。
　Ｙで表されるフッ素原子を有していてもよいアルキレン基は、直鎖状構造、又は、分岐鎖状構造を有していてもよい。なかでも、上記アルキレン基は、直鎖状構造が好ましい。
　Ｙで表されるアルキレン基の炭素数は１～３であり、２～３が好ましく、３がより好ましい。
　上記アルキレン基はフッ素原子を有することが好ましく、アルキレン基が有するフッ素原子の数は２～６が好ましく、２～４がより好ましい。 Y represents an alkylene group having 1 to 3 carbon atoms, which may have a fluorine atom.
The alkylene group which may have a fluorine atom represented by Y may have a linear structure or a branched chain structure. Among them, the alkylene group preferably has a linear structure.
The alkylene group represented by Y has 1 to 3 carbon atoms, preferably 2 to 3 and more preferably 3.
The alkylene group preferably has a fluorine atom, and the number of fluorine atoms contained in the alkylene group is preferably 2 to 6, more preferably 2 to 4.
　フッ素系溶剤の沸点（℃）は、４０℃以上が好ましい。上限は特に制限されないが、１００℃以下が好ましく、８０℃以下がより好ましく、６０℃以下が更に好ましい。上記沸点は、１気圧における沸点である。 The boiling point (° C) of the fluorine-based solvent is preferably 40 ° C or higher. The upper limit is not particularly limited, but is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 60 ° C. or lower. The boiling point is the boiling point at 1 atm.
　フッ素系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The fluorine-based solvent may be used alone or in combination of two or more.
　フッ素系溶剤の含有量は特に制限されず、処理液の全質量に対して、５～９５質量％の場合が多く、本発明の効果がより優れる点で、１０～８０質量％が好ましく、１０～７０質量％がより好ましく、１０～５０質量％が更に好ましい。 The content of the fluorosolvent is not particularly limited, and is often 5 to 95% by mass with respect to the total mass of the treatment liquid, and 10 to 80% by mass is preferable because the effect of the present invention is more excellent. It is more preferably from 70% by mass, further preferably from 10 to 50% by mass.
〔炭素数３～５のフッ素系溶剤以外の有機溶剤（第二溶剤）〕
　本発明の処理液は、第二溶剤を含む。第二溶剤は、炭素数３～５のフッ素系溶剤以外の溶剤であればよく、フッ素原子を含む溶剤であっても、フッ素原子を含まない溶剤（非フッ素系溶剤）であってもよい。非フッ素系溶剤とは、分子内にフッ素原子を有さない有機溶剤を意味する。
　第二溶剤は、ヘテロ原子を有していてもよい炭化水素を含むことが好ましい。ヘテロ原子としては、炭素原子及び水素原子以外の原子であればよく、例えば、酸素原子、窒素原子、及び、硫黄原子等が挙げられる。 [Organic solvent other than fluorine-based solvent with 3 to 5 carbon atoms (second solvent)]
The treatment liquid of the present invention contains a second solvent. The second solvent may be a solvent other than the fluorine-based solvent having 3 to 5 carbon atoms, and may be a solvent containing a fluorine atom or a solvent not containing a fluorine atom (non-fluorine-based solvent). The non-fluorine-based solvent means an organic solvent having no fluorine atom in the molecule.
The second solvent preferably contains a hydrocarbon which may have a heteroatom. The hetero atom may be an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
　第二溶剤としては、非フッ素系溶剤が好ましい。
　第二溶剤としては、例えば、エステル系溶剤、エーテル系溶剤、アルコール系溶剤、ケトン系溶剤、及び、炭化水素系溶剤が挙げられる。なお、上記第二溶剤は、直鎖状構造、分岐鎖状構造、又は、環状構造を有していてもよい。
　なかでも、本発明の効果がより優れる点で、第二溶剤としては、非環状エステル系溶剤、非環状エーテル系溶剤、非環状アルコール系溶剤、非環状ケトン系溶剤、及び、炭化水素系溶剤からなる群から選ばれる少なくとも１種が好ましく、非環状エステル系溶剤、非環状エーテル系溶剤、非環状アルコール系溶剤、又は、非環状ケトン系溶剤がより好ましい。 As the second solvent, a non-fluorine solvent is preferable.
Examples of the second solvent include ester-based solvents, ether-based solvents, alcohol-based solvents, ketone-based solvents, and hydrocarbon-based solvents. The second solvent may have a linear structure, a branched chain structure, or a cyclic structure.
Among them, in that the effect of the present invention is more excellent, the second solvent is selected from acyclic ester-based solvent, acyclic ether-based solvent, acyclic alcohol-based solvent, acyclic ketone-based solvent, and hydrocarbon-based solvent. At least one selected from the above group is preferable, and acyclic ester-based solvent, acyclic ether-based solvent, acyclic alcohol-based solvent, or acyclic ketone-based solvent is more preferable.
＜エステル系溶剤＞
　第二溶剤は、エステル系溶剤を含んでいてもよい。なお、本明細書中のエステル系溶剤には、炭酸エステル系溶剤も含まれる。 <Ester solvent>
The second solvent may contain an ester solvent. The ester solvent in the present specification also includes a carbonic acid ester solvent.
　エステル系溶剤としては、例えば、プロピオン酸イソプロピル、酢酸ｓｅｃ－ブチル、ギ酸イソアミル、酢酸ブチル、炭酸ジエチル、酪酸ブチル、酪酸アミル、酪酸イソブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸イソアミル、酢酸アミル、酢酸ヘキシル、酢酸－２－エチルブチル、ギ酸アミル、ギ酸ヘキシル、ギ酸イソヘキシル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸プロピル、プロピオン酸ヘキシル、酪酸エチル、イソ酪酸エチル、酪酸ヘキシル、イソ酪酸イソブチル、ヘキサン酸エチル、ｎ－オクタン酸メチル、ｎ－オクタン酸エチル、及び、安息香酸メチルが挙げられる。
　なかでも、本発明の効果がより優れる点で、プロピオン酸イソプロピル、酢酸ｓｅｃ－ブチル、ギ酸イソアミル、酢酸ブチル、炭酸ジエチル、酪酸ブチル、酪酸アミル、酪酸イソブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸イソアミル、酢酸アミル、酢酸ヘキシル、酢酸－２－エチルブチル、ギ酸アミル、ギ酸ヘキシル、ギ酸イソヘキシル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸プロピル、プロピオン酸ヘキシル、酪酸エチル、イソ酪酸エチル、酪酸ヘキシル、イソ酪酸イソブチル、ヘキサン酸エチル、ｎ－オクタン酸メチル、及び、ｎ－オクタン酸エチルからなる群から選ばれる少なくとも１種が好ましく、プロピオン酸イソプロピル、酢酸ｓｅｃ－ブチル、ギ酸イソアミル、酢酸ブチル、炭酸ジエチル、酪酸ブチル、又は、酪酸アミルがより好ましい。 Examples of the ester solvent include isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate, amyl acetate and acetic acid. Hexil, -2-ethylbutyl acetate, amyl formate, hexyl formate, isohexyl formate, butyl propionate, isobutyl propionate, propyl propionate, hexyl propionate, ethyl butyrate, ethyl isobutyrate, hexyl butyrate, isobutyl isobutyrate, ethyl hexanoate , N-Methyl octanoate, ethyl n-octanoate, and methyl benzoate.
Among them, isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate are the most excellent points of the present invention. , Amil acetate, hexyl acetate, -2-ethylbutyl acetate, amyl formate, hexyl formate, isohexyl formate, butyl propionate, isobutyl propionate, propyl propionate, hexyl propionate, ethyl butyrate, ethyl isobutyrate, hexyl butyrate, isobutyric acid At least one selected from the group consisting of isobutyl, ethyl hexanoate, methyl n-octanoate, and ethyl n-octanoate is preferable, and isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyrate. Butyl or amyl butyrate is more preferred.
　エステル系溶剤は、直鎖状構造、又は、分岐鎖状構造を有していてもよい。また、エステル系溶剤は、環状構造を有していてもよい。なかでも、本発明の効果がより優れる点で、エステル系溶剤は、環状構造を有さないことが好ましい。つまり、エステル系溶剤は、非環状エステル系溶剤（環状構造を有さないエステル系溶剤）であることが好ましい。
　エステル系溶剤は、例えば、直鎖状アルキル基、又は、分岐鎖状アルキル基を有していてもよい。
　なかでも、本発明の効果がより優れる点で、エステル系溶剤は、エステル結合、及び、直鎖状アルキル基又は分岐鎖状アルキル基のみから構成されることが好ましい。 The ester solvent may have a linear structure or a branched chain structure. Further, the ester solvent may have a cyclic structure. Among them, the ester solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ester solvent is preferably a non-cyclic ester solvent (ester solvent having no cyclic structure).
The ester solvent may have, for example, a linear alkyl group or a branched chain alkyl group.
Among them, in that the effect of the present invention is more excellent, the ester solvent is preferably composed of only an ester bond and a linear alkyl group or a branched alkyl group.
　エステル系溶剤の炭素数は特に制限されないが、炭素数５以上が好ましい。上限は特に制限されないが、１５以下が好ましく、１２以下がより好ましく、１０以下が更に好ましく、８以下が特に好ましい。
　非環状エステル系溶剤の炭素数の好適範囲も、上記のエステル系溶剤の炭素数の好適範囲と同じである。 The carbon number of the ester solvent is not particularly limited, but is preferably 5 or more. The upper limit is not particularly limited, but is preferably 15 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
The preferable range of the carbon number of the acyclic ester-based solvent is also the same as the preferable range of the carbon number of the above-mentioned ester-based solvent.
　エステル系溶剤の沸点（℃）と、フッ素系溶剤の沸点（℃）との差の絶対値は特に制限されないが、５０℃以上が好ましい。上限は特に制限されないが、２００℃以下が好ましく、１５０℃以下がより好ましく、１２０℃以下が更に好ましい。上記沸点は、１気圧における沸点である。
　非環状エステル系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲も、上記のエステル系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲と同じである。 The absolute value of the difference between the boiling point (° C.) of the ester solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and even more preferably 120 ° C. or lower. The boiling point is the boiling point at 1 atm.
The preferable range of the absolute value of the difference between the boiling point of the acyclic ester solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ester solvent and the boiling point of the fluorine solvent. ..
　エステル系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The ester solvent may be used alone or in combination of two or more.
＜エーテル系溶剤＞
　第二溶剤は、エーテル系溶剤を含んでいてもよい。
　エーテル系溶剤としては、例えば、ジイソアミルエーテル、アミルエーテル、ジイソアミルエーテル、アミルエーテル、及び、アニソールが挙げられる。
　なかでも、本発明の効果がより優れる点で、エーテル系溶剤としては、ジイソアミルエーテル、アミルエーテル、ジイソアミルエーテル、又は、アミルエーテルが好ましい。 <Ether solvent>
The second solvent may contain an ether solvent.
Examples of the ether solvent include diisoamyl ether, amyl ether, diisoamyl ether, amyl ether, and anisole.
Among them, diisoamyl ether, amyl ether, diisoamyl ether, or amyl ether is preferable as the ether solvent because the effect of the present invention is more excellent.
　エーテル系溶剤は、直鎖状構造、又は、分岐鎖状構造を有していてもよい。また、エーテル系溶剤は、環状構造を有していてもよい。なかでも、本発明の効果がより優れる点で、エーテル系溶剤は、環状構造を有さないことが好ましい。つまり、エーテル系溶剤は、非環状エーテル系溶剤（環状構造を有さないエーテル系溶剤）であることが好ましい。
　エーテル系溶剤は、例えば、直鎖状アルキル基、又は、分岐鎖状アルキル基を有していてもよい。
　なかでも、本発明の効果がより優れる点で、エーテル系溶剤は、エーテル結合、及び、直鎖状アルキル基又は分岐鎖状アルキル基のみから構成されることが好ましい。 The ether solvent may have a linear structure or a branched chain structure. Further, the ether solvent may have a cyclic structure. Among them, the ether solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ether solvent is preferably a non-cyclic ether solvent (an ether solvent having no cyclic structure).
The ether solvent may have, for example, a linear alkyl group or a branched chain alkyl group.
Among them, in that the effect of the present invention is more excellent, the ether solvent is preferably composed of only an ether bond and a linear alkyl group or a branched alkyl group.
　エーテル系溶剤の炭素数は特に制限されないが、５以上が好ましく、８以上がより好ましく、１０以上が更に好ましい。上限は特に制限されないが、２０以下が好ましく、１７以下がより好ましく、１５以下が更に好ましい。
　非環状エーテル系溶剤の炭素数の好適範囲も、上記のエーテル系溶剤の炭素数の好適範囲と同じである。 The number of carbon atoms of the ether solvent is not particularly limited, but 5 or more is preferable, 8 or more is more preferable, and 10 or more is further preferable. The upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
The preferable range of the carbon number of the acyclic ether solvent is also the same as the preferable range of the carbon number of the above-mentioned ether solvent.
　エーテル系溶剤の沸点（℃）と、フッ素系溶剤の沸点（℃）との差の絶対値は特に制限されないが、５０℃以上が好ましく、９０℃以上がより好ましく、１０５℃超が更に好ましい。上限は特に制限されないが、２００℃以下が好ましく、１５０℃以下がより好ましい。上記沸点は、１気圧における沸点である。
　非環状エーテル系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲も、上記のエーテル系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲と同じである。 The absolute value of the difference between the boiling point (° C.) of the ether solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher, more preferably 90 ° C. or higher, and even more preferably over 105 ° C. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. The boiling point is the boiling point at 1 atm.
The preferable range of the absolute value of the difference between the boiling point of the acyclic ether solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ether solvent and the boiling point of the fluorine solvent. ..
　エーテル系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The ether solvent may be used alone or in combination of two or more.
＜アルコール系溶剤＞
　第二溶剤は、アルコール系溶剤を含んでいてもよい。 <Alcohol solvent>
The second solvent may contain an alcohol solvent.
　アルコール系溶剤としては、例えば、２，６－ジメチル－４－ヘプタノール、３－オクタノール、２－エチルヘキサノール、１－オクタノール、２－オクタノール、３，５－ジメチル－１－ヘキシン－３－オール、１－オクチン－３－オール、３，７－ジメチル－３－オクタノール、３，５，５－トリメチル－１－ヘキサノール、３－エチル－３－ペンタノール－４－メチルペンタノール、及び、１－ヘプタノールが挙げられる。
　なかでも、本発明の効果がより優れる点で、アルコール系溶剤としては、２，６－ジメチル－４－ヘプタノール、又は、３－オクタノールが好ましい。 Examples of the alcohol-based solvent include 2,6-dimethyl-4-heptanol, 3-octanol, 2-ethylhexanol, 1-octanol, 2-octanol, 3,5-dimethyl-1-hexin-3-ol, and 1, -Octin-3-ol, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol-4-methylpentanol, and 1-heptanol Can be mentioned.
Among them, 2,6-dimethyl-4-heptanol or 3-octanol is preferable as the alcohol solvent because the effect of the present invention is more excellent.
　アルコール系溶剤は、直鎖状構造、又は、分岐鎖状構造を有していてもよい。また、アルコール系溶剤は、環状構造を有していてもよい。なかでも、本発明の効果がより優れる点で、アルコール系溶剤は、環状構造を有さないことが好ましい。つまり、アルコール系溶剤は、非環状アルコール系溶剤（環状構造を有さないアルコール系溶剤）であることが好ましい。
　アルコール系溶剤は、例えば、直鎖状アルキル基、又は、分岐鎖状アルキル基を有していてもよい。
　また、本発明の効果がより優れる点で、アルコール系溶剤は、ヒドロキシル基、及び、直鎖状アルキル基又は分岐鎖状アルキル基のみから構成されることが好ましい。 The alcohol solvent may have a linear structure or a branched chain structure. Further, the alcohol solvent may have a cyclic structure. Among them, the alcohol solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the alcohol solvent is preferably a non-cyclic alcohol solvent (alcohol solvent having no cyclic structure).
The alcohol solvent may have, for example, a linear alkyl group or a branched chain alkyl group.
Further, in that the effect of the present invention is more excellent, the alcohol solvent is preferably composed of only a hydroxyl group and a linear alkyl group or a branched alkyl group.
　アルコール系溶剤の炭素数は特に制限されないが、７以上が好ましく、８以上がより好ましい。上限は特に制限されないが、２０以下が好ましく、１７以下がより好ましく、１５以下が更に好ましい。
　非環状アルコール系溶剤の炭素数の好適範囲も、上記のアルコール系溶剤の炭素数の好適範囲と同じである。 The carbon number of the alcohol solvent is not particularly limited, but is preferably 7 or more, and more preferably 8 or more. The upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
The preferable range of the carbon number of the acyclic alcohol solvent is also the same as the preferable range of the carbon number of the alcohol-based solvent described above.
　アルコール系溶剤の沸点（℃）と、フッ素系溶剤の沸点（℃）との差の絶対値は特に制限されないが、１００℃以上が好ましく、１２０℃以上がより好ましい。上限は特に制限されないが、２００℃以下が好ましく、１５０℃以下がより好ましい。上記沸点は、１気圧における沸点である。
　非環状アルコール系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲も、上記のアルコール系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲と同じである。 The absolute value of the difference between the boiling point (° C.) of the alcohol solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. The boiling point is the boiling point at 1 atm.
The preferable range of the absolute value of the difference between the boiling point of the acyclic alcohol solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the alcohol solvent and the boiling point of the fluorine solvent. ..
　アルコール系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The alcohol solvent may be used alone or in combination of two or more.
＜ケトン系溶剤＞
　第二溶剤は、ケトン系溶剤を含んでいてもよい。 <Ketone solvent>
The second solvent may contain a ketone solvent.
　ケトン系溶剤としては、例えば、ジイソブチルケトン、３－オクタノン、２，４－ジメチル－３－ペンタノン、２，６－ジメチル－４－ヘプタノン、５－ノナノン、及び、２，５－ジメチル－３－ヘキサノンが挙げられる。
　なかでも、本発明の効果がより優れる点で、ケトン系溶剤としては、ジイソブチルケトン、３－オクタノン、又は、２，４－ジメチル－３－ペンタノンが好ましい。 Examples of the ketone solvent include diisobutyl ketone, 3-octanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 5-nonanonone, and 2,5-dimethyl-3-hexanone. Can be mentioned.
Among them, diisobutyl ketone, 3-octanone, or 2,4-dimethyl-3-pentanone is preferable as the ketone solvent because the effect of the present invention is more excellent.
　ケトン系溶剤は、直鎖状構造、又は、分岐鎖状構造を有していてもよい。また、ケトン系溶剤は、環状構造を有していてもよい。なかでも、本発明の効果がより優れる点で、ケトン系溶剤は、環状構造を有さないことが好ましい。つまり、ケトン系溶剤は、非環状ケトン系溶剤（環状構造を有さないケトン系溶剤）であることが好ましい。
　ケトン系溶剤は、例えば、直鎖状アルキル基、又は、分岐鎖状アルキル基を有していてもよい。
　また、本発明の効果がより優れる点で、ケトン系溶剤は、ケトン結合、及び、直鎖状アルキル基又は分岐鎖状アルキル基のみから構成されることが好ましい。 The ketone solvent may have a linear structure or a branched chain structure. Further, the ketone solvent may have a cyclic structure. Among them, the ketone solvent preferably does not have a cyclic structure because the effect of the present invention is more excellent. That is, the ketone solvent is preferably a non-cyclic ketone solvent (a ketone solvent having no cyclic structure).
The ketone solvent may have, for example, a linear alkyl group or a branched chain alkyl group.
Further, from the viewpoint that the effect of the present invention is more excellent, it is preferable that the ketone solvent is composed of only a ketone bond and a linear alkyl group or a branched alkyl group.
　ケトン系溶剤の炭素数は特に制限されないが、５以上が好ましく、７以上がより好ましい。上限は特に制限されないが、２０以下が好ましく、１７以下がより好ましく、１５以下が更に好ましい。
　非環状ケトン系溶剤の炭素数の好適範囲も、上記のケトン系溶剤の炭素数の好適範囲と同じである。 The carbon number of the ketone solvent is not particularly limited, but is preferably 5 or more, and more preferably 7 or more. The upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
The preferable range of the carbon number of the acyclic ketone solvent is also the same as the preferable range of the carbon number of the above-mentioned ketone solvent.
　ケトン系溶剤の沸点（℃）と、フッ素系溶剤の沸点（℃）との差の絶対値は特に制限されないが、５０℃以上が好ましく、７０℃以上がより好ましい。上限は特に制限されないが、２００℃以下が好ましく、１５０℃以下がより好ましい。上記沸点は、１気圧における沸点である。
　非環状ケトン系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲も、上記のケトン系溶剤の沸点とフッ素系溶剤の沸点との差の絶対値の好適範囲と同じである。 The absolute value of the difference between the boiling point (° C.) of the ketone solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 50 ° C. or higher, more preferably 70 ° C. or higher. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. The boiling point is the boiling point at 1 atm.
The preferable range of the absolute value of the difference between the boiling point of the acyclic ketone solvent and the boiling point of the fluorine solvent is also the same as the preferable range of the absolute value of the difference between the boiling point of the ketone solvent and the boiling point of the fluorine solvent. ..
　ケトン系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The ketone solvent may be used alone or in combination of two or more.
＜炭化水素系溶剤＞
　第二溶剤は、炭化水素系溶剤を含んでいてもよい。 <Hydrocarbon solvent>
The second solvent may contain a hydrocarbon solvent.
　芳香族系溶剤としては、例えば、デカン、メシチレン、ウンデカン、ノナノン、３－メチルノナノン、４－メチルノナノン、及び、５－メチルノナンが挙げられる。
　なかでも、本発明の効果がより優れる点で、芳香族系溶剤としては、デカン、又は、メシチレンが好ましい。 Examples of the aromatic solvent include decane, mesitylene, undecane, nonanone, 3-methylnonanone, 4-methylnonanone, and 5-methylnonanone.
Among them, decane or mesitylene is preferable as the aromatic solvent because the effect of the present invention is more excellent.
　炭化水素系溶剤は、直鎖状構造、分岐鎖状構造、又は、環状構造を有していてもよい。
　炭化水素系溶剤は、例えば、直鎖状アルキル基、分岐鎖状アルキル基、脂環基、又は、芳香族基を有していてもよい。なかでも、本発明の効果がより優れる点で、炭化水素系溶剤は、直鎖状アルキル基、又は、芳香族基を有することが好ましい。
　また、本発明の効果がより優れる点で、炭化水素系溶剤は、芳香族環、又は、直鎖状アルキル基若しくは分岐鎖状アルキル基のみから構成されることが好ましい。 The hydrocarbon solvent may have a linear structure, a branched chain structure, or a cyclic structure.
The hydrocarbon solvent may have, for example, a linear alkyl group, a branched chain alkyl group, an alicyclic group, or an aromatic group. Among them, the hydrocarbon solvent preferably has a linear alkyl group or an aromatic group because the effect of the present invention is more excellent.
Further, from the viewpoint that the effect of the present invention is more excellent, the hydrocarbon-based solvent is preferably composed of only an aromatic ring or a linear alkyl group or a branched alkyl group.
　炭化水素系溶剤の炭素数は特に制限されないが、７以上が好ましく、８以上がより好ましい。上限は特に制限されないが、２０以下が好ましく、１７以下がより好ましく、１５以下が更に好ましい。 The number of carbon atoms in the hydrocarbon solvent is not particularly limited, but 7 or more is preferable, and 8 or more is more preferable. The upper limit is not particularly limited, but 20 or less is preferable, 17 or less is more preferable, and 15 or less is further preferable.
　炭化水素系溶剤の沸点（℃）と、フッ素系溶剤の沸点（℃）との差の絶対値は特に制限されないが、１００℃以上が好ましく、１０５℃以上がより好ましい。上限は特に制限されないが、２００℃以下が好ましく、１５０℃以下がより好ましい。上記沸点は、１気圧における沸点である。 The absolute value of the difference between the boiling point (° C.) of the hydrocarbon solvent and the boiling point (° C.) of the fluorine-based solvent is not particularly limited, but is preferably 100 ° C. or higher, more preferably 105 ° C. or higher. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. The boiling point is the boiling point at 1 atm.
　炭化水素系溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The hydrocarbon solvent may be used alone or in combination of two or more.
　第二溶剤の含有量は特に制限されず、処理液の全質量に対して、５～９５質量％の場合が多く、本発明の効果がより優れる点で、２０～９０質量％が好ましく、３０～９０質量％がより好ましく、５０～９０質量％が更に好ましい。 The content of the second solvent is not particularly limited, and is often 5 to 95% by mass with respect to the total mass of the treatment liquid, and 20 to 90% by mass is preferable in that the effect of the present invention is more excellent. It is more preferably from 90% by mass, still more preferably from 50 to 90% by mass.
〔その他の成分〕
　本発明の処理液は、上述以外のその他の成分を含んでいてもよい。 [Other ingredients]
The treatment liquid of the present invention may contain other components other than those described above.
＜金属成分＞
　処理液は、金属成分を含んでいてもよい。
　金属成分としては、金属粒子及び金属イオンが挙げられ、例えば、金属成分の含有量という場合、金属粒子及び金属イオンの合計含有量を示す。
　処理液は、金属粒子及び金属イオンのいずれか一方を含んでいてもよく、両方を含んでいてもよい。 <Metal component>
The treatment liquid may contain a metal component.
Examples of the metal component include metal particles and metal ions. For example, the content of the metal component indicates the total content of the metal particles and the metal ions.
The treatment liquid may contain either metal particles or metal ions, or may contain both.
　金属成分に含まれる金属原子としては、例えば、Ａｇ、Ａｌ、Ａｓ、Ａｕ、Ｂａ、Ｃａ、Ｃｄ、Ｃｏ、Ｃｒ、Ｃｕ、Ｆｅ、Ｇａ、Ｇｅ、Ｋ、Ｌｉ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎａ、Ｎｉ、Ｐｂ、Ｓｎ、Ｓｒ、Ｔｉ、及び、Ｚｎからなる群から選ばれる金属原子が挙げられる。
　金属成分は、金属原子を１種含んでいてもよいし、２種以上含んでいてもよい。
　金属粒子は、単体でも合金でもよく、金属が有機物と会合した形態で存在していてもよい。
　金属成分は、処理液に含まれる各成分（原料）に不可避的に含まれている金属成分でもよいし、処理液の製造、貯蔵、及び／又は、移送時に不可避的に含まれる金属成分でもよいし、意図的に添加してもよい。 Examples of the metal atom contained in the metal component include Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na. Examples thereof include metal atoms selected from the group consisting of Ni, Pb, Sn, Sr, Ti, and Zn.
The metal component may contain one kind of metal atom or two or more kinds.
The metal particles may be simple substances or alloys, and may exist in a form in which the metal is associated with an organic substance.
The metal component may be a metal component unavoidably contained in each component (raw material) contained in the treatment liquid, or may be a metal component unavoidably contained during the production, storage, and / or transfer of the treatment liquid. However, it may be added intentionally.
　処理液が金属成分を含む場合、金属成分の含有量は、処理液の全質量に対して、０質量ｐｐｔ超１質量ｐｐｍ以下が好ましく、０質量ｐｐｔ超１０質量ｐｐｂ以下がより好ましく、０質量ｐｐｔ超１０質量ｐｐｔ以下が更に好ましい。
　なお、処理液中の金属成分の種類及び含有量は、ＩＣＰ－ＭＳ法（誘導結合プラズマ質量分析法）で測定できる。 When the treatment liquid contains a metal component, the content of the metal component is preferably more than 0 mass ppt and 1 mass ppm or less, more preferably more than 0 mass ppt and 10 mass ppb or less, and 0 mass with respect to the total mass of the treatment liquid. More than 10 mass ppt or less is more preferable.
The type and content of the metal component in the treatment liquid can be measured by the ICP-MS method (inductively coupled plasma mass spectrometry).
＜イオン性液体＞
　本発明の処理液は、以下のイオン性液体を含んでいてもよい。なお、処理液がイオン性液体を含む場合には、イオン性液体は、フッ素系溶剤、及び、第二溶剤には含まれないものとする。
　イオン性液体としては、例えば、陽イオンとして、ピリジニウムイオン若しくはイミダゾリウムイオン等の芳香族系イオン、又は、トリメチルヘキシルアンモニウムイオン等の脂肪族アミン系イオン等を有する。陰イオンとしては、ＮＯ３ －、ＣＨ３ＣＯ２ －、ＢＦ６ －、若しくは、ＰＦ６ －等の無機イオン系、又は、（ＣＦ３ＳＯ２）２Ｎ－、ＣＦ３ＣＯ２ －、若しくは、ＣＦ３ＳＯ２ －等のフッ素含有有機陰イオン等を有するイオン性液体；４級アンモニウム塩系イオン性液体が好ましい。 <Ionic liquid>
The treatment liquid of the present invention may contain the following ionic liquids. When the treatment liquid contains an ionic liquid, the ionic liquid shall not be contained in the fluorine-based solvent and the second solvent.
Examples of the ionic liquid include aromatic ions such as pyridinium ion and imidazolium ion, and aliphatic amine ions such as trimethylhexyl ammonium ion as cations. The anion, NO 3 -, CH 3 CO 2 -, BF 6 -, or, PF 6 - or the like inorganic ionic or, (CF 3 SO 2) 2 N -, CF 3 CO 2 -, or, - CF 3 SO 2 ionic liquids having fluorine-containing organic anions such as, quaternary ammonium salt-based ionic liquid preferably.
　イオン性液体の市販品としては、例えば、ＩＬ－Ｐ１４、及び、ＩＬ－Ａ２（広栄化学工業社製）；エレガンＳＳ－１００（日本油脂社製）等の４級アンモニウム塩系イオン性液体等が挙げられる。
　イオン性液体は、１種を単独使用してもよいし、２種以上を併用してもよい。 Examples of commercially available ionic liquids include IL-P14 and IL-A2 (manufactured by Koei Chemical Industry Co., Ltd.); quaternary ammonium salt-based ionic liquids such as Elegan SS-100 (manufactured by NOF CORPORATION). Can be mentioned.
As the ionic liquid, one type may be used alone, or two or more types may be used in combination.
　本発明の処理液がイオン性液体を含む場合、イオン性液体の含有量は、処理液の全質量に対して、０．５～１５質量％が好ましく、１～１０質量％がより好ましく、１～５質量％が更に好ましい。 When the treatment liquid of the present invention contains an ionic liquid, the content of the ionic liquid is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of the treatment liquid. It is more preferably ~ 5% by mass.
＜界面活性剤＞
　本発明の処理液は、界面活性剤を含んでいてもよい。
　処理液が界面活性剤を含む場合、処理液のレジスト膜に対する濡れ性が向上して、現像及び／又はリンスがより効果的に進行する。
　界面活性剤としては、後述するレジスト組成物に含まれ得る界面活性剤と同様のものを使用できる。
　界面活性剤は、１種を単独使用してもよいし、２種以上を併用してもよい。
　本発明の処理液が界面活性剤を含む場合、界面活性剤の含有量は、処理液の全質量に対して、０．００１～５質量％が好ましく、０．００５～２質量％がより好ましく、０．０１～０．５質量％が更に好ましい。 <Surfactant>
The treatment liquid of the present invention may contain a surfactant.
When the treatment liquid contains a surfactant, the wettability of the treatment liquid with respect to the resist film is improved, and development and / or rinsing proceeds more effectively.
As the surfactant, the same surfactant as that which can be contained in the resist composition described later can be used.
One type of surfactant may be used alone, or two or more types may be used in combination.
When the treatment liquid of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the treatment liquid. , 0.01-0.5% by mass is more preferable.
＜酸化防止剤＞
　本発明の処理液は、酸化防止剤を含んでいてもよい。
　酸化防止剤としては、アミン系酸化防止剤、又は、フェノール系酸化防止剤であることが好ましい。
　酸化防止剤は、１種を単独使用してもよいし、２種以上を併用してもよい。
　本発明の処理液が酸化防止剤を含む場合、酸化防止剤の含有量は、処理液の全質量に対して、０．０００１～１質量％が好ましく、０．０００１～０．１質量％がより好ましく、０．０００１～０．０１質量％が更に好ましい。 <Antioxidant>
The treatment liquid of the present invention may contain an antioxidant.
The antioxidant is preferably an amine-based antioxidant or a phenol-based antioxidant.
One type of antioxidant may be used alone, or two or more types may be used in combination.
When the treatment liquid of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.0001 to 1% by mass, preferably 0.0001 to 0.1% by mass, based on the total mass of the treatment liquid. More preferably, 0.0001 to 0.01% by mass is further preferable.
＜塩基性化合物＞
　本発明の処理液は、塩基性化合物を含んでいてもよい。
　塩基性化合物の具体例としては、後述するレジスト組成物に含まれ得る酸拡散制御剤として例示する化合物が挙げられる。
　塩基性化合物は、１種を単独使用してもよいし、２種以上を併用してもよい。
　本発明の処理液が塩基性化合物を含む場合、塩基性化合物の含有量は、処理液全質量に対して、１０質量％以下が好ましく、０．５～５質量％がより好ましい。
　なお、本発明において、上記塩基性化合物は、１種のみを使用してもよいし、化学構造が異なる２種以上を併用してもよい。 <Basic compound>
The treatment liquid of the present invention may contain a basic compound.
Specific examples of the basic compound include compounds exemplified as acid diffusion control agents that can be contained in the resist composition described later.
As the basic compound, one type may be used alone, or two or more types may be used in combination.
When the treatment liquid of the present invention contains a basic compound, the content of the basic compound is preferably 10% by mass or less, more preferably 0.5 to 5% by mass, based on the total mass of the treatment liquid.
In the present invention, only one kind of the basic compound may be used, or two or more kinds having different chemical structures may be used in combination.
＜沸点３００℃以上の有機物＞
　沸点３００℃以上の有機物を含む処理液を半導体デバイス製造プロセスに適用した場合、高沸点の上記有機物が揮発せずに残存し、基板の欠陥不良の原因になる場合がある。
　沸点３００℃以上の有機物は、例えば、製造装置の部材に用いられたプラスチック材料（例えば、Ｏ－リング等）中に含まれる樹脂成分又は可塑剤等が考えられ、製造過程のいずれかの時点で液中に溶出したものと推測される。
　処理液に沸点３００℃以上の有機物を含む場合、上記沸点３００℃以上の有機物の含有量が、半導体デバイス製造プロセスに用いた場合に基板の欠陥不良の抑制の観点から、処理液全質量に対して、０．００１～５０質量ｐｐｍが好ましく、０．００１～３０質量ｐｐｍがより好ましく、０．００１～１５質量ｐｐｍが更に好ましく、０．００１～１０質量ｐｐｍが特に好ましく、０．００１～１質量ｐｐｍが最も好ましい。 <Organic matter with a boiling point of 300 ° C or higher>
When a treatment liquid containing an organic substance having a boiling point of 300 ° C. or higher is applied to a semiconductor device manufacturing process, the organic substance having a high boiling point may remain without volatilization, which may cause defects in the substrate.
The organic substance having a boiling point of 300 ° C. or higher may be, for example, a resin component or a plasticizer contained in a plastic material (for example, an O-ring) used for a member of a manufacturing apparatus, and at any time in the manufacturing process. It is presumed that it was eluted in the liquid.
When the treatment liquid contains an organic substance having a boiling point of 300 ° C. or higher, the content of the organic substance having a boiling point of 300 ° C. or higher is based on the total mass of the treatment liquid from the viewpoint of suppressing defects in the substrate when used in the semiconductor device manufacturing process. Therefore, 0.001 to 50 mass ppm is preferable, 0.001 to 30 mass ppm is more preferable, 0.001 to 15 mass ppm is further preferable, 0.001 to 10 mass ppm is particularly preferable, and 0.001 to 1 mass ppm is particularly preferable. Mass ppm is most preferred.
　上記沸点が３００℃以上の有機物の含有量が、処理液全質量に対して３０質量ｐｐｍ以下であることが、例えば、上記処理液を現像液として使用して基板に接触させた場合に、上記有機物が揮発せずに基板表面に残存し、欠陥不良となることを抑制する点で好ましい。
　上記沸点が３００℃以上の有機物の含有量が、処理液全質量に対して１５質量ｐｐｍ以下であることが、例えば、上記処理液を現像液として使用して基板に接触させた場合に、ベーク工程後にも沸点が３００℃以上の有機物が基板上に残存することを防ぐため、欠陥の原因（現像不良）を抑制する観点で更に好ましい。
　処理液中、含まれ得る沸点３００℃以上の有機物としては、Ｏ－リングから溶出するフタル酸ジオクチル（ＤＯＰ、沸点３８５℃）等の成分、フタル酸ジイソノニル（ＤＩＮＰ、沸点４０３℃）、アジピン酸ジオクチル（ＤＯＡ、沸点３３５℃）、フタル酸ジブチル（ＤＢＰ、沸点３４０℃）、及び、エチレンプロピレンゴム（ＥＰＤＭ、沸点３００～４５０℃）等が確認されている。 The content of an organic substance having a boiling point of 300 ° C. or higher is 30% by mass or less with respect to the total mass of the treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate. It is preferable in that organic substances are not volatilized and remain on the surface of the substrate to prevent defects from occurring.
The content of organic substances having a boiling point of 300 ° C. or higher is 15% by mass or less with respect to the total mass of the treatment liquid, for example, when the treatment liquid is used as a developing solution and brought into contact with a substrate, it is baked. It is more preferable from the viewpoint of suppressing the cause of defects (development failure) in order to prevent organic substances having a boiling point of 300 ° C. or higher from remaining on the substrate even after the step.
Organic substances having a boiling point of 300 ° C. or higher that can be contained in the treatment liquid include components such as diisononyl phthalate (DOP, boiling point 385 ° C.) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403 ° C.), and dioctyl adipate. (DOA, boiling point 335 ° C.), dibutyl phthalate (DBP, boiling point 340 ° C.), ethylene propylene rubber (EPDM, boiling point 300 to 450 ° C.) and the like have been confirmed.
　処理液中の沸点が３００℃以上の有機物の含有量を上記範囲内にする方法としては、後述する精製工程で挙げる方法が挙げられる。 Examples of the method for keeping the content of organic substances having a boiling point of 300 ° C. or higher in the treatment liquid within the above range include the methods mentioned in the purification step described later.
〔パターン形成方法〕
　本発明は上記処理液を用いたパターン形成方法にも関する。
　パターン形成方法は、例えば、
（ｉ）レジスト組成物を使用してレジスト膜を形成するレジスト膜形成工程と、
（ｉｉ）上記レジスト膜を露光する露光工程と、
（ｉｉｉ）露光された上記レジスト膜を上述した処理液によって処理する処理工程と、を備える。 [Pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned treatment liquid.
The pattern forming method is, for example,
(I) A resist film forming step of forming a resist film using a resist composition, and
(Ii) An exposure step for exposing the resist film and
(Iii) The present invention includes a treatment step of treating the exposed resist film with the above-mentioned treatment liquid.
　以下、パターン形成方法が有する各工程について説明する。また、処理工程の一例として、現像工程及びリンス工程のそれぞれについて説明する。 Hereinafter, each process of the pattern forming method will be described. Further, as an example of the processing process, each of the developing process and the rinsing process will be described.
＜（ｉ）レジスト膜形成工程＞
　レジスト膜形成工程は、レジスト組成物を使用してレジスト膜を形成する工程である。
　レジスト組成物を使用してレジスト膜を形成するにあたっては、例えば、後述する各成分を溶剤に溶解してレジスト組成物を調製し、必要に応じてフィルタろ過した後、支持体（基板）上にレジスト組成物を塗布してレジスト膜を形成する。フィルタの孔径としては、０．１μｍ以下が好ましく、０．０５μｍ以下がより好ましく、０．０３μｍ以下が更に好ましい。フィルタの材質としては、ポリテトラフルオロエチレン、ポリエチレン、又は、ナイロンが好ましい。 <(I) Resist film forming step>
The resist film forming step is a step of forming a resist film using a resist composition.
In forming a resist film using a resist composition, for example, each component described later is dissolved in a solvent to prepare a resist composition, which is filtered as necessary, and then placed on a support (substrate). A resist composition is applied to form a resist film. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. As the material of the filter, polytetrafluoroethylene, polyethylene, or nylon is preferable.
　レジスト組成物は、例えば、支持体（基板）上に、スピナー等の適当な塗布方法により塗布される。その後、塗膜（塗布されたレジスト組成物の塗膜）を乾燥し、レジスト膜を形成する。必要により、レジスト膜の下層に、各種下地膜（無機膜、有機膜、及び、反射防止膜）を形成してもよい。 The resist composition is applied onto a support (substrate), for example, by an appropriate coating method such as a spinner. Then, the coating film (the coating film of the applied resist composition) is dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, and antireflection film) may be formed under the resist film.
　レジスト膜を形成する支持体は、特に制限されるものではなく、ＩＣ等の半導体の製造工程、又は、液晶若しくはサーマルヘッド等の回路基板の製造工程の他、その他のフォトファブリケーションのリソグラフィー工程等で一般的に用いられる基板を使用できる。
　支持体の具体例としては、シリコン、ＳｉＯ２、及び、ＳｉＮ等の無機基板等も挙げられる。
　上記基板には、単層からなる半導体基板、及び、多層からなる半導体基板も含まれる。
　単層からなる半導体基板を構成する材料は特に制限されず、一般的に、シリコン、シリコンゲルマニウム、ＧａＡｓのような第ＩＩＩ－Ｖ族化合物、又は、それらの任意の組み合わせから構成されることが好ましい。
　多層からなる半導体基板である場合には、その構成は特に制限されず、例えば、上述のシリコン等の半導体基板上に金属線及び誘電材料のような相互接続構造（ｉｎｔｅｒｃｏｎｎｅｃｔ　ｆｅａｔｕｒｅｓ）等の露出した集積回路構造を有していてもよい。相互接続構造に用いられる金属及び合金としては、アルミニウム及び銅と、合金化されたアルミニウム、銅、チタン、タンタル、コバルト、シリコン、窒化チタン、窒化タンタル、及び、タングステンが挙げられるが、これらに制限されるものではない。また、半導体基板上に、層間誘電体層、酸化シリコン、窒化シリコン、炭化シリコン、及び、炭素ドープ酸化シリコン等の層を有していてもよい。 The support that forms the resist film is not particularly limited, and is not particularly limited, such as a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal or a thermal head, and other photolithography lithography processes. Commonly used substrates can be used in.
Specific examples of the support include an inorganic substrate such as silicon, SiO 2 , and SiN.
The substrate also includes a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers.
The material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of a group III-V compound such as silicon, silicon germanium, or GaAs, or any combination thereof. ..
In the case of a multi-layered semiconductor substrate, its configuration is not particularly limited, and for example, an interconnect structure such as a metal wire and a dielectric material is exposed and integrated on the above-mentioned semiconductor substrate such as silicon. It may have a circuit structure. Metals and alloys used in the interconnect structure include, but are limited to, aluminum and copper and alloyed aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It is not something that is done. Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on the semiconductor substrate.
　乾燥方法としては、加熱して乾燥する方法が一般的に用いられる。
　加熱温度としては、８０～１８０℃が好ましく、８０～１５０℃がより好ましく、８０～１４０℃が更に好ましく、８０～１３０℃が特に好ましい。
　加熱時間としては、３０～１０００秒が好ましく、６０～８００秒がより好ましく、６０～６００秒が更に好ましい。 As a drying method, a method of heating and drying is generally used.
The heating temperature is preferably 80 to 180 ° C., more preferably 80 to 150 ° C., further preferably 80 to 140 ° C., and particularly preferably 80 to 130 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
　レジスト膜の膜厚は、一般的には２００ｎｍ以下であり、１００ｎｍ以下が好ましい。
　例えば３０ｎｍ以下のサイズの１：１ラインアンドスペースパターンを解像させるためには、レジスト膜の膜厚は、５０ｎｍ以下が好ましい。膜厚が５０ｎｍ以下であれば、後述する現像工程を適用した際に、パターン倒れがより起こりにくくなり、より優れた解像性能が得られる。
　膜厚は、エッチング耐性と解像性がより優れる点で、１５～７０ｎｍが好ましく、１５～６５ｎｍがより好ましい。 The film thickness of the resist film is generally 200 nm or less, preferably 100 nm or less.
For example, in order to resolve a 1: 1 line-and-space pattern having a size of 30 nm or less, the film thickness of the resist film is preferably 50 nm or less. When the film thickness is 50 nm or less, pattern collapse is less likely to occur when the development step described later is applied, and more excellent resolution performance can be obtained.
The film thickness is preferably 15 to 70 nm, more preferably 15 to 65 nm, in that it is more excellent in etching resistance and resolution.
　また、必要に応じて、レジスト膜と支持体との間にレジスト下層膜（例えば、ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）、ＳＯＣ（Ｓｐｉｎ　Ｏｎ　Ｃａｒｂｏｎ）、及び、反射防止膜）を形成してもよい。レジスト下層膜を構成する材料としては、公知の有機系又は無機系の材料を適宜使用できる。
　レジスト膜の上層に、保護膜（トップコート）を形成してもよい。保護膜としては、公知の材料を適宜使用できる。例えば、米国特許出願公開第２００７／０１７８４０７号明細書、米国特許出願公開第２００８／００８５４６６号明細書、米国特許出願公開第２００７／０２７５３２６号明細書、米国特許出願公開第２０１６／０２９９４３２号明細書、米国特許出願公開第２０１３／０２４４４３８号明細書、国際特許出願公開第２０１６／１５７９８８Ａ号明細書に開示された保護膜形成用組成物を好適に使用できる。保護膜形成用組成物としては、上述した酸拡散制御剤を含むものが好ましい。また、例えば、特開２０１４－０５９５４３号公報の段落［００７２］～［００８２］の記載に基づいて上層膜を形成してもよい。
　保護膜の膜厚は、１０～２００ｎｍが好ましく、２０～１００ｎｍがより好ましく、４０～８０ｎｍが更に好ましい。 Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent. Further, for example, the upper layer film may be formed based on the description in paragraphs [0072] to [2002] of JP-A-2014-059543.
The film thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.
＜（ｉｉ）露光工程＞
　パターン形成方法は、（ｉｉ）露光工程における露光方法が、液浸露光であってもよい。
　パターン形成方法は、（ｉｉ）露光工程の前に、（ｉｖ）前加熱（ＰＢ：ＰｒｅＢａｋｅ、以下、「塗布後ベーク」ともいう。）工程を含むことが好ましい。
　パターン形成方法は、（ｉｉ）露光工程の後、かつ、（ｉｉｉ）現像工程の前に、（ｖ）露光後加熱（ＰＥＢ：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ、露光後ベークもいう）工程を含むことが好ましい。
　パターン形成方法は、（ｉｉ）露光工程を、複数回含んでいてもよい。
　パターン形成方法は、（ｉｖ）前加熱工程を、複数回含んでいてもよい。
　パターン形成方法は、（ｖ）露光後加熱工程を、複数回含んでいてもよい。 <(Ii) exposure process>
As for the pattern forming method, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method preferably includes (iv) preheating (PB: PreBake, hereinafter also referred to as "post-coating bake") step before the (ii) exposure step.
The pattern forming method preferably includes (v) post-exposure heating (PEB: Post Exposure Bake, also referred to as post-exposure bake) step after the (ii) exposure step and before the (iii) development step.
The pattern forming method may include (ii) exposure steps a plurality of times.
The pattern forming method may include (iv) a preheating step a plurality of times.
The pattern forming method may include (v) a post-exposure heating step a plurality of times.
　パターン形成方法において、（ｉｉ）露光工程は、一般的に知られている方法により行うことができる。 In the pattern forming method, the (ii) exposure step can be performed by a generally known method.
　加熱温度は、（ｉｖ）前加熱工程及び（ｖ）露光後加熱工程のいずれにおいても、８０～１５０℃が好ましく、８０～１４０℃がより好ましく、８０～１３０℃が更に好ましい。
　加熱時間は、（ｉｖ）前加熱工程及び（ｖ）露光後加熱工程のいずれにおいても、３０～１０００秒が好ましく、６０～８００秒がより好ましく、６０～６００秒が更に好ましい。
　加熱は、露光装置及び現像装置に備わっている手段で行うことができ、ホットプレート等を使用して行ってもよい。 The heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., still more preferably 80 to 130 ° C. in both the (iv) preheating step and the (v) post-exposure heating step.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, still more preferably 60 to 600 seconds in both the (iv) preheating step and the (v) post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.
　露光工程に用いられる光源波長に制限はないが、例えば、赤外光、可視光、紫外光、遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、及び、電子線等が挙げられる。これらのなかでも遠紫外線が好ましく、その波長は２５０ｎｍ以下が好ましく、２２０ｎｍ以下がより好ましく、１～２００ｎｍが更に好ましい。具体的には、ＫｒＦエキシマレーザー（２４８ｎｍ）、ＡｒＦエキシマレーザー（１９３ｎｍ）、Ｆ２エキシマレーザー（１５７ｎｍ）、Ｘ線、ＥＵＶ（１３ｎｍ）、及び、電子線等であり、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、ＥＵＶ、又は、電子線が好ましく、ＥＵＶ又は電子線がより好ましい。 The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam. Among these, far ultraviolet rays are preferable, and the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, further preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), and an electron beam or the like, KrF excimer laser, ArF excimer laser , EUV, or electron beam is preferable, and EUV or electron beam is more preferable.
＜（ｉｉｉ）露光された膜を処理する工程＞
　（ｉｉｉ）露光された膜を処理する工程は、通常、（ｖｉ）現像液によって現像する現像工程（現像工程）と、（ｖｉｉ）リンス液によって洗浄するリンス工程（リンス工程）とを含む。
　本発明の処理液は、現像工程における現像液として使用されてもよいし、リンス工程におけるリンス液として使用されてもよい。なかでも、リンス工程におけるリンス液として使用されることが好ましい。
　本発明の処理液をリンス工程におけるリンス液として使用する場合、現像工程における現像液としては、本発明の処理液以外のその他の処理液を使用することが好ましい。 <(Iii) Step of processing the exposed film>
(Iii) The step of treating the exposed film usually includes (vi) a developing step of developing with a developing solution (developing step) and (vii) a rinsing step of washing with a rinsing solution (rinsing step).
The treatment liquid of the present invention may be used as a developing solution in a developing step, or may be used as a rinsing liquid in a rinsing step. Above all, it is preferable to use it as a rinsing liquid in the rinsing process.
When the treatment liquid of the present invention is used as a rinsing liquid in the rinsing step, it is preferable to use a treatment liquid other than the treatment liquid of the present invention as the developing liquid in the developing step.
（現像工程）
　現像工程は、露光された上記レジスト膜を現像液によって現像する工程である。 (Development process)
The developing step is a step of developing the exposed resist film with a developing solution.
　現像方法としては、例えば、現像液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面に現像液を表面張力によって盛り上げて一定時間静止する方法（パドル法）、基板表面に現像液を噴霧する方法（スプレー法）、及び、一定速度で回転している基板上に一定速度で現像液吐出ノズルをスキャンしながら現像液を吐出しつづける方法（ダイナミックディスペンス法）等が挙げられる。
　また、現像工程の後に、他の溶剤に置換しながら、現像を停止する工程を実施してもよい。
　現像時間としては、１０～３００秒が好ましく、２０～１２０秒がより好ましい。
　現像液の温度としては、０～５０℃が好ましく、１５～３５℃がより好ましい。 Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate. There are methods such as spraying the developer on the surface (spray method) and continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method). Can be mentioned.
Further, after the developing step, a step of stopping the development may be carried out while substituting with another solvent.
The development time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
　現像液としては、上述した処理液を使用してもよいし、その他の現像液を使用してもよい。
　処理液を用いた現像に加えて、アルカリ現像液による現像を行ってもよい（いわゆる二重現像）。 As the developing solution, the above-mentioned processing solution may be used, or other developing solution may be used.
In addition to development using a treatment liquid, development with an alkaline developer may be performed (so-called double development).
≪その他の現像液≫
　以下において、その他の現像液（本発明の処理液以外の現像液）について説明する。
　現像液に使用される有機溶剤の蒸気圧（混合溶剤である場合は全体としての蒸気圧）は、２０℃において、５ｋＰａ以下が好ましく、３ｋＰａ以下がより好ましく、２ｋＰａ以下が更に好ましい。有機溶剤の蒸気圧を５ｋＰａ以下にすることにより、現像液の基板上又は現像カップ内での蒸発が抑制され、基板面内の温度均一性が向上し、結果として基板面内の寸法均一性が良化する。
　現像液に使用される有機溶剤としては特に制限されないが、例えば、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、及び、炭化水素系溶剤等の溶剤が挙げられる。 ≪Other developers≫
Hereinafter, other developing solutions (developing solutions other than the processing solution of the present invention) will be described.
The vapor pressure of the organic solvent used in the developing solution (in the case of a mixed solvent, the overall vapor pressure) is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C. By reducing the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the substrate surface is improved, and as a result, the dimensional uniformity in the substrate surface is improved. Improve.
The organic solvent used in the developing solution is not particularly limited, and examples thereof include solvents such as ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
　現像液としては、なかでも、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、及び、エーテル系溶剤からなる群から選ばれる溶剤を１種以上含むことが好ましい。 The developer preferably contains at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent.
　エステル系溶剤としては、例えば、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸ｓｅｃ－ブチル、酢酸ペンチル、酢酸プロピル、酢酸イソプロピル、酢酸アミル（酢酸ペンチル）、酢酸イソアミル（酢酸イソペンチル、酢酸３－メチルブチル）、酢酸２－メチルブチル、酢酸１－メチルブチル、酢酸ヘキシル、酢酸イソヘキシル、酢酸ヘプチル、酢酸オクチル、メトキシ酢酸エチル、エトキシ酢酸エチル、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；別名１－メトキシ－２－アセトキシプロパン）、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、２－メトキシブチルアセテート、３－メトキシブチルアセテート、４－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、３－エチル－３－メトキシブチルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、２－エトキシブチルアセテート、４－エトキシブチルアセテート、４－プロポキシブチルアセテート、２－メトキシペンチルアセテート、３－メトキシペンチルアセテート、４－メトキシペンチルアセテート、２－メチル－３－メトキシペンチルアセテート、３－メチル－３－メトキシペンチルアセテート、３－メチル－４－メトキシペンチルアセテート、４－メチル－４－メトキシペンチルアセテート、プロピレングリコールジアセテート、ギ酸メチル、ギ酸エチル、ギ酸ブチル、ギ酸プロピル、ギ酸アミル、ギ酸イソアミル、ギ酸ヘキシル、乳酸エチル、乳酸ブチル、乳酸プロピル、炭酸エチル、炭酸プロピル、炭酸ブチル、炭酸ジエチル、炭酸ジブチル、ブタン酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、ピルビン酸ブチル、アセト酢酸メチル、アセト酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸イソプロピル、プロピオン酸ブチル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸ヘキシル、酪酸エチル、イソ酪酸エチル、酪酸ブチル、酪酸イソブチル、酪酸ペンチル、酪酸ヘキシル、イソ酪酸イソブチル、イソ吉草酸エチル、イソ吉草酸ブチル、吉草酸プロピル、吉草酸イソプロピル、吉草酸ブチル、吉草酸ペンチル、ヘキサン酸エチル、ヘキサン酸プロピル、ヘキサン酸ブチル、ヘキサン酸イソブチル、ヘプタン酸メチル、ヘプタン酸エチル、ヘプタン酸プロピル、酢酸シクロヘキシル、酢酸シクロヘプチル、酢酸２－エチルヘキシル、プロピオン酸シクロペンチル、２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル、メチル－３－メトキシプロピオネート、エチル－３－メトキシプロピオネート、エチル－３－エトキシプロピオネート、プロピル－３－メトキシプロピオネート、及び、３－メチル吉草酸エチル等が挙げられる。
　なかでも、酢酸ブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸ｓｅｃ－ブチル、酢酸アミル、酢酸イソアミル、ギ酸アミル、ギ酸イソアミル、ギ酸ヘキシル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸イソプロピル、プロピオン酸プロピル、酪酸エチル、イソ酪酸エチル、炭酸ジエチル、炭酸ジブチル、ブタン酸ブチル、イソ酪酸イソブチル、イソ吉草酸エチル、イソ吉草酸ブチル、ヘプタン酸プロピル、ヘプタン酸エチル、ヘキサン酸ブチル、ヘキサン酸プロピル、又は、３－メチル吉草酸エチルが好ましい。 Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (acetate). Isopentyl, 3-methylbutyl acetate), 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy) -2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl- 3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-Methyl-3-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate , Methyl formate, ethyl formate, butyl formate, propyl formate, amyl formate, isoamyl formate, hexyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, diethyl carbonate, dibutyl carbonate, butyl butano, Methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethiacetate Lu, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, amyl propionate, isoamyl propionate, hexyl propionate, ethyl butyrate, ethyl isobutyrate, butyl butyrate, isobutyl butyrate, pentyl butyrate, Hexyl butyrate, isobutyl isobutyrate, ethyl isovalerate, butyl isovalerate, propyl valerate, isopropyl valerate, butyl valerate, pentyl valerate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexagonate, heptane Methyl acid, ethyl heptate, propyl heptate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, Examples thereof include ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and ethyl 3-methylvalerate.
Among them, butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, amyl formate, isoamyl formate, hexyl formate, amyl propionate, isoamyl propionate, isopropyl propionate, propyl propionate, Ethyl butyrate, ethyl isobutyrate, diethyl carbonate, dibutyl carbonate, butyl butanoate, isobutyl isobutyrate, ethyl isovalerate, butyl isovalerate, propyl heptate, ethyl heptate, butyl hexanoate, propyl hexanoate, or 3. -Ethyl methyl valerate is preferred.
　ケトン系溶剤としては、例えば、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、アセトン、２－ヘプタノン、４－ヘプタノン、１－ヘキサノン、２－ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、イソホロン、プロピレンカーボネート、及び、γ－ブチロラクトン等が挙げられる。なかでも、２－ヘプタノンが好ましい。 Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, and the like. Examples thereof include phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and γ-butyrolactone. Of these, 2-heptanone is preferable.
　アルコール系溶剤としては、例えば、メタノール、エタノール、１－プロパノール、イソプロパノール、１－ブタノール、２－ブタノール、３－メチル－１－ブタノール、ｔｅｒｔ―ブチルアルコール、１－ペンタノール、２－ペンタノール、１－ヘキサノール、１－ヘプタノール、１－オクタノール、１－デカノール、２－ヘキサノール、２－ヘプタノール、２－オクタノール、３－ヘキサノール、３－ヘプタノール、３－オクタノール、４－オクタノール、３－メチル－３－ペンタノール、シクロペンタノール、２，３－ジメチル－２－ブタノール、３，３－ジメチル－２－ブタノール、２－メチル－２－ペンタノール、２－メチル－３－ペンタノール、３－メチル－２－ペンタノール、３－メチル－３－ペンタノール、４－メチル－２－ペンタノール、４－メチル－３－ペンタノール、シクロヘキサノール、５－メチル－２－ヘキサノール、４－メチル－２－ヘキサノール、４，５－ジチル－２－ヘキサール、６－メチル－２－ヘプタノール、７－メチル－２－オクタノール、８－メチル－２－ノナール、９－メチル－２－デカノール、及び、３－メトキシ－１－ブタノール等のアルコール（１価のアルコール）；エチレングリコール、ジエチレングリコール、及び、トリエチレングリコール等のグリコール系溶剤；エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ；別名１－メトキシ－２－プロパノール）、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、メトキシメチルブタノール、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、及び、プロピレングリコールモノフェニルエーテル等の水酸基を含むグリコールエーテル系溶剤；等が挙げられる。なかでも、グリコールエーテル系溶剤が好ましい。 Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4 , 5-Dityl-2-hexal, 6-methyl-2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, and 3-methoxy-1-butanol. Alcohols such as (monohydric alcohol); glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl. Ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene. Glycol ether-based solvents containing hydroxyl groups such as glycol monophenyl ether; and the like. Of these, glycol ether solvents are preferable.
　エーテル系溶剤としては、例えば、上記水酸基を含むグリコールエーテル系溶剤の他、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、及び、ジエチレングリコールジエチルエーテル等の水酸基を含まないグリコールエーテル系溶剤；アニソール、及び、フェネトール等の芳香族エーテル溶剤；ジオキサン、テトラヒドロフラン、テトラヒドロピラン、パーフルオロ－２－ブチルテトラヒドロフラン、パーフルオロテトラヒドロフラン、１，４－ジオキサン、及び、イソプロピルエーテル等が挙げられる。なかでも、グリコールエーテル系溶剤、又は、アニソール等の芳香族エーテル溶剤が好ましい。 Examples of the ether-based solvent include, in addition to the above-mentioned glycol ether-based solvent containing a hydroxyl group, a glycol ether-based solvent containing no hydroxyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; anisole, and , Aromatic ether solvents such as phenetol; examples include dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyl tetrahydrofuran, perfluorotetratetra, 1,4-dioxane, isopropyl ether and the like. Of these, glycol ether solvents or aromatic ether solvents such as anisole are preferable.
　アミド系溶剤としては、例えば、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、及び、１，３－ジメチル－２－イミダゾリジノン等が挙げられる。 Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. And so on.
　炭化水素系溶剤としては、例えば、ペンタン、ヘキサン、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカン、２，２，４－トリメチルペンタン、２，２，３－トリメチルヘキサン、パーフルオロヘキサン、及び、パーフルオロヘプタン等の脂肪族炭化水素系溶剤；トルエン、キシレン、エチルベンゼン、プロピルベンゼン、１－メチルプロピルベンゼン、２－メチルプロピルベンゼン、ジメチルベンゼン、ジエチルベンゼン、エチルメチルベンゼン、トリメチルベンゼン、エチルジメチルベンゼン、及び、ジプロピルベンゼン等の芳香族炭化水素系溶剤；が挙げられる。
　また、炭化水素系溶剤としては、不飽和炭化水素系溶剤も使用でき、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、及び、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素系溶剤が有する二重結合又は三重結合の数は特に制限されず、また、炭化水素鎖のいずれの位置に有してもよい。また、不飽和炭化水素系溶剤が二重結合を有する場合には、ｃｉｓ体及びｔｒａｎｓ体が混在していてもよい。
　なお、炭化水素系溶剤である脂肪族炭化水素系溶剤においては、同じ炭素数で異なる構造の化合物の混合物であってもよい。例えば、脂肪族炭化水素系溶剤としてデカンを使用した場合、同じ炭素数で異なる構造の化合物である２－メチルノナン、２，２－ジメチルオクタン、４－エチルオクタン、及び、イソオクタン等が脂肪族炭化水素系溶剤に含まれていてもよい。
　また、上記同じ炭素数で異なる構造の化合物は、１種のみが含まれていてもよいし、上記のように複数種含まれていてもよい。 Examples of the hydrocarbon solvent include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and per. Hydrocarbon solvents such as fluoroheptane; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and Aromatic hydrocarbon-based solvents such as dipropylbenzene; can be mentioned.
Further, as the hydrocarbon-based solvent, an unsaturated hydrocarbon-based solvent can also be used, and examples thereof include unsaturated hydrocarbon-based solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene. The number of double bonds or triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position of the hydrocarbon chain. When the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.
The aliphatic hydrocarbon-based solvent, which is a hydrocarbon-based solvent, may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as an aliphatic hydrocarbon-based solvent, compounds having the same carbon number and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, are aliphatic hydrocarbons. It may be contained in a system solvent.
Further, the above-mentioned compounds having the same number of carbon atoms and different structures may contain only one kind, or may contain a plurality of kinds as described above.
　現像液としては、上述した露光工程において、ＥＵＶ光及び電子線を用いる場合にレジスト膜の膨潤をより抑制できるという点で、炭素数が６以上（６～１４が好ましく、６～１２がより好ましく、６～１０が更に好ましい）、かつ、ヘテロ原子数が２以下のエステル系溶剤が好ましい。
　上記ヘテロ原子としては、炭素原子及び水素原子以外の原子であればよく、例えば、酸素原子、窒素原子、及び、硫黄原子等が挙げられる。ヘテロ原子数は、２以下が好ましい。
　炭素数が６以上、かつ、ヘテロ原子数が２以下のエステル系溶剤の具体例としては、酢酸ブチル、酢酸アミル、酢酸イソアミル、酢酸２－メチルブチル、酢酸１－メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ヘプチル、ブタン酸ブチル、イソブタン酸ブチル、及び、イソブタン酸イソブチルからなる群から選ばれるものが好ましく、酢酸イソアミル、又は、イソブタン酸ブチルがより好ましい。 The developer has 6 or more carbon atoms (preferably 6 to 14, more preferably 6 to 12) in that the swelling of the resist film can be further suppressed when EUV light and an electron beam are used in the above-mentioned exposure step. , 6 to 10 is more preferable), and an ester-based solvent having 2 or less heteroatoms is preferable.
The hetero atom may be an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.
Specific examples of ester-based solvents having 6 or more carbon atoms and 2 or less heteroatomic atoms include butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and pentyl propionate. It is preferably selected from the group consisting of hexyl propionate, heptyl propionate, butyl butanoate, butyl isobutate, and isobutyl isobutate, and isoamyl acetate or butyl isobutate is more preferable.
　現像液としては、上述した露光工程において、ＥＵＶ光及び電子線を用いる場合において、レジスト膜の膨潤の抑制をより抑制する点で、上述した炭素数が６以上、かつ、ヘテロ原子数が２以下のエステル系溶剤に代えて、エステル系溶剤及び炭化水素系溶剤の混合溶剤、又は、ケトン系溶剤及び炭化水素系溶剤の混合溶剤を使用してもよい。 When the developing solution uses EUV light and an electron beam in the above-mentioned exposure step, the above-mentioned carbon number is 6 or more and the heteroatom number is 2 or less in that the suppression of swelling of the ester film is further suppressed. A mixed solvent of an ester solvent and a hydrocarbon solvent, or a mixed solvent of a ketone solvent and a hydrocarbon solvent may be used instead of the ester solvent.
　上記混合溶剤において、炭化水素系溶剤の含有量は、レジスト膜の溶剤溶解性に依存するため特に制限されず、適宜調製して必要量を決定すればよい。 In the above mixed solvent, the content of the hydrocarbon solvent depends on the solvent solubility of the resist film and is not particularly limited, and the required amount may be determined as appropriate.
　エステル系溶剤及び炭化水素系溶剤の混合溶剤において、エステル系溶剤としては、酢酸イソアミルが好ましい。炭化水素系溶剤としては、レジスト膜の溶解性を調整しやすい点で、飽和炭化水素系溶剤（例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、及び、ヘキサデカン等）が好ましい。 In the mixed solvent of the ester solvent and the hydrocarbon solvent, isoamyl acetate is preferable as the ester solvent. As the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferable because the solubility of the resist film can be easily adjusted.
　ケトン系溶剤及び炭化水素系溶剤の混合溶剤において、ケトン系溶剤としては、例えば、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、アセトン、２－ヘプタノン（メチルアミルケトン）、４－ヘプタノン、１－ヘキサノン、２－ヘキサノン、ジイソブチルケトン、２，５－ジメチル－４－ヘキサノン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、イソホロン、及び、プロピレンカーボネート等が挙げられ、ジイソブチルケトン、又は、２，５－ジメチル－４－ヘキサノンが好ましい。炭化水素系溶剤としては、レジスト膜の溶解性を調整しやすい点で、飽和炭化水素系溶剤（例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、及び、ヘキサデカン等）が好ましい。 In the mixed solvent of the ketone solvent and the hydrocarbon solvent, examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-. Heptanone, 1-hexanone, 2-hexanone, diisobutylketone, 2,5-dimethyl-4-hexanone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, Examples thereof include acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate, and diisobutyl ketone or 2,5-dimethyl-4-hexanone is preferable. As the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferable because the solubility of the resist film can be easily adjusted.
　上記の溶剤は、複数混合してもよいし、上記以外の溶剤、又は、水と混合してもよい。現像液全体としての含水率は、５０質量％未満が好ましく、２０質量％未満がより好ましく、１０質量％未満が更に好ましく、実質的に水分を含まないことが特に好ましい。
　有機系現像液に対する有機溶剤の含有量は、現像液の全質量に対して、５０～１００質量％が好ましく、８０～１００質量％がより好ましく、９０～１００質量％が更に好ましく、９５～１００質量％が特に好ましい。 A plurality of the above solvents may be mixed, or a solvent other than the above, or water may be mixed. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total mass of the developer. Mass% is particularly preferred.
　現像液は、必要に応じて公知の界面活性剤を適当量含んでいてもよい。 The developer may contain an appropriate amount of a known surfactant, if necessary.
　界面活性剤の含有量は、現像液の全量に対して、通常、０．００１～５質量％であり、０．００５～２質量％が好ましく、０．０１～０．５質量％がより好ましい。 The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution. ..
　現像液は、塩基性化合物を含んでいてもよい。塩基性化合物の具体例としては、後述するレジスト組成物に含まれ得る酸拡散制御剤として例示する化合物が挙げられる。 The developer may contain a basic compound. Specific examples of the basic compound include compounds exemplified as acid diffusion control agents that can be contained in the resist composition described later.
　現像液として用いる有機溶剤としては、上述したエステル系溶剤以外に、下記一般式（Ｓ１）又は下記一般式（Ｓ２）で表される溶剤も好ましい。
　上記エステル系溶剤としては、一般式（Ｓ１）で表される溶剤がより好ましく、酢酸アルキルが更に好ましく、酢酸ブチル、酢酸アミル（酢酸ペンチル）、又は、酢酸イソアミル（酢酸イソペンチル）が特に好ましい。 As the organic solvent used as the developing solution, in addition to the above-mentioned ester-based solvent, a solvent represented by the following general formula (S1) or the following general formula (S2) is also preferable.
As the ester solvent, the solvent represented by the general formula (S1) is more preferable, alkyl acetate is more preferable, and butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isoamyl acetate) is particularly preferable.
　Ｒ－Ｃ（＝Ｏ）－Ｏ－Ｒ’　一般式（Ｓ１） RC (= O) -OR'general formula (S1)
　一般式（Ｓ１）において、Ｒ及びＲ’は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシル基、アルコキシカルボニル基、カルボキシル基、ヒドロキシル基、シアノ基、又は、ハロゲン原子を表す。Ｒ及びＲ’は、互いに結合して環を形成してもよい。
　Ｒ及びＲ’で表されるアルキル基、アルコキシル基、及び、アルコキシカルボニル基の炭素数としては１～１５が好ましく、シクロアルキル基の炭素数としては３～１５が好ましい。
　Ｒ及びＲ’で表されるアルキル基、シクロアルキル基、アルコキシル基、及び、アルコキシカルボニル基、並びに、ＲとＲ’とが互いに結合して形成する環は、置換基を有していてもよい。置換基としては特に制限されないが、例えば、水酸基、カルボニル基を含む基（例えば、アシル基、アルデヒド基、及び、アルコキシカルボニル等）、及び、シアノ基等が挙げられる。
　Ｒ及びＲ’としては、なかでも、水素原子又はアルキル基が好ましい。 In the general formula (S1), R and R'independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom. R and R'may combine with each other to form a ring.
The alkyl group represented by R and R', the alkoxyl group, and the alkoxycarbonyl group preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
The alkyl group represented by R and R', the cycloalkyl group, the alkoxyl group, the alkoxycarbonyl group, and the ring formed by bonding R and R'to each other may have a substituent. .. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, an alkoxycarbonyl, etc.), a cyano group, and the like.
Among them, R and R'preferably a hydrogen atom or an alkyl group.
　一般式（Ｓ１）で表される溶剤としては、例えば、酢酸メチル、酢酸ブチル、酢酸エチル、酢酸イソプロピル、酢酸アミル、酢酸イソアミル、ギ酸メチル、ギ酸エチル、ギ酸ブチル、ギ酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル、炭酸エチル、炭酸プロピル、炭酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、ピルビン酸ブチル、アセト酢酸メチル、アセト酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸イソプロピル、２－ヒドロキシプロピオン酸メチル、及び、２－ヒドロキシプロピオン酸エチル等が挙げられる。 Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate. , Propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, propion Examples thereof include isopropyl acid acid, methyl 2-hydroxypropionate, and ethyl 2-hydroxypropionate.
　なかでも、Ｒ及びＲ’としては、無置換アルキル基が好ましい。
　一般式（Ｓ１）で表される溶剤としては、酢酸アルキルが好ましく、酢酸ブチル、酢酸アミル（酢酸ペンチル）、又は、酢酸イソアミル（酢酸イソペンチル）がより好ましく、酢酸イソアミルが更に好ましい。 Of these, unsubstituted alkyl groups are preferable as R and R'.
As the solvent represented by the general formula (S1), alkyl acetate is preferable, butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isoamyl acetate) is more preferable, and isoamyl acetate is even more preferable.
　現像液が一般式（Ｓ１）で表される溶剤を含む場合、現像液は更に他の有機溶剤（以下、「併用溶剤」ともいう。）を１種以上含んでいてもよい。併用溶剤としては、一般式（Ｓ１）で表される溶剤に分離することなく混合できれば特に制限はなく、一般式（Ｓ１）で表される溶剤以外のエステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、及び、炭化水素系溶剤からなる群から選択される溶剤が挙げられる。
　併用溶剤は１種でも２種以上であってもよいが、安定した性能を得る上では、１種が好ましい。
　現像液が一般式（Ｓ１）で表される溶剤と１種の併用溶剤との混合溶剤である場合、併用溶剤に対する、一般式（Ｓ１）で表される溶剤の含有量の質量比［一般式（Ｓ１）で表される溶剤の含有質量／併用溶剤の含有質量］は、通常２０／８０～９９／１であり、５０／５０～９７／３が好ましく、６０／４０～９５／５がより好ましく、６０／４０～９０／１０が更に好ましい。 When the developer contains a solvent represented by the general formula (S1), the developer may further contain one or more other organic solvents (hereinafter, also referred to as "combined solvent"). The combined solvent is not particularly limited as long as it can be mixed with the solvent represented by the general formula (S1) without separation, and is an ester solvent, a ketone solvent, or an alcohol solvent other than the solvent represented by the general formula (S1). , Amid solvent, ether solvent, and solvent selected from the group consisting of hydrocarbon solvent.
The combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
When the developing solution is a mixed solvent of a solvent represented by the general formula (S1) and one type of combined solvent, the mass ratio of the content of the solvent represented by the general formula (S1) to the combined solvent [general formula] The mass of the solvent represented by (S1) / the mass of the combined solvent] is usually 20/80 to 99/1, preferably 50/50 to 97/3, and more preferably 60/40 to 95/5. It is preferable, and 60/40 to 90/10 is more preferable.
　現像液として用いる有機溶剤としては、下記一般式（Ｓ２）で表される溶剤も好ましい。 As the organic solvent used as the developing solution, a solvent represented by the following general formula (S2) is also preferable.
　Ｒ’’－Ｃ（＝Ｏ）－Ｏ－Ｒ’’’－Ｏ－Ｒ’’’’　一般式（Ｓ２） R "-C (= O) -OR"-OR "" General formula (S2)
　一般式（Ｓ２）において、Ｒ’’及びＲ’’’’は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシル基、アルコキシカルボニル基、カルボキシル基、ヒドロキシル基、シアノ基、又は、ハロゲン原子を表す。Ｒ’’及びＲ’’’’は、互いに結合して環を形成してもよい。
　Ｒ’’及びＲ’’’’としては、水素原子又はアルキル基が好ましい。
　Ｒ’’及びＲ’’’’で表されるアルキル基、アルコキシル基、及び、アルコキシカルボニル基の炭素数としては１～１５が好ましく、シクロアルキル基の炭素数としては３～１５が好ましい。
　Ｒ’’’は、アルキレン基又はシクロアルキレン基を表し、アルキレン基が好ましい。
Ｒ’’’で表されるアルキレン基の炭素数としては１～１０が好ましく、Ｒ’’’で表されるシクロアルキレン基の炭素数としては３～１０が好ましい。
　なお、Ｒ’’’で表されるアルキレン基としては、アルキレン鎖中にエーテル結合を有していてもよい。
　Ｒ’’及びＲ’’’’で表されるアルキル基、シクロアルキル基、アルコキシル基、及び、アルコキシカルボニル基、Ｒ’’’で表されるアルキレン基及びシクロアルキレン基、並びに、Ｒ’’とＲ’’’’とが互いに結合して形成する環は、置換基を有していてもよい。置換基としては特に制限されないが、例えば、水酸基、カルボニル基を含む基（例えば、アシル基、アルデヒド基、及び、アルコキシカルボニル等）、及び、シアノ基等が挙げられる。 In the general formula (S2), R'' and R'''' are independently hydrogen atoms, alkyl groups, cycloalkyl groups, alkoxyl groups, alkoxycarbonyl groups, carboxyl groups, hydroxyl groups, cyano groups, or Represents a halogen atom. R'' and R'''' may be combined with each other to form a ring.
As R'' and R'''', a hydrogen atom or an alkyl group is preferable.
The alkyl group represented by R'' and R'''', the alkoxyl group, and the alkoxycarbonyl group preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
R ′ ″ represents an alkylene group or a cycloalkylene group, and an alkylene group is preferable.
The alkylene group represented by R ″ ″ preferably has 1 to 10 carbon atoms, and the cycloalkylene group represented by R ″ ″ preferably has 3 to 10 carbon atoms.
The alkylene group represented by R ″ may have an ether bond in the alkylene chain.
An alkyl group represented by R'' and R'''', a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, an alkylene group represented by R'''', a cycloalkylene group, and R''. The ring formed by bonding R'''' to each other may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, an alkoxycarbonyl, etc.), a cyano group, and the like.
　一般式（Ｓ２）で表される溶剤としては、例えば、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、メチル－３－メトキシプロピオネート、エチル－３－メトキシプロピオネート、エチル－３－エトキシプロピオネート、プロピル－３－メトキシプロピオネート、メトキシ酢酸エチル、エトキシ酢酸エチル、２－メトキシブチルアセテート、３－メトキシブチルアセテート、４－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、３－エチル－３－メトキシブチルアセテート、２－エトキシブチルアセテート、４－エトキシブチルアセテート、４－プロポキシブチルアセテート、２－メトキシペンチルアセテート、３－メトキシペンチルアセテート、４－メトキシペンチルアセテート、２－メチル－３－メトキシペンチルアセテート、３－メチル－３－メトキシペンチルアセテート、３－メチル－４－メトキシペンチルアセテート、及び、４－メチル－４－メトキシペンチルアセテート等が挙げられる。なかでも、プロピレングリコールモノメチルエーテルアセテートが好ましい。
　これらのなかでも、Ｒ’’及びＲ’’’’が無置換アルキル基であり、Ｒ’’’が無置換のアルキレン基であることが好ましく、Ｒ’’及びＲ’’’’がメチル基及びエチル基のいずれかであることがより好ましく、Ｒ’’及びＲ’’’’がメチル基であることが更により好ましい。 Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, and diethylene glycol monomethyl. Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl -3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl Acetate, 3-Methyl-3-methoxybutyl acetate, 3-Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl Acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, etc. Can be mentioned. Of these, propylene glycol monomethyl ether acetate is preferable.
Among these, it is preferable that R'' and R'''' are unsubstituted alkyl groups, R'''' is an unsubstituted alkylene group, and R'' and R'''' are methyl groups. And an ethyl group is more preferable, and R'' and R'''' are even more preferably a methyl group.
　現像液が一般式（Ｓ２）で表される溶剤を含む場合、現像液は更に併用溶剤を１種以上含んでいてもよい。併用溶剤としては、一般式（Ｓ２）で表される溶剤に分離することなく混合できれば特に制限はなく、一般式（Ｓ２）で表される溶剤以外のエステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、及び、炭化水素系溶剤からなる群から選択される溶剤が挙げられる。
　併用溶剤は１種でも２種以上であってもよいが、安定した性能を得る上では、１種が好ましい。
　現像液が一般式（Ｓ２）で表される溶剤と１種の併用溶剤との混合溶剤である場合、併用溶剤に対する、一般式（Ｓ２）で表される溶剤の含有量の質量比［一般式（Ｓ２）で表される溶剤の含有質量／併用溶剤の含有質量］は、通常２０／８０～９９／１であり、５０／５０～９７／３が好ましく、６０／４０～９５／５がより好ましく、６０／４０～９０／１０が更に好ましい。 When the developing solution contains a solvent represented by the general formula (S2), the developing solution may further contain one or more kinds of combined solvents. The combined solvent is not particularly limited as long as it can be mixed with the solvent represented by the general formula (S2) without being separated, and is an ester solvent, a ketone solvent, or an alcohol solvent other than the solvent represented by the general formula (S2). , Amid solvent, ether solvent, and solvent selected from the group consisting of hydrocarbon solvent.
The combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
When the developing solution is a mixed solvent of the solvent represented by the general formula (S2) and one type of combined solvent, the mass ratio of the content of the solvent represented by the general formula (S2) to the combined solvent [general formula] The mass of the solvent represented by (S2) / the mass of the combined solvent] is usually 20/80 to 99/1, preferably 50/50 to 97/3, and more preferably 60/40 to 95/5. It is preferable, and 60/40 to 90/10 is more preferable.
　また、現像液として用いる有機溶剤としては、芳香環を一つ以上含むエーテル系溶剤も好ましく、下記一般式（Ｓ３）で表される溶剤がより好ましく、アニソールが更に好ましい。 Further, as the organic solvent used as the developing solution, an ether solvent containing one or more aromatic rings is preferable, a solvent represented by the following general formula (S3) is more preferable, and anisole is further preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（Ｓ３）において、ＲＳは、アルキル基を表す。アルキル基としては、炭素数１～４が好ましく、メチル基又はエチル基がより好ましく、メチル基が更に好ましい。 In the general formula (S3), RS represents an alkyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
　現像液（その他の現像液）として、水系のアルカリ現像液を使用してもよい。 A water-based alkaline developer may be used as the developer (other developer).
（リンス工程）
　リンス工程は、上記現像工程の後にリンス液によって洗浄（リンス）する工程である。 (Rinse process)
The rinsing step is a step of washing (rinsing) with a rinsing liquid after the above-mentioned developing step.
　リンス工程においては、現像を行った基板を上記のリンス液を使用して洗浄処理する。
　洗浄処理の方法は特に制限されないが、例えば、一定速度で回転している基板上にリンス液を吐出しつづける方法（回転吐出法）、リンス液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面にリンス液を噴霧する方法（スプレー法）、等を適用することができ、このなかでも回転吐出方法で洗浄処理を行い、洗浄後に基板を２０００～４０００ｒｐｍの回転数で回転させ、リンス液を基板上から除去することが好ましい。
　リンス時間としては、１０～３００秒が好ましく、１０～１８０秒がより好ましく、２０～１２０秒が更に好ましい。
　リンス液の温度としては、０～５０℃が好ましく、１５～３５℃がより好ましい。 In the rinsing step, the developed substrate is washed with the above rinsing solution.
The cleaning treatment method is not particularly limited. For example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary discharge method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinse liquid on the surface of the substrate (spray method), etc. can be applied. Among them, the cleaning treatment is performed by the rotary discharge method, and the substrate is rotated at 2000 to 4000 rpm after cleaning. It is preferable to remove the rinse liquid from the substrate by rotating with.
The rinsing time is preferably 10 to 300 seconds, more preferably 10 to 180 seconds, and even more preferably 20 to 120 seconds.
The temperature of the rinsing liquid is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
　リンス液としては、上述した処理液を使用してもよいし、その他のリンス液を使用してもよい。
　その他のリンス液としては、例えば、上述のその他の現像液、及び、水が挙げられる。 As the rinsing liquid, the above-mentioned treatment liquid may be used, or other rinsing liquid may be used.
Examples of other rinsing solutions include the above-mentioned other developing solutions and water.
　また、現像処理又はリンス処理の後に、パターン上に付着している現像液又はリンス液を超臨界流体により除去する処理を行うことができる。
　更に、現像処理、リンス処理、又は、超臨界流体による処理の後、パターン中に残存する溶剤を除去するために乾燥処理を実施してもよい。
　乾燥温度は、４０～１６０℃が好ましく、５０～１５０℃がより好ましく、５０～１１０℃が更に好ましい。
　乾燥時間としては、１５～３００秒が好ましく、１５～１８０秒がより好ましい。 Further, after the developing treatment or the rinsing treatment, a treatment of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid can be performed.
Further, after the development treatment, the rinsing treatment, or the treatment with the supercritical fluid, a drying treatment may be carried out to remove the solvent remaining in the pattern.
The drying temperature is preferably 40 to 160 ° C, more preferably 50 to 150 ° C, and even more preferably 50 to 110 ° C.
The drying time is preferably 15 to 300 seconds, more preferably 15 to 180 seconds.
　本発明に関するパターン形成方法においては、現像液及びリンス液の少なくとも一方に本発明の処理液が使用される。なかでも、本発明の処理液がリンス液として使用されることが好ましい。 In the pattern forming method according to the present invention, the treatment liquid of the present invention is used as at least one of the developing solution and the rinsing solution. Above all, it is preferable that the treatment liquid of the present invention is used as a rinsing liquid.
　例えば、現像工程における現像液としてエステル系溶剤を使用し、リンス工程におけるリンス液として本発明の処理液を使用してパターン形成を実施する場合、露光後のレジスト膜に対する現像液とリンス液の供給間隔を１秒以上あけることが好ましい。現像液とリンス液の供給間隔を所定時間以上あけることで、露光後のレジスト膜の未露光領域の溶解性の悪化が抑制でき、かつ、ソルベントショックによる欠陥増加を抑制できる。 For example, when pattern formation is performed using an ester solvent as the developing solution in the developing step and the treatment solution of the present invention as the rinsing solution in the rinsing step, the developing solution and the rinsing solution are supplied to the resist film after exposure. It is preferable to leave an interval of 1 second or more. By setting the supply interval between the developing solution and the rinsing solution for a predetermined time or longer, deterioration of the solubility of the unexposed region of the resist film after exposure can be suppressed, and the increase of defects due to the solvent shock can be suppressed.
　また、一般的に、現像液及びリンス液は、使用後に配管を通して共通の廃液タンクに収容される。その際、現像工程における現像液としてエステル系溶剤を使用し、リンス工程におけるリンス液として本発明の処理液を使用すると、現像液中に溶解したレジストが析出してしまい、基板の背面や、配管側面等に付着してしまい、装置を汚してしまう恐れがある。
　上記問題を解決するためには、再度、レジストが溶解する溶剤を配管に通す方法がある。配管に通す方法としては、リンス液での洗浄後に基板の背面や側面等をレジストが溶解する溶剤で洗浄して流す方法や、レジストに接触させずにレジストが溶解する溶剤を配管を通るように流す方法が挙げられる。
　配管に通す溶剤としては、レジストを溶解し得るものであれば特に制限されず、例えば上述した現像液として用いられる有機溶剤が挙げられる。具体的には、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エチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、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ルモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２－ヘプタノン、乳酸エチル、１－プロパノール、及び、アセトン等が挙げられる。なかでも、ＰＧＭＥＡ、ＰＧＭＥ、又は、シクロヘキサノンが好ましい。 Further, in general, the developer and the rinse liquid are stored in a common waste liquid tank through a pipe after use. At that time, if an ester solvent is used as the developing solution in the developing process and the treatment solution of the present invention is used as the rinsing solution in the rinsing process, the resist dissolved in the developing solution is precipitated, and the back surface of the substrate and the piping It may adhere to the side surface or the like and stain the device.
In order to solve the above problem, there is a method of passing a solvent in which the resist dissolves through the pipe again. As a method of passing through the pipe, a method of cleaning the back surface and side surfaces of the substrate with a solvent that dissolves the resist after cleaning with a rinsing liquid and flowing it, or a method of passing a solvent that dissolves the resist without contacting the resist is passed through the pipe. There is a method of flowing.
The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvent used as the developer described above. Specifically, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate. , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Examples thereof include 2-heptanone, ethyl lactate, 1-propanol, and acetone. Of these, PGMEA, PGME, or cyclohexanone is preferable.
　また、上記問題を解決するその他の方法としては、使用後に配管を通して廃液タンクへ流される廃液中にてレジストの析出が生じることを未然に防ぐため、使用後に配管に流される現像液とリンス液の量比をレジストが析出しない量比に調整する方法、及び、使用後に配管に流される現像液及びリンス液に、更にレジストに対して高溶解性の溶剤を混合する方法が挙げられる。具体的な方法としては、例えば、現像工程及びリンス工程の間、本発明の処理液中に含まれるフッ素系溶剤及び／又は第二溶剤よりもＳＰ値が高い有機溶剤をウエハの背面に連続して供給することで、使用後に配管を通して廃液タンクへ流される廃液中でのレジストの析出・沈殿を抑制する方法が挙げられる。 In addition, as another method for solving the above problem, in order to prevent the precipitation of resist in the waste liquid flowing through the pipe to the waste liquid tank after use, the developing solution and the rinsing liquid flowing in the pipe after use are used. Examples thereof include a method of adjusting the amount ratio so that the resist does not precipitate, and a method of further mixing a solvent having a high solubility in the resist with the developing solution and the rinsing solution which are passed through the pipe after use. As a specific method, for example, during the developing step and the rinsing step, a fluorosolvent contained in the treatment liquid of the present invention and / or an organic solvent having a higher SP value than the second solvent is continuously applied to the back surface of the wafer. A method of suppressing the precipitation / precipitation of the resist in the waste liquid flowing to the waste liquid tank through the pipe after use can be mentioned.
　更に、現像液及びリンス液は、使用後にそれぞれ別の廃液タンクに収容されることも好ましい。
　例えば、現像工程における現像液としてエステル系溶剤を使用し、リンス工程におけるリンス液として本発明の処理液を使用してパターン形成を実施する場合、使用後に配管を通して共通の廃液タンクに収容されると、現像液中に溶解した樹脂等のレジスト組成物に含まれる成分が析出（沈殿・固体化）してしまい、装置の汚染を引き起こし得る。具体的には、析出した成分によって、廃液配管の詰まりの他、処理チャンバー内の汚染が発生する。上記問題を解決するためには、現像液及びリンス液は、使用後に配管切替えにより、又は、処理チャンバーの切替えにより、それぞれ別の廃液タンクに収容されることが好ましい。また、処理チャンバー内は、処理チャンバー内に付着し得るレジスト成分を除去すべく、処理後に、本発明の処理液に含まれるフッ素系溶剤よりもＳＰ値が高い溶剤で洗浄されることが好ましい。 Further, it is also preferable that the developer and the rinse liquid are stored in separate waste liquid tanks after use.
For example, when pattern formation is performed using an ester solvent as the developer in the developing process and the treatment solution of the present invention as the rinse solution in the rinsing process, it is stored in a common waste liquid tank through a pipe after use. , Components contained in the resist composition such as resin dissolved in the developing solution may precipitate (precipitate / solidify), which may cause contamination of the apparatus. Specifically, the precipitated components cause clogging of the waste liquid pipe and contamination of the treatment chamber. In order to solve the above problems, it is preferable that the developer and the rinse liquid are stored in separate waste liquid tanks after use by switching the piping or by switching the treatment chamber. Further, it is preferable that the inside of the treatment chamber is washed with a solvent having a higher SP value than the fluorine-based solvent contained in the treatment liquid of the present invention after the treatment in order to remove the resist component that may adhere to the inside of the treatment chamber.
〔レジスト組成物〕
　次に、本発明の処理液と組み合わせて使用するレジスト組成物としては、例えば、樹脂、光酸発生剤、及び／又は、酸拡散制御剤等を含む、いわゆる化学増幅型レジスト組成物でもよく、樹脂の代わりに低分子フェノール化合物を含む分子レジスト組成物でもよく、金属酸化物系化合物を含むメタルレジスト組成物でもよく、露光によりポリマー主鎖が切断して低分子量化する主鎖切断型レジスト組成物でもよい。
　レジスト組成物は、ネガ型のレジスト組成物でもよく、ポジ型のレジスト組成物でもよい。
　以下、本発明の処理液と組み合わせて使用できるレジスト組成物の一形態である、化学増幅型レジスト組成物について詳述する。
　なお、以下において、化学増幅型レジスト組成物を指して、単に、レジスト組成物ともいう。 [Resist composition]
Next, the resist composition used in combination with the treatment liquid of the present invention may be a so-called chemically amplified resist composition containing, for example, a resin, a photoacid generator, and / or an acid diffusion control agent. A molecular resist composition containing a low-molecular-weight phenol compound instead of the resin may be used, or a metal resist composition containing a metal oxide-based compound may be used. It may be a thing.
The resist composition may be a negative type resist composition or a positive type resist composition.
Hereinafter, a chemically amplified resist composition, which is a form of a resist composition that can be used in combination with the treatment liquid of the present invention, will be described in detail.
In the following, the chemical amplification type resist composition is referred to, and is also simply referred to as a resist composition.
＜樹脂（Ａ）＞
　レジスト組成物は、酸の作用により分解して極性が増大する樹脂（以下、「酸分解性樹脂」又は「樹脂（Ａ）」ともいう。）を含む。
　つまり、パターン形成方法において、典型的には、現像液としてアルカリ現像液を採用した場合には、ポジ型パターンが好適に形成され、現像液として有機系現像液を採用した場合には、ネガ型パターンが好適に形成される。
　樹脂（Ａ）は、通常、酸の作用により分解し極性が増大する基（以下、「酸分解性基」ともいう。）を含み、酸分解性基を有する繰り返し単位を含むことが好ましい。 <Resin (A)>
The resist composition contains a resin (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)") which is decomposed by the action of an acid to increase the polarity.
That is, in the pattern forming method, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative type is formed. The pattern is preferably formed.
The resin (A) usually contains a group that is decomposed by the action of an acid and whose polarity is increased (hereinafter, also referred to as “acid-degradable group”), and preferably contains a repeating unit having an acid-decomposable group.
≪酸分解性基を有する繰り返し単位≫
　酸分解性基とは、酸の作用により分解して極性基を生じる基をいう。酸分解性基は、酸の作用により脱離する脱離基で極性基が保護された構造を有することが好ましい。つまり、樹脂（Ａ）は、酸の作用により分解し、極性基を生じる基を有する繰り返し単位を有する。この繰り返し単位を有する樹脂は、酸の作用により極性が増大してアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
　極性基としては、アルカリ可溶性基が好ましく、例えば、カルボキシル基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、リン酸基、スルホンアミド基、スルホニルイミド基、（アルキルスルホニル）（アルキルカルボニル）メチレン基、（アルキルスルホニル）（アルキルカルボニル）イミド基、ビス（アルキルカルボニル）メチレン基、ビス（アルキルカルボニル）イミド基、ビス（アルキルスルホニル）メチレン基、ビス（アルキルスルホニル）イミド基、トリス（アルキルカルボニル）メチレン基、及び、トリス（アルキルスルホニル）メチレン基等の酸性基、並びに、アルコール性水酸基等が挙げられる。
　なかでも、極性基としては、カルボキシル基、フェノール性水酸基、フッ素化アルコール基（好ましくはヘキサフルオロイソプロパノール基）、又は、スルホン酸基が好ましい。 ≪Repeating unit with acid-degradable group≫
An acid-degradable group is a group that is decomposed by the action of an acid to form a polar group. The acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, the resin (A) has a repeating unit having a group which is decomposed by the action of an acid to produce a polar group. The polarity of the resin having this repeating unit is increased by the action of the acid, the solubility in the alkaline developer is increased, and the solubility in the organic solvent is decreased.
As the polar group, an alkali-soluble group is preferable, and for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene. Group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) Examples thereof include an acidic group such as a methylene group and a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
　酸の作用により脱離する脱離基としては、例えば、式（Ｙ１）～（Ｙ４）で表される基が挙げられる。
式（Ｙ１）：－Ｃ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ２）：－Ｃ（＝Ｏ）ＯＣ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ３）：－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３８）
式（Ｙ４）：－Ｃ（Ｒｎ）（Ｈ）（Ａｒ） Examples of the leaving group that are eliminated by the action of an acid include groups represented by the formulas (Y1) to (Y4).
Equation (Y1): -C (Rx 1 ) (Rx 2 ) (Rx 3 )
Equation (Y2): -C (= O) OC (Rx 1 ) (Rx 2 ) (Rx 3 )
Equation (Y3): -C (R 36 ) (R 37 ) (OR 38 )
Formula (Y4): -C (Rn) (H) (Ar)
　式（Ｙ１）及び式（Ｙ２）中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、アルキル基（直鎖状若しくは分岐鎖状）、シクロアルキル基（単環若しくは多環）、アルケニル基（直鎖状若しくは分岐鎖状）、又は、アリール基（単環若しくは多環）を表す。なお、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖状若しくは分岐鎖状）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　なかでも、Ｒｘ１～Ｒｘ３は、それぞれ独立に、直鎖状又は分岐鎖状アルキル基を表すことが好ましく、Ｒｘ１～Ｒｘ３は、それぞれ独立に、直鎖状アルキル基を表すことがより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環又は多環を形成してもよい。
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～５のアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のアリール基としては、炭素数６～１０のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基等が挙げられる。
　Ｒｘ１～Ｒｘ３のアルケニル基としては、ビニル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成される環としては、シクロアルキル基が好ましい。　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、若しくは、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、若しくは、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数５～６の単環のシクロアルキル基がより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又は、ビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　式（Ｙ１）又は式（Ｙ２）で表される基は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 In the formula (Y1) and the formula (Y2), Rx 1 to Rx 3 are independently an alkyl group (linear or branched chain), a cycloalkyl group (monocyclic or polycyclic), and an alkenyl group (straight chain). (Mole or branched chain) or aryl group (monocyclic or polycyclic). When all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups.
Among them, Rx 1 to Rx 3 preferably independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. preferable.
Two of Rx 1 to Rx 3 may be combined to form a monocyclic ring or a polycyclic ring.
Examples of the alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like. The polycyclic cycloalkyl group of is preferred.
The aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
As the alkenyl group of Rx 1 to Rx 3 , a vinyl group is preferable.
A cycloalkyl group is preferable as the ring formed by combining two of Rx 1 to Rx 3. The cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododeca. A polycyclic cycloalkyl group such as an nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
The group represented by the formula (Y1) or the formula (Y2) is, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group. Is preferable.
　式（Ｙ３）中、Ｒ３６～Ｒ３８は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｒ３７とＲ３８とは、互いに結合して環を形成してもよい。１価の有機基としては、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等が挙げられる。Ｒ３６は水素原子であることも好ましい。
　なお、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基には、酸素原子等のヘテロ原子及び／又はカルボニル基等のヘテロ原子を有する基が含まれていてもよい。例えば、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基は、例えば、メチレン基の１つ以上が、酸素原子等のヘテロ原子及び／又はカルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　また、Ｒ３８は、繰り返し単位の主鎖が有する別の置換基と互いに結合して、環を形成してもよい。Ｒ３８と繰り返し単位の主鎖が有する別の置換基とが互いに結合して形成する基は、メチレン基等のアルキレン基が好ましい。 In formula (Y3), R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group. R 37 and R 38 may be combined with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R 36 is a hydrogen atom.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one or more methylene groups are replaced with a group having a hetero atom such as an oxygen atom and / or a hetero atom such as a carbonyl group. You may.
Further, R 38 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring. The group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
　式（Ｙ３）としては、下記式（Ｙ３－１）で表される基が好ましい。 As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　ここで、Ｌ１及びＬ２は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又は、これらを組み合わせた基（例えば、アルキル基とアリール基とを組み合わせた基）を表す。
　Ｍは、単結合又は２価の連結基を表す。
　Ｑは、ヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、又は、これらを組み合わせた基（例えば、アルキル基とシクロアルキル基とを組み合わせた基）を表す。
　アルキル基及びシクロアルキル基は、例えば、メチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　なお、Ｌ１及びＬ２のうち一方は水素原子であり、他方はアルキル基、シクロアルキル基、アリール基、又は、アルキレン基と、アリール基とを組み合わせた基であることが好ましい。
　Ｑ、Ｍ、及び、Ｌ１の少なくとも２つが結合して環（好ましくは、５員若しくは６員環）を形成してもよい。
　パターンの微細化の点では、Ｌ２が２級又は３級アルキル基であることが好ましく、３級アルキル基であることがより好ましい。２級アルキル基としては、イソプロピル基、シクロヘキシル基、又は、ノルボルニル基が挙げられ、３級アルキル基としては、ｔｅｒｔ－ブチル基又はアダマンタン基が挙げられる。これらの態様では、Ｔｇ（ガラス転移温度）及び活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。 Here, L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined). ..
M represents a single bond or a divalent linking group.
Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, and an aldehyde. Represents a group or a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
As for the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.
It is preferable that one of L 1 and L 2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
Q, M, and, at least two members to the ring (preferably, 5-membered or 6-membered ring) L 1 may be formed.
From the viewpoint of pattern miniaturization, L 2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and an adamantane group. In these aspects, Tg (glass transition temperature) and activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.
　式（Ｙ４）中、Ａｒは、芳香環基を表す。Ｒｎは、アルキル基、シクロアルキル基、又は、アリール基を表す。Ｒｎ及びＡｒは、互いに結合して非芳香族環を形成してもよい。Ａｒは、好ましくはアリール基である。 In the formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is preferably an aryl group.
　繰り返し単位の酸分解性が優れる観点から、極性基を保護する脱離基において、極性基（又はその残基）に非芳香族環が直接結合している場合、上記非芳香族環中の、上記極性基（又はその残基）と直接結合している環員原子に隣接する環員原子は、置換基としてフッ素原子等のハロゲン原子を有さないのも好ましい。 From the viewpoint of excellent acid decomposition of the repeating unit, in the leaving group that protects the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the non-aromatic ring in the non-aromatic ring. It is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.
　酸の作用により脱離する脱離基は、他にも、３－メチル－２－シクロペンテニル基のような置換基（アルキル基等）を有する２－シクロペンテニル基、及び、１，１，４，４－テトラメチルシクロヘキシル基のような置換基（アルキル基等）を有するシクロヘキシル基でもよい。 Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, and 1,1,4. , A cyclohexyl group having a substituent (alkyl group, etc.) such as 4-tetramethylcyclohexyl group may be used.
　酸分解性基を有する繰り返し単位としては、式（Ａ）で表される繰り返し単位も好ましい。 As the repeating unit having an acid-decomposable group, the repeating unit represented by the formula (A) is also preferable.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　Ｌ１は、フッ素原子又はヨウ素原子を有していてもよい２価の連結基を表し、Ｒ１は水素原子、フッ素原子、ヨウ素原子、フッ素原子、若しくは、ヨウ素原子を有していてもよいアルキル基、又は、フッ素原子若しくはヨウ素原子を有していてもよいアリール基を表し、Ｒ２は酸の作用によって脱離し、フッ素原子又はヨウ素原子を有していてもよい脱離基を表す。ただし、Ｌ１、Ｒ１、及び、Ｒ２のうち少なくとも１つは、フッ素原子又はヨウ素原子を有する。
　Ｌ１は、フッ素原子又はヨウ素原子を有していてもよい２価の連結基を表す。フッ素原子又はヨウ素原子を有していてもよい２価の連結基としては、－ＣＯ－、－Ｏ－、－Ｓ―、－ＳＯ－、―ＳＯ２－、フッ素原子、又は、ヨウ素原子を有していてもよい炭化水素基（例えば、アルキレン基、シクロアルキレン基、アルケニレン基、及び、アリーレン基等）、及び、これらの複数が連結した連結基等が挙げられる。なかでも、Ｌ１としては、－ＣＯ－、又は、－アリーレン基－フッ素原子若しくはヨウ素原子を有するアルキレン基－が好ましい。
　アリーレン基としては、フェニレン基が好ましい。
　アルキレン基は、直鎖状であっても、分岐鎖状であってもよい。アルキレン基の炭素数は特に制限されないが、１～１０が好ましく、１～３がより好ましい。
　フッ素原子又はヨウ素原子を有するアルキレン基に含まれるフッ素原子及びヨウ素原子の合計数は特に制限されないが、２以上が好ましく、２～１０がより好ましく、３～６が更に好ましい。 L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom, and R 1 may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, or an iodine atom. It represents an alkyl group or an aryl group which may have a fluorine atom or an iodine atom, and R 2 represents a desorbing group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. However, at least one of L 1 , R 1 , and R 2 has a fluorine atom or an iodine atom.
L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom. The fluorine atom or an iodine atom divalent linking group may have, -CO -, - O -, - S -, - SO -, - SO 2 -, a fluorine atom, or a iodine atom Yes Examples thereof include a hydrocarbon group which may be used (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.), a linking group in which a plurality of these groups are linked, and the like. Among them, as the L 1, -CO-, or, - arylene - fluorine atom or an alkylene group having iodine atom - are preferred.
As the arylene group, a phenylene group is preferable.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
　Ｒ１は、水素原子、フッ素原子、ヨウ素原子、フッ素原子、若しくは、ヨウ素原子が有していてもよいアルキル基、又は、フッ素原子若しくはヨウ素原子を有していてもよいアリール基を表す。
　アルキル基は、直鎖状であっても、分岐鎖状であってもよい。アルキル基の炭素数は特に制限されないが、１～１０が好ましく、１～３がより好ましい。
　フッ素原子又はヨウ素原子を有するアルキル基に含まれるフッ素原子及びヨウ素原子の合計数は特に制限されないが、１以上が好ましく、１～５がより好ましく、１～３が更に好ましい。
　上記アルキル基は、ハロゲン原子以外の酸素原子等のヘテロ原子を含んでいてもよい。 R 1 represents a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, an alkyl group which may have an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
The alkyl group may contain a hetero atom such as an oxygen atom other than the halogen atom.
　Ｒ２は、酸の作用によって脱離し、フッ素原子又はヨウ素原子を有していてもよい脱離基を表す。
　なかでも、脱離基としては、式（Ｚ１）～（Ｚ４）で表される基が挙げられる。
式（Ｚ１）：－Ｃ（Ｒｘ１１）（Ｒｘ１２）（Ｒｘ１３）
式（Ｚ２）：－Ｃ（＝Ｏ）ＯＣ（Ｒｘ１１）（Ｒｘ１２）（Ｒｘ１３）
式（Ｚ３）：－Ｃ（Ｒ１３６）（Ｒ１３７）（ＯＲ１３８）
式（Ｚ４）：－Ｃ（Ｒｎ１）（Ｈ）（Ａｒ１） R 2 represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
Among them, examples of the leaving group include groups represented by the formulas (Z1) to (Z4).
Equation (Z1): -C (Rx 11 ) (Rx 12 ) (Rx 13 )
Equation (Z2): -C (= O) OC (Rx 11 ) (Rx 12 ) (Rx 13 )
Equation (Z3): -C (R 136 ) (R 137 ) (OR 138 )
Equation (Z4): -C (Rn 1 ) (H) (Ar 1 )
　式（Ｚ１）、（Ｚ２）中、Ｒｘ１１～Ｒｘ１３は、それぞれ独立に、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基（直鎖状若しくは分岐鎖状）、フッ素原子若しくはヨウ素原子を有していてもよいシクロアルキル基（単環若しくは多環）、フッ素原子若しくはヨウ素原子を有していてもよいアルケニル基（直鎖状若しくは分岐鎖状）、又は、フッ素原子若しくはヨウ素原子を有していてもよいアリール基（単環若しくは多環）を表す。なお、Ｒｘ１１～Ｒｘ１３の全てがアルキル基（直鎖状若しくは分岐鎖状）である場合、Ｒｘ１１～Ｒｘ１３のうち少なくとも２つはメチル基であることが好ましい。
　Ｒｘ１１～Ｒｘ１３は、フッ素原子又はヨウ素原子を有していてもよい点以外は、上述した（Ｙ１）、（Ｙ２）中のＲｘ１～Ｒｘ３と同じであり、アルキル基、シクロアルキル基、アルケニル基、及び、アリール基の定義及び好適範囲と同じである。 In the formulas (Z1) and (Z2), Rx 11 to Rx 13 are alkyl groups (linear or branched), fluorine atoms or iodine atoms which may independently have a fluorine atom or an iodine atom, respectively. A cycloalkyl group (monocyclic or polycyclic) that may have a fluorine atom or an alkenyl group that may have a fluorine atom or an iodine atom (linear or branched chain), or a fluorine atom or an iodine atom. Represents an aryl group (monocyclic or polycyclic) that may have. When all of Rx 11 to Rx 13 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 11 to Rx 13 are methyl groups.
Rx 11 to Rx 13 are the same as Rx 1 to Rx 3 in (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and are an alkyl group or a cycloalkyl group. , Alkyl group, and aryl group are the same as the definition and preferred range.
　式（Ｚ３）中、Ｒ１３６～Ｒ１３８は、それぞれ独立に、水素原子、又は、フッ素原子若しくはヨウ素原子を有していてもよい１価の有機基を表す。Ｒ１３７及びＲ１３８は、互いに結合して環を形成してもよい。フッ素原子又はヨウ素原子を有していてもよい１価の有機基としては、フッ素原子又はヨウ素原子を有していてもよいアルキル基、フッ素原子又はヨウ素原子を有していてもよいシクロアルキル基、フッ素原子又はヨウ素原子を有していてもよいアリール基、フッ素原子又はヨウ素原子を有していてもよいアラルキル基、及び、これらを組み合わせた基（例えば、アルキル基とシクロアルキル基とを組み合わせた基）が挙げられる。
　なお、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基には、フッ素原子及びヨウ素原子以外に、酸素原子等のヘテロ原子が含まれていてもよい。つまり、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基は、例えば、メチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　また、Ｒ１３８は、繰り返し単位の主鎖が有する別の置換基と互いに結合して、環を形成してもよい。この場合、Ｒ１３８と繰り返し単位の主鎖が有する別の置換基とが互いに結合して形成する基は、メチレン基等のアルキレン基が好ましい。 In the formula (Z3), R 136 to R 138 each independently represent a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. R 137 and R 138 may be combined with each other to form a ring. The monovalent organic group which may have a fluorine atom or an iodine atom includes an alkyl group which may have a fluorine atom or an iodine atom, and a cycloalkyl group which may have a fluorine atom or an iodine atom. , An aryl group that may have a fluorine atom or an iodine atom, an aralkyl group that may have a fluorine atom or an iodine atom, and a group that combines these (for example, a combination of an alkyl group and a cycloalkyl group). Atom).
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom. That is, in the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, even if one of the methylene groups is replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. good.
Further, R 138 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring. In this case, the group formed by bonding R 138 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
　式（Ｚ３）としては、下記式（Ｚ３－１）で表される基が好ましい。 As the formula (Z3), a group represented by the following formula (Z3-1) is preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　ここで、Ｌ１１及びＬ１２は、それぞれ独立に、水素原子；フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいアルキル基；フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいシクロアルキル基；フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいアリール基；又はこれらを組み合わせた基（例えば、フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよい、アルキル基とシクロアルキル基とを組み合わせた基）を表す。
　Ｍ１は、単結合又は２価の連結基を表す。
　Ｑ１は、フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいアルキル基；フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいシクロアルキル基；フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよいアリール基；アミノ基；アンモニウム基；メルカプト基；シアノ基；アルデヒド基；又はこれらを組み合わせた基（例えば、フッ素原子、ヨウ素原子、及び、酸素原子からなる群から選択されるヘテロ原子を有していてもよい、アルキル基とシクロアルキル基とを組み合わせた基）を表す。 Here, L 11 and L 12 each independently may have a hetero atom selected from the group consisting of a hydrogen atom; a fluorine atom, an iodine atom, and an oxygen atom; an alkyl group; a fluorine atom, an iodine. A cycloalkyl group which may have a hetero atom selected from the group consisting of an atom and an oxygen atom; having a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom. A combination of an alkyl group and a cycloalkyl group, which may have a hetero atom selected from the group consisting of an aryl group; or a group combining these (for example, a fluorine atom, an iodine atom, and an oxygen atom). Represents an atom).
M 1 represents a single bond or a divalent linking group.
Q 1 may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom. Cycloalkyl group which may have a heteroatom; aryl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an amino group; an ammonium group; a mercapto group. An alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of a cyano group; an aldehyde group; or a group combining these (for example, a fluorine atom, an iodine atom, and an oxygen atom). Represents a group that combines.
　式（Ｚ４）中、Ａｒ１は、フッ素原子又はヨウ素原子を有していてもよい芳香環基を表す。Ｒｎ１は、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいシクロアルキル基、又は、フッ素原子若しくはヨウ素原子を有していてもよいアリール基を表す。Ｒｎ１及びＡｒ１は、互いに結合して非芳香族環を形成してもよい。 In formula (Z4), Ar 1 represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn 1 may have an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl which may have a fluorine atom or an iodine atom. Represents a group. Rn 1 and Ar 1 may be combined with each other to form a non-aromatic ring.
　酸分解性基を有する繰り返し単位としては、一般式（ＡＩ）で表される繰り返し単位も好ましい。 As the repeating unit having an acid-decomposable group, a repeating unit represented by the general formula (AI) is also preferable.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　一般式（ＡＩ）において、
　Ｘａ１は、水素原子、又は、置換基を有していてもよいアルキル基を表す。
　Ｔは、単結合又は２価の連結基を表す。
　Ｒｘ１～Ｒｘ３は、それぞれ独立に、アルキル基（直鎖状若しくは分岐鎖状）、シクロアルキル基（単環若しくは多環）、アルケニル基（直鎖状若しくは分岐鎖状）、又は、アリール（単環若しくは多環）基を表す。ただし、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖状、又は分岐鎖状）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環又は多環（単環又は多環のシクロアルキル基等）を形成してもよい。 In the general formula (AI)
Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx 1 to Rx 3 are independently alkyl groups (linear or branched), cycloalkyl groups (monocyclic or polycyclic), alkenyl groups (linear or branched), or aryl (linear or branched). Represents a monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups.
Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, etc.).
　Ｘａ１により表される、置換基を有していてもよいアルキル基としては、例えば、メチル基、又は、－ＣＨ２－Ｒ１１で表される基が挙げられる。Ｒ１１は、ハロゲン原子（フッ素原子等）、水酸基、又は、１価の有機基を表し、例えば、ハロゲン原子が置換していてもよい炭素数５以下のアルキル基、ハロゲン原子が置換していてもよい炭素数５以下のアシル基、及び、ハロゲン原子が置換していてもよい炭素数５以下のアルコキシ基が挙げられ、炭素数３以下のアルキル基が好ましく、メチル基がより好ましい。Ｘａ１としては、水素原子、メチル基、トリフルオロメチル基、又は、ヒドロキシメチル基が好ましい。 Represented by xa 1, as the alkyl group which may have a substituent, e.g., methyl group, or a group represented by the -CH 2 -R 11. R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, and for example, an alkyl group having 5 or less carbon atoms, which may be substituted by the halogen atom, or a halogen atom is substituted. Examples thereof include an acyl group having 5 or less carbon atoms and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xa 1 , a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
　Ｔの２価の連結基としては、アルキレン基、芳香環基、－ＣＯＯ－Ｒｔ－基、及び、－Ｏ－Ｒｔ－基等が挙げられる。式中、Ｒｔは、アルキレン基、又は、シクロアルキレン基を表す。
　Ｔは、単結合、又は、－ＣＯＯ－Ｒｔ－基が好ましい。Ｔが－ＣＯＯ－Ｒｔ－基を表す場合、Ｒｔは、炭素数１～５のアルキレン基が好ましく、－ＣＨ２－基、－（ＣＨ２）２－基、又は、－（ＣＨ２）３－基がより好ましい。 Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -O-Rt- group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH 2- group,- (CH 2 ) 2- group, or- (CH 2 ) 3- Groups are more preferred.
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～４のアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のアリール基としては、炭素数６～１０のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基等が挙げられる。
　Ｒｘ１～Ｒｘ３のアルケニル基としては、ビニル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基が好ましく、その他にも、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数５～６の単環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又は、ビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　一般式（ＡＩ）で表される繰り返し単位は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 Examples of the alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The polycyclic cycloalkyl group of is preferred.
The aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
As the alkenyl group of Rx 1 to Rx 3 , a vinyl group is preferable.
As the cycloalkyl group formed by combining two of Rx 1 to Rx 3 , a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used. , Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
The cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
As the repeating unit represented by the general formula (AI), for example, it is preferable that Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
　上記各基が置換基を有する場合、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、及び、アルコキシカルボニル基（炭素数２～６）等が挙げられる。置換基中の炭素数は、８以下が好ましい。 When each of the above groups has a substituent, the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like. The number of carbon atoms in the substituent is preferably 8 or less.
　一般式（ＡＩ）で表される繰り返し単位としては、好ましくは、酸分解性（メタ）アクリル酸３級アルキルエステル系繰り返し単位（Ｘａ１が水素原子又はメチル基を表し、かつ、Ｔが単結合を表す繰り返し単位）である。 The repeating unit represented by the general formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. It is a repeating unit that represents.
　酸分解性基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１５モル％以上が好ましく、２０モル％以上がより好ましく、２５モル％以上が更に好ましく、３０モル％以上が特に好ましい。また、その上限値としては特に制限されないが、９０モル％以下好ましく、８０モル％以下がより好ましく、７０モル％が更により好ましい。 The content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, more preferably 30 mol% or more, based on all the repeating units in the resin (A). More than mol% is particularly preferable. The upper limit thereof is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol%.
　酸分解性基を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。なお、式中、Ｘａ１はＨ、ＣＨ３、ＣＦ３、及び、ＣＨ２ＯＨのいずれかを表し、Ｒｘａ及びＲｘｂは、それぞれ炭素数１～５の直鎖状又は分岐鎖状アルキル基を表す。 Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa 1 represents any of H, CH 3 , CF 3 , and CH 2 OH, and Rxa and Rxb represent linear or branched-chain alkyl groups having 1 to 5 carbon atoms, respectively. ..
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　樹脂（Ａ）は、上述した繰り返し単位以外の繰り返し単位を含んでいてもよい。
　例えば、樹脂（Ａ）は、以下のＡ群からなる群から選択される少なくとも１種の繰り返し単位、及び／又は、以下のＢ群からなる群から選択される少なくとも１種の繰り返し単位を含んでいてもよい。
Ａ群：以下の（２０）～（２９）の繰り返し単位からなる群。
（２０）後述する、酸基を有する繰り返し単位
（２１）後述する、フッ素原子又はヨウ素原子を有する繰り返し単位
（２２）後述する、ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位
（２３）後述する、光酸発生基を有する繰り返し単位
（２４）後述する、一般式（Ｖ－１）、又は、下記一般式（Ｖ－２）で表される繰り返し単位
（２５）後述する、式（Ａ）で表される繰り返し単位
（２６）後述する、式（Ｂ）で表される繰り返し単位
（２７）後述する、式（Ｃ）で表される繰り返し単位
（２８）後述する、式（Ｄ）で表される繰り返し単位
（２９）後述する、式（Ｅ）で表される繰り返し単位
Ｂ群：以下の（３０）～（３２）の繰り返し単位からなる群。
（３０）後述する、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及び、アルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位
（３１）後述する、脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位
（３２）後述する、水酸基及びシアノ基のいずれも有さない、一般式（ＩＩＩ）で表される繰り返し単位 The resin (A) may contain a repeating unit other than the repeating unit described above.
For example, the resin (A) contains at least one repeating unit selected from the group consisting of the following groups A and / or at least one repeating unit selected from the group consisting of the following groups B. You may.
Group A: A group consisting of the following repeating units (20) to (29).
(20) Repeating unit having an acid group described later (21) Repeating unit having a fluorine atom or iodine atom described later (22) Repeating unit having a lactone group, sulton group or carbonate group described later (23) A repeating unit having a photoacid generating group (24) described later, a repeating unit (25) represented by the general formula (V-1) or the following general formula (V-2) described later, and a formula (A) described later. ), The repeating unit (26) described later, the repeating unit represented by the formula (B) (27), the repeating unit represented by the formula (C) (28), the formula (D) described later. Represented repeating unit (29) The repeating unit represented by the formula (E), which will be described later, Group B: A group consisting of the following repeating units (30) to (32).
(30) A repeating unit having at least one group selected from a lactone group, a sulton group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, which will be described later. However, a repeating unit (32) that does not exhibit acid decomposition property, which will be described later, is a repeating unit represented by the general formula (III) that does not have either a hydroxyl group or a cyano group.
　レジスト組成物がＥＵＶ露光用途又は電子線露光用途で用いられる場合、樹脂（Ａ）は上記Ａ群からなる群から選択される少なくとも１種の繰り返し単位を有することが好ましい。
　また、レジスト組成物がＥＵＶ露光用途又は電子線露光用途で用いられる場合、樹脂（Ａ）は、フッ素原子及びヨウ素原子の少なくとも一方を含むことも好ましい。樹脂（Ａ）がフッ素原子及びヨウ素原子の両方を含む場合、樹脂（Ａ）は、フッ素原子及びヨウ素原子の両方を含む１つの繰り返し単位を有していてもよいし、樹脂（Ａ）は、フッ素原子を有する繰り返し単位とヨウ素原子を含む繰り返し単位との２種を含んでいてもよい。
　また、レジスト組成物がＥＵＶ露光用途又は電子線露光用途で用いられる場合、樹脂（Ａ）が、芳香族基を有する繰り返し単位を有するのも好ましい。
　レジスト組成物がＡｒＦ露光用途で用いられる場合、樹脂（Ａ）は上記Ｂ群からなる群から選択される少なくとも１種の繰り返し単位を有することが好ましい。
　また、レジスト組成物がＡｒＦ露光用途で用いられる場合、樹脂（Ａ）は、フッ素原子及び珪素原子のいずれも含まないことが好ましい。
　また、組成物がＡｒＦ用途で用いられる場合、樹脂（Ａ）は、芳香族基を有さないことが好ましい。 When the resist composition is used for EUV exposure or electron beam exposure, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above group A.
When the resist composition is used for EUV exposure or electron beam exposure, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) may have one repeating unit. It may contain two kinds of a repeating unit having a fluorine atom and a repeating unit containing an iodine atom.
Further, when the resist composition is used for EUV exposure or electron beam exposure, it is also preferable that the resin (A) has a repeating unit having an aromatic group.
When the resist composition is used for ArF exposure, the resin (A) preferably has at least one repeating unit selected from the group consisting of group B.
When the resist composition is used for ArF exposure, the resin (A) preferably contains neither fluorine atoms nor silicon atoms.
Further, when the composition is used for ArF applications, the resin (A) preferably has no aromatic group.
≪酸基を有する繰り返し単位≫
　樹脂（Ａ）は、酸基を有する繰り返し単位を有していてもよい。
　酸基としては、ｐＫａが１３以下の酸基が好ましい。
　酸基としては、例えば、カルボキシル基、フェノール性水酸基、フッ素化アルコール基（好ましくはヘキサフルオロイソプロパノール基）、スルホン酸基、スルホンアミド基、又は、イソプロパノール基等が好ましい。
　また、上記ヘキサフルオロイソプロパノール基は、フッ素原子の１つ以上（好ましくは１～２つ）が、フッ素原子以外の基（アルコキシカルボニル基等）で置換されてもよい。
このように形成された－Ｃ（ＣＦ３）（ＯＨ）－ＣＦ２－も、酸基として好ましい。また、フッ素原子の１つ以上がフッ素原子以外の基に置換されて、－Ｃ（ＣＦ３）（ＯＨ）－ＣＦ２－を含む環を形成してもよい。
　酸基を有する繰り返し単位は、上述の酸の作用により脱離する脱離基で極性基が保護された構造を有する繰り返し単位、及び、後述するラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位とは異なる繰り返し単位であるのが好ましい。 ≪Repeating unit with acid group≫
The resin (A) may have a repeating unit having an acid group.
As the acid group, an acid group having a pKa of 13 or less is preferable.
As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, an isopropanol group and the like are preferable.
Further, in the hexafluoroisopropanol group, one or more (preferably one or two) fluorine atoms may be substituted with a group other than the fluorine atom (alkoxycarbonyl group or the like).
-C (CF 3 ) (OH) -CF 2- thus formed is also preferable as an acid group. Further, one or more of the fluorine atoms may be substituted with a group other than the fluorine atom to form a ring containing −C (CF 3 ) (OH) −CF 2-.
The repeating unit having an acid group is a repeating unit having a structure in which a polar group is protected by a leaving group desorbed by the action of the above-mentioned acid, and a repeating unit having a lactone group, a sulton group or a carbonate group described later. It is preferably a repeating unit different from the unit.
　酸基を有する繰り返し単位は、フッ素原子又はヨウ素原子を有していてもよい。 The repeating unit having an acid group may have a fluorine atom or an iodine atom.
　酸基を有する繰り返し単位としては、式（Ｂ）で表される繰り返し単位が好ましい。 As the repeating unit having an acid group, the repeating unit represented by the formula (B) is preferable.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　Ｒ３は、水素原子、又は、フッ素原子若しくはヨウ素原子を有していてもよい１価の有機基を表す。
　フッ素原子又はヨウ素原子を有していてもよい１価の有機基としては、－Ｌ４－Ｒ８で表される基が好ましい。Ｌ４は、単結合又はエステル基を表す。Ｒ８は、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいシクロアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいアリール基、又は、これらを組み合わせた基が挙げられる。 R 3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.
Examples of the fluorine atom or an organic group may monovalent optionally having iodine atom, a group represented by -L 4 -R 8 are preferred. L 4 represents a single bond or ester group. R 8 is an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, and the like. Alternatively, a group combining these can be mentioned.
　Ｒ４及びＲ５は、それぞれ独立に、水素原子、フッ素原子、ヨウ素原子、又は、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基を表す。 R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.
　Ｌ２は、単結合又はエステル基を表す。
　Ｌ３は、（ｎ＋ｍ＋１）価の芳香族炭化水素環基、又は、（ｎ＋ｍ＋１）価の脂環式炭化水素環基を表す。芳香族炭化水素環基としては、ベンゼン環基、及び、ナフタレン環基が挙げられる。脂環式炭化水素環基としては、単環であっても、多環であってもよく、例えば、シクロアルキル環基が挙げられる。
　Ｒ６は、水酸基、又は、フッ素化アルコール基（好ましくは、ヘキサフルオロイソプロパノール基）を表す。なお、Ｒ６が水酸基の場合、Ｌ３は（ｎ＋ｍ＋１）価の芳香族炭化水素環基であることが好ましい。
　Ｒ７は、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、又は、ヨウ素原子が挙げられる。
　ｍは、１以上の整数を表す。ｍは、１～３の整数が好ましく、１～２の整数が好ましい。
　ｎは、０又は１以上の整数を表す。ｎは、１～４の整数が好ましい。
　なお、（ｎ＋ｍ＋１）は、１～５の整数が好ましい。 L 2 represents a single bond or an ester group.
L 3 represents a (n + m + 1) -valent aromatic hydrocarbon ring group or a (n + m + 1) -valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R 6 is a hydroxyl group, L 3 is preferably an aromatic hydrocarbon ring group having a (n + m + 1) valence.
R 7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
m represents an integer of 1 or more. For m, an integer of 1 to 3 is preferable, and an integer of 1 to 2 is preferable.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1 to 4.
In addition, (n + m + 1) is preferably an integer of 1 to 5.
　酸基を有する繰り返し単位としては、下記一般式（Ｉ）で表される繰り返し単位も好ましい。 As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferable.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（Ｉ）中、
　Ｒ４１、Ｒ４２、及び、Ｒ４３は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又は、アルコキシカルボニル基を表す。但し、Ｒ４２はＡｒ４と結合して環を形成していてもよく、その場合のＲ４２は単結合又はアルキレン基を表す。
　Ｘ４は、単結合、－ＣＯＯ－、又は、－ＣＯＮＲ６４－を表し、Ｒ６４は、水素原子又はアルキル基を表す。
　Ｌ４は、単結合又はアルキレン基を表す。
　Ａｒ４は、（ｎ＋１）価の芳香環基を表し、Ｒ４２と結合して環を形成する場合には（ｎ＋２）価の芳香環基を表す。
　ｎは、１～５の整数を表す。 In general formula (I),
R 41 , R 42 , and R 43 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R 42 may be bonded to Ar 4 to form a ring, in which case R 42 represents a single bond or an alkylene group.
X 4 represents a single bond, -COO-, or -CONR 64- , and R 64 represents a hydrogen atom or an alkyl group.
L 4 represents a single bond or an alkylene group.
Ar 4 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with R 42 to form a ring.
n represents an integer from 1 to 5.
　一般式（Ｉ）におけるＲ４１、Ｒ４２、及び、Ｒ４３のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、及び、ドデシル基等の炭素数２０以下のアルキル基が好ましく、炭素数８以下のアルキル基がより好ましく、炭素数３以下のアルキル基が更に好ましい。 The alkyl groups of R 41 , R 42 , and R 43 in the general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl. Alkyl groups having 20 or less carbon atoms such as groups, octyl groups, and dodecyl groups are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are further preferable.
　一般式（Ｉ）におけるＲ４１、Ｒ４２、及び、Ｒ４３のシクロアルキル基としては、単環型でも、多環型でもよい。なかでも、シクロプロピル基、シクロペンチル基、及び、シクロヘキシル基等の炭素数３～８個で単環型のシクロアルキル基が好ましい。
　一般式（Ｉ）におけるＲ４１、Ｒ４２、及び、Ｒ４３のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられ、フッ素原子が好ましい。一般式（Ｉ）におけるＲ４１、Ｒ４２、及び、Ｒ４３のアルコキシカルボニル基に含まれるアルキル基としては、上記Ｒ４１、Ｒ４２、及び、Ｒ４３におけるアルキル基と同様のものが好ましい。 The cycloalkyl groups of R 41 , R 42 , and R 43 in the general formula (I) may be monocyclic or polycyclic. Of these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable.
Examples of the halogen atoms of R 41 , R 42 , and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. The alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 , and R 43 in the general formula (I) is preferably the same as the alkyl group in R 41 , R 42 , and R 43.
　上記各基における好ましい置換基としては、例えば、アルキル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、水酸基、カルボキシル基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基、及び、ニトロ基が挙げられる。置換基の炭素数は８以下が好ましい。 Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl group. , Achilloxy group, alkoxycarbonyl group, cyano group, and nitro group. The substituent preferably has 8 or less carbon atoms.
　Ａｒ４は、（ｎ＋１）価の芳香環基を表す。ｎが１である場合における２価の芳香環基は、例えば、フェニレン基、トリレン基、ナフチレン基、及び、アントラセニレン基等の炭素数６～１８のアリーレン基、又は、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、及び、チアゾール環等のヘテロ環を含む２価の芳香環基が好ましい。なお、上記芳香環基は、置換基を有していてもよい。 Ar 4 represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a trilene group, a naphthylene group, and an anthracenylene group, or a thiophene ring, a furan ring, or a pyrrole. A divalent aromatic ring group containing a heterocycle such as a ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiazol ring, and a thiazole ring is preferable. The aromatic ring group may have a substituent.
　ｎが２以上の整数である場合における（ｎ＋１）価の芳香環基の具体例としては、２価の芳香環基の上記した具体例から、（ｎ－１）個の任意の水素原子を除してなる基が挙げられる。
　（ｎ＋１）価の芳香環基は、更に置換基を有していてもよい。 As a specific example of the (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of.
The (n + 1) -valent aromatic ring group may further have a substituent.
　上述したアルキル基、シクロアルキル基、アルコキシカルボニル基、アルキレン基、及び、（ｎ＋１）価の芳香環基が有し得る置換基としては、例えば、一般式（Ｉ）におけるＲ４１、Ｒ４２、及び、Ｒ４３で挙げたアルキル基、メトキシ基、エトキシ基、ヒドロキシエトキシ基、プロポキシ基、ヒドロキシプロポキシ基、及び、ブトキシ基等のアルコキシ基；フェニル基等のアリール基；等が挙げられる。
　Ｘ４により表される－ＣＯＮＲ６４－（Ｒ６４は、水素原子又はアルキル基を表す）におけるＲ６４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、及び、ドデシル基等の炭素数２０以下のアルキル基が挙げられ、炭素数８以下のアルキル基が好ましい。
　Ｘ４としては、単結合、－ＣＯＯ－、又は、－ＣＯＮＨ－が好ましく、単結合、又は－ＣＯＯ－がより好ましい。 Examples of the substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group can have include R 41 , R 42 , and R 41 in the general formula (I). , R 43 , an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like.
-CONR 64 represented by X 4 - (R 64 represents a hydrogen atom or an alkyl group) The alkyl group for R 64 in, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec Examples thereof include alkyl groups having 20 or less carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
As X 4 , a single bond, -COO-, or -CONH- is preferable, and a single bond, or -COO- is more preferable.
　Ｌ４におけるアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、及び、オクチレン基等の炭素数１～８のアルキレン基が好ましい。
　Ａｒ４としては、炭素数６～１８の芳香環基が好ましく、ベンゼン環基、ナフタレン環基、及び、ビフェニレン環基がより好ましい。
　一般式（Ｉ）で表される繰り返し単位は、ヒドロキシスチレン構造を備えていることが好ましい。Ａｒ４は、ベンゼン環基であることが好ましい。 The alkylene group for L 4, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and is preferably an alkylene group having 1 to 8 carbon atoms such as octylene group.
As Ar 4 , an aromatic ring group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferable.
The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. Ar 4 is preferably a benzene ring group.
　一般式（１）で表される繰り返し単位としては、下記一般式（１）で表される繰り返し単位が好ましい。 As the repeating unit represented by the general formula (1), the repeating unit represented by the following general formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　一般式（１）中、
　Ａは水素原子、アルキル基、シクロアルキル基、ハロゲン原子、又は、シアノ基を表す。
　Ｒは、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルケニル基、アラルキル基、アルコキシ基、アルキルカルボニルオキシ基、アルキルスルホニルオキシ基、アルキルオキシカルボニル基、又は、アリールオキシカルボニル基を表し、複数個ある場合には同じであっても異なっていてもよい。複数のＲを有する場合には、互いに共同して環を形成していてもよい。Ｒとしては水素原子が好ましい。
　ａは１～３の整数を表す。
　ｂは０～（５－ａ）の整数を表す。 In general formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. If there are, they may be the same or different. When having a plurality of Rs, they may form a ring jointly with each other. A hydrogen atom is preferable as R.
a represents an integer of 1 to 3.
b represents an integer from 0 to (5-a).
　なかでも、レジスト組成物が含む樹脂は、ヒドロキシスチレン系繰り返し単位を有することが好ましい。
　ヒドロキシスチレン系繰り返し単位としては、例えば、上記一般式（１）において、Ａが水素原子を表す繰り返し単位が挙げられる。 Among them, the resin contained in the resist composition preferably has a hydroxystyrene-based repeating unit.
Examples of the hydroxystyrene-based repeating unit include a repeating unit in which A represents a hydrogen atom in the above general formula (1).
　以下、酸基を有する繰り返し単位を以下に例示する。式中、ａは１又は２を表す。 Hereinafter, repeating units having an acid group will be exemplified below. In the formula, a represents 1 or 2.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　なお、上記繰り返し単位のなかでも、以下に具体的に記載する繰り返し単位が好ましい。式中、Ｒは水素原子又はメチル基を表し、ａは２又は３を表す。 Among the above repeating units, the repeating units specifically described below are preferable. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　酸基を有する繰り返し単位（好ましくはヒドロキシスチレン系繰り返し単位）の含有量は、樹脂（Ａ）中の全繰り返し単位に対し、５モル％以上が好ましく、１０モル％以上が好ましい。また、その上限値としては特に制限されないが、５０モル％以下が好ましく、４５モル％以下がより好ましく、４０モル％以下が更に好ましい。 The content of the repeating unit having an acid group (preferably a hydroxystyrene-based repeating unit) is preferably 5 mol% or more, preferably 10 mol% or more, based on all the repeating units in the resin (A). The upper limit is not particularly limited, but is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.
≪フッ素原子又はヨウ素原子を有する繰り返し単位≫
　樹脂（Ａ）は、上述した≪酸分解性基を有する繰り返し単位≫、及び、≪酸基を有する繰り返し単位≫とは別に、フッ素原子又はヨウ素原子を有する繰り返し単位を有していてもよい。また、ここでいう≪フッ素原子又はヨウ素原子を有する繰り返し単位≫は、後述の≪ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位≫、及び、≪光酸発生基を有する繰り返し単位≫等の、Ａ群に属する他の種類の繰り返し単位とは異なるのが好ましい。 ≪Repeating unit with fluorine atom or iodine atom≫
The resin (A) may have a repeating unit having a fluorine atom or an iodine atom, in addition to the above-mentioned << repeating unit having an acid-degradable group >> and << repeating unit having an acid group >>. Further, the << repeating unit having a fluorine atom or an iodine atom >> referred to here is << a repeating unit having a lactone group, a sultone group, or a carbonate group >>, << a repeating unit having a photoacid generating group >>, etc. It is preferable that the unit is different from other types of repeating units belonging to the group A.
　フッ素原子又はヨウ素原子を有する繰り返し単位としては、式（Ｃ）で表される繰り返し単位が好ましい。 As the repeating unit having a fluorine atom or an iodine atom, the repeating unit represented by the formula (C) is preferable.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　Ｌ５は、単結合、又は、エステル基を表す。
　Ｒ９は、水素原子、又は、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基を表す。
　Ｒ１０は、水素原子、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいシクロアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいアリール基、又は、これらを組み合わせた基を表す。 L 5 represents a single bond or an ester group.
R 9 represents an alkyl group which may have a hydrogen atom or a fluorine atom or an iodine atom.
R 10 may have an alkyl group which may have a hydrogen atom, a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom. Represents an aryl group or a group in which these are combined.
　フッ素原子又はヨウ素原子を有する繰り返し単位を以下に例示する。 The repeating unit having a fluorine atom or an iodine atom is illustrated below.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　フッ素原子又はヨウ素原子を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対し、０モル％以上が好ましく、５モル％以上がより好ましく、１０モル％以上が更に好ましい。また、その上限値としては、５０モル％以下が好ましく、４５モル％以下がより好ましく、４０モル％以下が更に好ましい。
　なお、上述したように、フッ素原子又はヨウ素原子を有する繰り返し単位には、≪酸分解性基を有する繰り返し単位≫、及び、≪酸基を有する繰り返し単位≫は含まれないことから、上記フッ素原子又はヨウ素原子を有する繰り返し単位の含有量も、≪酸分解性基を有する繰り返し単位≫、及び、≪酸基を有する繰り返し単位≫を除いたフッ素原子又はヨウ素原子を有する繰り返し単位の含有量を意図する。 The content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, based on all the repeating units in the resin (A). The upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.
As described above, since the repeating unit having a fluorine atom or the iodine atom does not include << repeating unit having an acid-degradable group >> and << repeating unit having an acid group >>, the above-mentioned fluorine atom. Alternatively, the content of the repeating unit having an iodine atom is also intended to be the content of the repeating unit having a fluorine atom or an iodine atom excluding << repeating unit having an acid-degradable group >> and << repeating unit having an acid group >>. do.
　樹脂（Ａ）の繰り返し単位のうち、フッ素原子及びヨウ素原子の少なくとも一方を含む繰り返し単位の合計含有量は、樹脂（Ａ）の全繰り返し単位に対して、２０モル％以上が好ましく、３０モル％以上がより好ましく、４０モル％以上が更に好ましい。上限値は特に制限されないが、例えば、１００モル％以下である。
　なお、フッ素原子及びヨウ素原子の少なくとも一方を含む繰り返し単位としては、例えば、フッ素原子又はヨウ素原子を有し、かつ、酸分解性基を有する繰り返し単位、フッ素原子又はヨウ素原子を有し、かつ、酸基を有する繰り返し単位、及び、フッ素原子又はヨウ素原子を有する繰り返し単位が挙げられる。 Of the repeating units of the resin (A), the total content of the repeating units containing at least one of a fluorine atom and an iodine atom is preferably 20 mol% or more, preferably 30 mol%, based on all the repeating units of the resin (A). The above is more preferable, and 40 mol% or more is further preferable. The upper limit is not particularly limited, but is, for example, 100 mol% or less.
The repeating unit containing at least one of a fluorine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom or an iodine atom and having an acid-degradable group, a fluorine atom or an iodine atom, and Examples thereof include a repeating unit having an acid group and a repeating unit having a fluorine atom or an iodine atom.
≪ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位≫
　樹脂（Ａ）は、ラクトン基、スルトン基、及び、カーボネート基からなる群から選択される少なくとも１種を有する繰り返し単位（以下、総称して「ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位」ともいう。）を有していてもよい。
　ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位は、ヘキサフルオロプロパノール基等の酸基を有さないのも好ましい。 << Repeating unit having a lactone group, sultone group, or carbonate group >>
The resin (A) is a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, collectively, a repeating unit having a lactone group, a sultone group, or a carbonate group). It may also have a "unit").
It is also preferable that the repeating unit having a lactone group, a sultone group, or a carbonate group does not have an acid group such as a hexafluoropropanol group.
　ラクトン基又はスルトン基としては、ラクトン構造又はスルトン構造を有していればよい。ラクトン構造又はスルトン構造は、５～７員環ラクトン構造又は５～７員環スルトン構造が好ましい。なかでも、ビシクロ構造若しくはスピロ構造を形成する形で５～７員環ラクトン構造に他の環構造が縮環しているもの、又は、ビシクロ構造若しくはスピロ構造を形成する形で５～７員環スルトン構造に他の環構造が縮環しているもの、がより好ましい。
　樹脂（Ａ）は、下記一般式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造、又は、下記一般式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造の環員原子から、水素原子を１つ以上引き抜いてなるラクトン基又はスルトン基を有する繰り返し単位を有することが好ましい。
　また、ラクトン基又はスルトン基が主鎖に直接結合していてもよい。例えば、ラクトン基又はスルトン基の環員原子が、樹脂（Ａ）の主鎖を構成してもよい。 The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo structure or a spiro structure, or a 5- to 7-membered ring in the form of a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.
The resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atom of the represented sultone structure.
Further, a lactone group or a sultone group may be directly bonded to the main chain. For example, a ring-membered atom of a lactone group or a sultone group may form the main chain of the resin (A).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記ラクトン構造又はスルトン構造部分は、置換基（Ｒｂ２）を有していてもよい。好ましい置換基（Ｒｂ２）としては、炭素数１～８のアルキル基、炭素数４～７のシクロアルキル基、炭素数１～８のアルコキシ基、炭素数１～８のアルコキシカルボニル基、カルボキシル基、ハロゲン原子、水酸基、シアノ基、及び、酸分解性基等が挙げられる。ｎ２は、０～４の整数を表す。ｎ２が２以上の時、複数存在するＲｂ２は、異なっていてもよく、また、複数存在するＲｂ２同士が結合して環を形成してもよい。 The lactone structure or sultone structure portion may have a substituent (Rb 2 ). Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like. n2 represents an integer of 0 to 4. When n2 is 2 or more, Rb 2 existing in plural numbers may be different or may be bonded to form a ring Rb 2 between the plurality of.
　一般式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造、又は、一般式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造を有する基を有する繰り返し単位としては、例えば、下記一般式（ＡＩ）で表される繰り返し単位等が挙げられる。 A group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulas (SL1-1) to (SL1-3). Examples of the repeating unit having the above include a repeating unit represented by the following general formula (AI).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　一般式（ＡＩ）中、Ｒｂ０は、水素原子、ハロゲン原子、又は、炭素数１～４のアルキル基を表す。
　Ｒｂ０のアルキル基が有していてもよい好ましい置換基としては、水酸基、及び、ハロゲン原子が挙げられる。
　Ｒｂ０のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられる。Ｒｂ０は、水素原子又はメチル基が好ましい。
　Ａｂは、単結合、アルキレン基、単環若しくは多環の脂環炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又は、これらを組み合わせた２価の基を表す。なかでも、単結合、又は、－Ａｂ１－ＣＯ２－で表される連結基が好ましい。Ａｂ１は、直鎖状若しくは分岐鎖状アルキレン基、又は、単環若しくは多環のシクロアルキレン基であり、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、又は、ノルボルニレン基が好ましい。
　Ｖは、一般式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造の環員原子から水素原子を１つ引き抜いてなる基、又は、一般式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造の環員原子から水素原子を１つ引き抜いてなる基を表す。 In the general formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
Ab is a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represents. Among them, a single bond, or, -Ab 1 -CO 2 - preferred linking group represented by. Ab 1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornene group is preferable.
V is a group formed by extracting one hydrogen atom from a ring member atom having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or a general formula (SL1-1) to V. It represents a group formed by extracting one hydrogen atom from a ring member atom having a sultone structure represented by any one of (SL1-3).
　ラクトン基又はスルトン基を有する繰り返し単位に、光学異性体が存在する場合、いずれの光学異性体を使用してもよい。また、１種の光学異性体を単独で使用しても、複数の光学異性体を混合して使用してもよい。１種の光学異性体を主に用いる場合、その光学純度（ｅｅ）は９０以上が好ましく、９５以上がより好ましい。 If an optical isomer is present in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Further, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
　カーボネート基としては、環状炭酸エステル基が好ましい。
　環状炭酸エステル基を有する繰り返し単位としては、下記一般式（Ａ－１）で表される繰り返し単位が好ましい。 As the carbonate group, a cyclic carbonate group is preferable.
As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferable.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　一般式（Ａ－１）中、ＲＡ １は、水素原子、ハロゲン原子、又は、１価の有機基（好ましくはメチル基）を表す。
　ｎは０以上の整数を表す。
　ＲＡ ２は、置換基を表す。ｎが２以上の場合、複数存在するＲＡ ２は、それぞれ同一でも異なっていてもよい。
　Ａは、単結合又は２価の連結基を表す。上記２価の連結基としては、アルキレン基、単環若しくは多環の脂環炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又は、これらを組み合わせた２価の基が好ましい。
　Ｚは、式中の－Ｏ－ＣＯ－Ｏ－で表される基と共に単環又は多環を形成する原子団を表す。 In the general formula (A-1), RA 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
n represents an integer greater than or equal to 0.
RA 2 represents a substituent. when n is 2 or more, R A 2 existing in plural, may each be the same or different.
A represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof. The valence group is preferred.
Z represents an atomic group forming a monocyclic or polycyclic ring with a group represented by —O—CO—O— in the formula.
　ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位を以下に例示する。 The repeating unit having a lactone group, a sultone group, or a carbonate group is illustrated below.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対し、１モル％以上が好ましく、５モル％以上がより好ましい。また、その上限値は特に制限されないが、６５モル％以下が好ましく、３０モル％以下がより好ましく、２５モル％以下が更に好ましく、２０モル％以下が特により好ましい。 The content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the repeating units in the resin (A). The upper limit thereof is not particularly limited, but is preferably 65 mol% or less, more preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 20 mol% or less.
≪光酸発生基を有する繰り返し単位≫
　樹脂（Ａ）は、上記以外の繰り返し単位として、活性光線又は放射線の照射により酸を発生する基（以下、「光酸発生基」ともいう。）を有する繰り返し単位を有していてもよい。
　この場合、この光酸発生基を有する繰り返し単位が、後述する活性光線又は放射線の照射により酸を発生する化合物（以下、「光酸発生剤」ともいう。）にあたると考えることができる。
　このような繰り返し単位としては、例えば、下記一般式（４）で表される繰り返し単位が挙げられる。 ≪Repeating unit with photoacid generating group≫
The resin (A) may have a repeating unit having a group that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “photoacid generating group”) as a repeating unit other than the above.
In this case, it can be considered that the repeating unit having this photoacid-generating group corresponds to a compound that generates an acid by irradiation with active light or radiation described later (hereinafter, also referred to as “photoacid generator”).
Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　Ｒ４１は、水素原子又はメチル基を表す。Ｌ４１は、単結合、又は、２価の連結基を表す。Ｌ４２は、２価の連結基を表す。Ｒ４０は、活性光線又は放射線の照射により分解して側鎖に酸を発生させる構造部位を表す。 R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linking group. L 42 represents a divalent linking group. R 40 represents a structural site that is decomposed by irradiation with active light or radiation to generate an acid in the side chain.
　光酸発生基を有する繰り返し単位を以下に例示する。 The repeating unit having a photoacid generating group is illustrated below.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　そのほか、一般式（４）で表される繰り返し単位としては、例えば、特開２０１４－０４１３２７号公報の段落［００９４］～［０１０５］に記載された繰り返し単位が挙げられる。 In addition, examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327.
　光酸発生基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１モル％以上が好ましく、５モル％以上がより好ましい。また、その上限値としては、４０モル％以下が好ましく、３５モル％以下がより好ましく、３０モル％以下が更に好ましい。 The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the repeating units in the resin (A). The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.
≪一般式（Ｖ－１）又は下記一般式（Ｖ－２）で表される繰り返し単位≫
　樹脂（Ａ）は、下記一般式（Ｖ－１）、又は、下記一般式（Ｖ－２）で表される繰り返し単位を有していてもよい。
　下記一般式（Ｖ－１）、及び、下記一般式（Ｖ－２）で表される繰り返し単位は上述の繰り返し単位とは異なる繰り返し単位であるのが好ましい。 << Repeat unit represented by the general formula (V-1) or the following general formula (V-2) >>
The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式中、
　Ｒ６及びＲ７は、それぞれ独立に、水素原子、水酸基、アルキル基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ又は－ＣＯＯＲ：Ｒは、炭素数１～６のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。アルキル基としては、炭素数１～１０の直鎖状、分岐鎖状又は環状のアルキル基が好ましい。
　ｎ３は、０～６の整数を表す。
　ｎ４は、０～４の整数を表す。
　Ｘ４は、メチレン基、酸素原子、又は、硫黄原子である。
　一般式（Ｖ－１）又は（Ｖ－２）で表される繰り返し単位を以下に例示する。 During the ceremony
R 6 and R 7 are independently hydrogen atom, hydroxyl group, alkyl group, alkoxy group, asyloxy group, cyano group, nitro group, amino group, halogen atom and ester group (-OCOR or -COOR: R is carbon. It represents an alkyl group of numbers 1 to 6 or a fluorinated alkyl group) or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable.
n 3 represents an integer from 0 to 6.
n 4 represents an integer from 0 to 4.
X 4 is a methylene group, an oxygen atom, or a sulfur atom.
The repeating unit represented by the general formula (V-1) or (V-2) is illustrated below.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
≪主鎖の運動性を低下させるための繰り返し単位≫
　樹脂（Ａ）は、発生酸の過剰な拡散又は現像時のパターン崩壊を抑制できる観点から、ガラス転移温度（Ｔｇ）が高い方が好ましい。Ｔｇは、９０℃より大きいことが好ましく、１００℃より大きいことがより好ましく、１１０℃より大きいことが更に好ましく、１２５℃より大きいことが特に好ましい。なお、過度な高Ｔｇ化は現像液への溶解速度低下を招くため、Ｔｇは４００℃以下が好ましく、３５０℃以下がより好ましい。
　なお、本明細書において、樹脂（Ａ）等のポリマーのガラス転移温度（Ｔｇ）は、以下の方法で算出する。まず、ポリマー中に含まれる各繰り返し単位のみからなるホモポリマーのＴｇを、Ｂｉｃｅｒａｎｏ法によりそれぞれ算出する。以後、算出されたＴｇを、「繰り返し単位のＴｇ」という。次に、ポリマー中の全繰り返し単位に対する、各繰り返し単位の質量割合（％）を算出する。次に、Ｆｏｘの式（Ｍａｔｅｒｉａｌｓ　Ｌｅｔｔｅｒｓ　６２（２００８）３１５２等に記載）を使用して各質量割合におけるＴｇを算出して、それらを総和して、ポリマーのＴｇ（℃）とする。
　Ｂｉｃｅｒａｎｏ法はＰｒｅｄｉｃｔｉｏｎ　ｏｆ　ｐｏｌｙｍｅｒ　ｐｒｏｐｅｒｔｉｅｓ，　Ｍａｒｃｅｌ　Ｄｅｋｋｅｒ　Ｉｎｃ，　Ｎｅｗ　Ｙｏｒｋ（１９９３）等に記載されている。またＢｉｃｅｒａｎｏ法によるＴｇの算出は、ポリマーの物性概算ソフトウェアＭＤＬ　Ｐｏｌｙｍｅｒ（ＭＤＬ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍｓ，　Ｉｎｃ．）を使用して行うことができる。 ≪Repeating unit to reduce the motility of the main chain≫
The resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern disintegration during development. Tg is preferably greater than 90 ° C, more preferably greater than 100 ° C, even more preferably greater than 110 ° C, and particularly preferably greater than 125 ° C. Since excessively high Tg causes a decrease in the dissolution rate in the developing solution, Tg is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
In the present specification, the glass transition temperature (Tg) of the polymer such as the resin (A) is calculated by the following method. First, the Tg of a homopolymer composed of only each repeating unit contained in the polymer is calculated by the Bicerano method. Hereinafter, the calculated Tg is referred to as "repeating unit Tg". Next, the mass ratio (%) of each repeating unit to all the repeating units in the polymer is calculated. Next, Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) and summed up to obtain the Tg (° C.) of the polymer.
The Bicerano method is described in the Precision of policies, Marcel Dekker Inc, New York (1993) and the like. Further, the calculation of Tg by the Bicerano method can be performed using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
　樹脂（Ａ）のＴｇを大きくする（好ましくは、Ｔｇを９０℃超とする）には、樹脂（Ａ）の主鎖の運動性を低下させることが好ましい。樹脂（Ａ）の主鎖の運動性を低下させる方法は、以下の（ａ）～（ｅ）の方法が挙げられる。
（ａ）主鎖への嵩高い置換基の導入
（ｂ）主鎖への複数の置換基の導入
（ｃ）主鎖近傍への樹脂（Ａ）間の相互作用を誘発する置換基の導入
（ｄ）環状構造での主鎖形成
（ｅ）主鎖への環状構造の連結
　なお、樹脂（Ａ）は、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位を有することが好ましい。
　なお、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位の種類は特に制限されず、Ｂｉｃｅｒａｎｏ法により算出されるホモポリマーのＴｇが１３０℃以上である繰り返し単位であればよい。なお、後述する式（Ａ）～式（Ｅ）で表される繰り返し単位中の官能基の種類によっては、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位に該当する。 In order to increase the Tg of the resin (A) (preferably, Tg exceeds 90 ° C.), it is preferable to reduce the motility of the main chain of the resin (A). Examples of the method for reducing the motility of the main chain of the resin (A) include the following methods (a) to (e).
(A) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between the resins (A) in the vicinity of the main chain ( d) Main chain formation in a cyclic structure (e) Connection of a cyclic structure to the main chain The resin (A) preferably has a repeating unit in which the Tg of the homopolymer is 130 ° C. or higher.
The type of repeating unit having a homopolymer Tg of 130 ° C. or higher is not particularly limited, and any repeating unit having a homopolymer Tg of 130 ° C. or higher calculated by the Bicerano method may be used. Depending on the type of the functional group in the repeating unit represented by the formulas (A) to (E) described later, the homopolymer corresponds to the repeating unit having a Tg of 130 ° C. or higher.
（式（Ａ）で表される繰り返し単位）
　上記（ａ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ａ）で表される繰り返し単位を導入する方法が挙げられる。 (Repeating unit represented by the formula (A))
As an example of the specific means for achieving the above (a), there is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（Ａ）、ＲＡは、多環構造を有する基を表す。Ｒｘは、水素原子、メチル基、又は、エチル基を表す。多環構造を有する基とは、複数の環構造を有する基であり、複数の環構造は縮合していても、縮合していなくてもよい。
　式（Ａ）で表される繰り返し単位の具体例としては、下記繰り返し単位が挙げられる。 The formula (A) and RA represent a group having a polycyclic structure. R x represents a hydrogen atom, a methyl group, or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed.
Specific examples of the repeating unit represented by the formula (A) include the following repeating units.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　上記式中、Ｒは、水素原子、メチル基、又は、エチル基を表す。
　Ｒａは、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’’又は－ＣＯＯＲ’’’：Ｒ’’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒａで表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　また、Ｒ’及びＲ’’は、それぞれ独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’’又は－ＣＯＯＲ’’’：Ｒ’’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換機を有してもよい。また、Ｒ’及びＲ’’で表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　Ｌは、単結合又は２価の連結基を表す。２価の連結基としては、例えば、―ＣＯＯ－、－ＣＯ－、－Ｏ－、－Ｓ―、－ＳＯ－、－ＳＯ２－、アルキレン基、シクロアルキレン基、アルケニレン基、及び、これらの複数が連結した連結基等が挙げられる。
　ｍ及びｎは、それぞれ独立に、０以上の整数を表す。ｍ及びｎの上限は特に制限されないが、２以下の場合が多く、１以下の場合がより多い。 In the above formula, R represents a hydrogen atom, a methyl group, or an ethyl group.
Ra is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group (-OCOR'''. Alternatively, -COOR "": R "" represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced with a fluorine atom or an iodine atom.
Further, R'and R'' are independently alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, asyloxy group, cyano group, nitro group, amino group, halogen atom, respectively. It represents an ester group (-OCOR ′ ″ or −COOR ′ ″: R ″ ″ is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R'and R'may be replaced with a fluorine atom or an iodine atom.
L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO- , -O-, -S-, -SO-, -SO 2- , an alkylene group, a cycloalkylene group, an alkaneylene group, and a plurality of these. Examples thereof include a linking group in which is linked.
m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are often 2 or less and more often 1 or less.
（式（Ｂ）で表される繰り返し単位）
　上記（ｂ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｂ）で表される繰り返し単位を導入する方法が挙げられる。 (Repeating unit represented by equation (B))
As an example of the specific means for achieving the above (b), there is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（Ｂ）中、Ｒｂ１～Ｒｂ４は、それぞれ独立に、水素原子又は有機基を表し、Ｒｂ１～Ｒｂ４のうち少なくとも２つ以上が有機基を表す。
　また、有機基の少なくとも１つが、繰り返し単位中の主鎖に直接環構造が連結している基である場合、他の有機基の種類は特に制限されない。
　また、有機基のいずれも繰り返し単位中の主鎖に直接環構造が連結している基ではない場合、有機基の少なくとも２つ以上は、水素原子を除く構成原子数が３つ以上である置換基である。 In the formula (B), R b1 to R b4 independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
Further, when at least one of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited.
Further, when none of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, at least two or more organic groups are substituted in which the number of constituent atoms excluding hydrogen atoms is three or more. It is a group.
　式（Ｂ）で表される繰り返し単位の具体例としては、下記繰り返し単位が挙げられる。 Specific examples of the repeating unit represented by the formula (B) include the following repeating units.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　上記式中、Ｒは、それぞれ独立に、水素原子又は有機基を表す。有機基としては、置換機を有してもよい、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等の有機基が挙げられる。
　Ｒ’は、それぞれ独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’又は－ＣＯＯＲ’’：Ｒ’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒ’で表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　ｍは０以上の整数を表す。ｍの上限は特に制限されないが、２以下の場合が多く、１以下の場合がより多い。 In the above formula, R independently represents a hydrogen atom or an organic group. Examples of the organic group include an organic group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
R'is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR'. 'Or-COOR'': R'' represents an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R'may be replaced with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
（式（Ｃ）で表される繰り返し単位）
　上記（ｃ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｃ）で表される繰り返し単位を導入する方法が挙げられる。 (Repeating unit represented by formula (C))
As an example of the specific means for achieving the above (c), there is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　式（Ｃ）中、Ｒｃ１～Ｒｃ４は、それぞれ独立に、水素原子又は有機基を表し、Ｒｃ１～Ｒｃ４のうち少なくとも１つが、主鎖炭素から原子数３以内に水素結合性の水素原子を有する基である。なかでも、樹脂（Ａ）の主鎖間の相互作用を誘発する上で、原子数２以内（より主鎖近傍側）に水素結合性の水素原子を有することが好ましい。 In the formula (C), R c1 to R c4 independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a hydrogen-bonding hydrogen within 3 atoms from the main chain carbon. It is a group having an atom. Among them, in order to induce the interaction between the main chains of the resin (A), it is preferable to have hydrogen-bonding hydrogen atoms within 2 atoms (closer to the main chain).
　式（Ｃ）で表される繰り返し単位の具体例としては、下記繰り返し単位が挙げられる。 Specific examples of the repeating unit represented by the formula (C) include the following repeating units.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　上記式中、Ｒは有機基を表す。有機基としては、置換基を有してもよい、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、及び、エステル基（－ＯＣＯＲ又は－ＣＯＯＲ：Ｒは、炭素数１～２０のアルキル基又はフッ素化アルキル基）等が挙げられる。
　Ｒ’は、水素原子又は有機基を表す。有機基としては、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等が挙げられる。なお、有機基中の水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。 In the above formula, R represents an organic group. The organic group may have a substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR: R has 1 to 20 carbon atoms. Alkyl group or fluorinated alkyl group) and the like.
R'represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. The hydrogen atom in the organic group may be replaced with a fluorine atom or an iodine atom.
（式（Ｄ）で表される繰り返し単位）
　上記（ｄ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｄ）で表される繰り返し単位を導入する方法が挙げられる。 (Repeating unit represented by formula (D))
As an example of the specific means for achieving the above (d), there is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（Ｄ）中、「ｃｙｌｉｃ」は、環状構造で主鎖を形成している基を表す。環の構成原子数は特に制限されない。 In formula (D), "cylic" represents a group forming a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited.
　式（Ｄ）で表される繰り返し単位の具体例としては、下記繰り返し単位が挙げられる。 Specific examples of the repeating unit represented by the formula (D) include the following repeating units.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　上記式中、Ｒは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’又は－ＣＯＯＲ’’：Ｒ’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒで表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　上記式中、Ｒ’は、それぞれ独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’又は－ＣＯＯＲ’’：Ｒ’’は、炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒ’で表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　ｍは０以上の整数を表す。ｍの上限は特に制限されないが、２以下の場合が多く、１以下の場合がより多い。 In the above formula, R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and the like. The ester group (-OCOR "or -COOR": R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
In the above formula, R'is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group. (-OCOR ″ or −COOR ″: R ″ represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R'may be replaced with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
（式（Ｅ）で表される繰り返し単位）
　上記（ｅ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｅ）で表される繰り返し単位を導入する方法が挙げられる。 (Repeating unit represented by formula (E))
As an example of the specific means for achieving the above (e), there is a method of introducing a repeating unit represented by the formula (E) into the resin (A).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　式（Ｅ）中、Ｒｅは、それぞれ独立に、水素原子又は有機基を表す。有機基としては、置換機を有してもよい、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等が挙げられる。
　「ｃｙｌｉｃ」は、主鎖の炭素原子を含む環状基である。環状基に含まれる原子数は特に制限されない。 In formula (E), Re independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like, which may have a substituent.
"Cylic" is a cyclic group containing a carbon atom in the main chain. The number of atoms contained in the cyclic group is not particularly limited.
　式（Ｅ）で表される繰り返し単位の具体例としては、下記繰り返し単位が挙げられる。 Specific examples of the repeating unit represented by the formula (E) include the following repeating units.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　上記式中、Ｒは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’又は－ＣＯＯＲ’’：Ｒ’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒで表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　Ｒ’は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’又は－ＣＯＯＲ’’：Ｒ’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又はカルボキシル基を表す。なお、上記アルキル基、上記シクロアルキル基、上記アリール基、上記アラルキル基、及び、上記アルケニル基は、それぞれ、置換基を有してもよい。また、Ｒ’で表される基中の炭素原子に結合している水素原子は、フッ素原子又はヨウ素原子で置換されていてもよい。
　ｍは０以上の整数を表す。ｍの上限は特に制限されないが、２以下の場合が多く、１以下の場合がより多い。
　また、式（Ｅ－２）、式（Ｅ－４）、式（Ｅ－６）、及び、式（Ｅ－８）中、２つＲは互いに結合して環を形成していてもよい。 In the above formula, R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen. It represents an atom, an ester group (-OCOR "or -COOR": R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
R'is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group. (-OCOR "or -COOR": R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R'may be replaced with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
Further, in the formula (E-2), the formula (E-4), the formula (E-6), and the formula (E-8), the two Rs may be bonded to each other to form a ring.
　式（Ｅ）で表される繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、５モル％以上が好ましく、１０モル％以上がより好ましい。また、その上限値としては、６０モル％以下が好ましく５５モル％以下がより好ましい。 The content of the repeating unit represented by the formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A). The upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.
≪ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及び、アルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位≫
　樹脂（Ａ）は、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及び、アルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位を有していてもよい。
　樹脂（Ａ）が有するラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位としては、上述した≪ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位≫で説明した繰り返し単位が挙げられる。好ましい含有量も上述した≪ラクトン基、スルトン基、又は、カーボネート基を有する繰り返し単位≫で説明した通りである。 << Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group >>
The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating unit described in the above-mentioned << Repeating unit having a lactone group, sultone group, or carbonate group >>. The preferred content is also as described above in << Repeating unit having a lactone group, sultone group, or carbonate group >>.
　樹脂（Ａ）は、水酸基又はシアノ基を有する繰り返し単位を有していてもよい。これにより基板密着性、現像液親和性が向上する。
　水酸基又はシアノ基を有する繰り返し単位は、水酸基又はシアノ基で置換された脂環炭化水素構造を有する繰り返し単位であることが好ましい。
　水酸基又はシアノ基を有する繰り返し単位は、酸分解性基を有さないことが好ましい。水酸基又はシアノ基を有する繰り返し単位としては、下記一般式（ＡＩＩａ）～（ＡＩＩｄ）で表される繰り返し単位が挙げられる。 The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.
The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
The repeating unit having a hydroxyl group or a cyano group preferably has no acid-degradable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIA) to (AIId).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　一般式（ＡＩＩａ）～（ＡＩＩｄ）において、
　Ｒ１ｃは、水素原子、メチル基、トリフロロメチル基、又は、ヒドロキメチル基を表す。
　Ｒ２ｃ～Ｒ４ｃは、それぞれ独立に、水素原子、水酸基、又は、シアノ基を表す。ただし、Ｒ２ｃ～Ｒ４ｃのうちの少なくとも１つは、水酸基又はシアノ基を表す。好ましくは、Ｒ２ｃ～Ｒ４ｃのうち、１つ又は２つが水酸基で、残りが水素原子である。より好ましくは、Ｒ２ｃ～Ｒ４ｃのうち、２つが水酸基で、残りが水素原子である。 In the general formulas (AIIA) to (AIID),
R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydrochimethyl group.
R 2c to R 4c independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R 2c to R 4c represents a hydroxyl group or a cyano group. Preferably, of R 2c to R 4c , one or two are hydroxyl groups and the rest are hydrogen atoms. More preferably, of R 2c to R 4c , two are hydroxyl groups and the rest are hydrogen atoms.
　水酸基又はシアノ基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、５モル％以上が好ましく、１０モル％以上がより好ましい。また、その上限値としては、４０モル％以下が好ましく、３５モル％以下がより好ましく、３０モル％以下が更に好ましい。 The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A). The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.
　水酸基又はシアノ基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。 Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　樹脂（Ａ）は、アルカリ可溶性基を有する繰り返し単位を有していてもよい。
　アルカリ可溶性基としては、カルボキシル基、スルホンアミド基、スルホニルイミド基、ビスルスルホニルイミド基、及び、α位が電子吸引性基で置換された脂肪族アルコール（例えば、ヘキサフロロイソプロパノール基）が挙げられ、カルボキシル基が好ましい。樹脂（Ａ）がアルカリ可溶性基を有する繰り返し単位を含むことにより、コンタクトホール用途での解像性が増す。
　アルカリ可溶性基を有する繰り返し単位としては、アクリル酸及びメタクリル酸による繰り返し単位のような樹脂の主鎖に直接アルカリ可溶性基が結合している繰り返し単位、又は、連結基を介して樹脂の主鎖にアルカリ可溶性基が結合している繰り返し単位が挙げられる。なお、連結基は、単環又は多環の環状炭化水素構造を有していてもよい。
　アルカリ可溶性基を有する繰り返し単位としては、アクリル酸又はメタクリル酸による繰り返し単位が好ましい。 The resin (A) may have a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol in which the α-position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group). A carboxyl group is preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased.
The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or a repeating unit in which the alkali-soluble group is directly bonded to the main chain of the resin via a linking group. Repeat units to which an alkali-soluble group is attached can be mentioned. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
As the repeating unit having an alkali-soluble group, a repeating unit made of acrylic acid or methacrylic acid is preferable.
　アルカリ可溶性基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、０モル％以上が好ましく、３モル％以上がより好ましく、５モル％以上が更に好ましい。その上限値としては、２０モル％以下が好ましく、１５モル％以下がより好ましく、１０モル％以下が更に好ましい。 The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, based on all the repeating units in the resin (A). The upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less.
　アルカリ可溶性基を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。具体例中、ＲｘはＨ、ＣＨ３、ＣＨ２ＯＨ、又は、ＣＦ３を表す。 Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific example, Rx represents H, CH 3 , CH 2 OH, or CF 3 .
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　ラクトン基、水酸基、シアノ基、及び、アルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位として、ラクトン基、水酸基、シアノ基、及び、アルカリ可溶性基から選ばれる少なくとも２つを有する繰り返し単位が好ましく、シアノ基とラクトン基を有する繰り返し単位がより好ましく、一般式（ＬＣ１－４）で表されるラクトン構造にシアノ基が置換した構造を有する繰り返し単位が更に好ましい。 A repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group as a repeating unit having at least one kind selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group. Is preferable, and a repeating unit having a cyano group and a lactone group is more preferable, and a repeating unit having a structure in which a cyano group is substituted with a lactone structure represented by the general formula (LC1-4) is further preferable.
≪脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位≫
　樹脂（Ａ）は、脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位を有してもよい。これにより液浸露光時にレジスト膜から液浸液への低分子成分の溶出が低減できる。このような繰り返し単位として、例えば、１－アダマンチル（メタ）アクリレート由来の繰り返し単位、ジアマンチル（メタ）アクリレート由来の繰り返し単位、トリシクロデカニル（メタ）アクリレート由来の繰り返し単位、及び、シクロヘキシル（メタ）アクリレート由来の繰り返し単位等が挙げられる。 ≪Repeating unit that has an alicyclic hydrocarbon structure and does not show acid degradability≫
The resin (A) may have an alicyclic hydrocarbon structure and may have a repeating unit that does not exhibit acid decomposition. This makes it possible to reduce the elution of small molecule components from the resist film to the immersion liquid during immersion exposure. Such repeating units include, for example, 1-adamantyl (meth) acrylate-derived repeating units, diamantyl (meth) acrylate-derived repeating units, tricyclodecanyl (meth) acrylate-derived repeating units, and cyclohexyl (meth). Examples include repeating units derived from acrylate.
≪水酸基及びシアノ基のいずれも有さない、一般式（ＩＩＩ）で表される繰り返し単位≫
　樹脂（Ａ）は、水酸基及びシアノ基のいずれも有さない、一般式（ＩＩＩ）で表される繰り返し単位を有していてもよい。 << Repeat unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group >>
The resin (A) may have a repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　一般式（ＩＩＩ）中、Ｒ５は少なくとも一つの環状構造を有し、水酸基及びシアノ基のいずれも有さない炭化水素基を表す。
　Ｒａは水素原子、アルキル基、又は、－ＣＨ２－Ｏ－Ｒａ２基を表す。式中、Ｒａ２は、水素原子、アルキル基、又は、アシル基を表す。 In the general formula (III), R 5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or, -CH 2 -O-Ra 2 group. In the formula, Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
　Ｒ５が有する環状構造には、単環式炭化水素基、及び、多環式炭化水素基が含まれる。単環式炭化水素基としては、例えば、炭素数３～１２（より好ましくは炭素数３～７）のシクロアルキル基、又は、炭素数３～１２のシクロアルケニル基が挙げられる。 The cyclic structure of R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.
　多環式炭化水素基としては、環集合炭化水素基、及び、架橋環式炭化水素基が挙げられる。
　架橋環式炭化水素環としては、２環式炭化水素環、３環式炭化水素環、及び、４環式炭化水素環等が挙げられる。また、架橋環式炭化水素環としては、５～８員シクロアルカン環が複数個縮合した縮合環も含まれる。
　架橋環式炭化水素基として、ノルボルニル基、アダマンチル基、ビシクロオクタニル基、又は、トリシクロ［５，２，１，０２，６］デカニル基が好ましく、ノルボニル基又はアダマンチル基がより好ましい。 Examples of the polycyclic hydrocarbon group include a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group.
Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The crosslinked cyclic hydrocarbon ring also includes a fused ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
Examples of the crosslinked cyclic hydrocarbon group, a norbornyl group, an adamantyl group, a bicyclooctanyl group, or, tricyclo [5,2,1,0 2,6] decanyl group are preferred, norbornyl group or more preferably an adamantyl group.
　脂環式炭化水素基は置換基を有していてもよく、置換基としては、ハロゲン原子、アルキル基、保護基で保護されたヒドロキシル基、及び、保護基で保護されたアミノ基が挙げられる。
　ハロゲン原子としては、臭素原子、塩素原子、又は、フッ素原子が好ましい。
　アルキル基としては、メチル基、エチル基、ブチル基、又は、ｔ－ブチル基が好ましい。上記アルキル基は更に置換基を有していてもよく、置換基としては、ハロゲン原子、アルキル基、保護基で保護されたヒドロキシル基、又は、保護基で保護されたアミノ基が挙げられる。 The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. ..
As the halogen atom, a bromine atom, a chlorine atom, or a fluorine atom is preferable.
As the alkyl group, a methyl group, an ethyl group, a butyl group, or a t-butyl group is preferable. The alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.
　保護基としては、例えば、アルキル基、シクロアルキル基、アラルキル基、置換メチル基、置換エチル基、アルコキシカルボニル基、及び、アラルキルオキシカルボニル基が挙げられる。
　アルキル基としては、炭素数１～４のアルキル基が好ましい。
　置換メチル基としては、メトキシメチル基、メトキシチオメチル基、ベンジルオキシメチル基、ｔ－ブトキシメチル基、又は、２－メトキシエトキシメチル基が好ましい。
　置換エチル基としては、１－エトキシエチル基、又は、１－メチル－１－メトキシエチル基が好ましい。
　アシル基としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、及び、ピバロイル基等の炭素数１～６の脂肪族アシル基が好ましい。
　アルコキシカルボニル基としては、炭素数１～４のアルコキシカルボニル基が好ましい。 Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.
As the substituted methyl group, a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, or a 2-methoxyethoxymethyl group is preferable.
As the substituted ethyl group, a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group is preferable.
As the acyl group, an aliphatic acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a pivaloyl group is preferable.
As the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferable.
　水酸基及びシアノ基のいずれも有さない、一般式（ＩＩＩ）で表される繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対し、０～４０モル％が好ましく、０～２０モル％がより好ましい。
　一般式（ＩＩＩ）で表される繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。式中、Ｒａは、Ｈ、ＣＨ３、ＣＨ２ＯＨ、又は、ＣＦ３を表す。 The content of the repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group, is preferably 0 to 40 mol%, preferably 0 to 20 mol%, based on all the repeating units in the resin (A). More preferably mol%.
Specific examples of the repeating unit represented by the general formula (III) are given below, but the present invention is not limited thereto. In the formula, Ra represents H, CH 3 , CH 2 OH, or CF 3 .
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
≪その他の繰り返し単位≫
　更に、樹脂（Ａ）は、上述した繰り返し単位以外の繰り返し単位を有してもよい。
　例えば樹脂（Ａ）は、オキサチアン環基を有する繰り返し単位、オキサゾロン環基を有する繰り返し単位、ジオキサン環基を有する繰り返し単位、及び、ヒダントイン環基を有する繰り返し単位からなる群から選択される繰り返し単位を有していてもよい。
　このような繰り返し単位を以下に例示する。 ≪Other repeating units≫
Further, the resin (A) may have a repeating unit other than the repeating unit described above.
For example, the resin (A) is a repeating unit selected from the group consisting of a repeating unit having an oxazolone ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may have.
Such repeating units are illustrated below.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　樹脂（Ａ）は、上記の繰り返し構造単位以外に、ドライエッチング耐性、標準現像液適性、基板密着性、レジストプロファイル、解像力、耐熱性、及び、感度等を調節する目的で様々な繰り返し構造単位を有していてもよい。 In addition to the above-mentioned repeating structural units, the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. You may have.
　樹脂（Ａ）としては、（特に、組成物がＡｒＦ用途で用いられる場合）繰り返し単位の全てが（メタ）アクリレート系繰り返し単位で構成されるのも好ましい。この場合、繰り返し単位の全てがメタクリレート系繰り返し単位であるもの、繰り返し単位の全てがアクリレート系繰り返し単位であるもの、繰り返し単位の全てがメタクリレート系繰り返し単位とアクリレート系繰り返し単位とによるもののいずれのものでも使用でき、アクリレート系繰り返し単位が全繰り返し単位の５０モル％以下であることが好ましい。 As the resin (A), it is also preferable that all of the repeating units (particularly when the composition is used for ArF applications) are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. It can be used, and the acrylate-based repeating unit is preferably 50 mol% or less of all the repeating units.
　樹脂（Ａ）は、常法に従って（例えばラジカル重合）合成できる。
　ＧＰＣ法によりポリスチレン換算値として、樹脂（Ａ）の重量平均分子量は、１０００～２０００００が好ましく、３０００～２００００がより好ましく、５０００～１５０００が更に好ましい。樹脂（Ａ）の重量平均分子量を、１０００～２０００００とすることにより、耐熱性及びドライエッチング耐性の劣化をより一層抑制できる。また、現像性の劣化、及び、粘度が高くなって製膜性が劣化することもより一層抑制できる。
　樹脂（Ａ）の分散度（分子量分布）は、通常１～５であり、１～３が好ましく、１．２～３．０がより好ましく、１．２～２．０が更に好ましい。分散度が小さいものほど、解像度、及び、レジスト形状がより優れ、更に、レジストパターンの側壁がよりスムーズである。 The resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
As a polystyrene conversion value by the GPC method, the weight average molecular weight of the resin (A) is preferably 1000 to 200,000, more preferably 3000 to 20000, and even more preferably 5000 to 15000. By setting the weight average molecular weight of the resin (A) to 1000 to 200,000, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developability and deterioration of film-forming property due to high viscosity can be further suppressed.
The dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern.
　レジスト組成物において、樹脂（Ａ）の含有量は、組成物の全固形分に対して、５０～９９．９質量％が好ましく、６０～９９．０質量％がより好ましい。
　なお、固形分とは、組成物中の溶剤を除いた成分を意図し、溶剤以外の成分であれば液状成分であっても固形分とみなす。
　また、樹脂（Ａ）は、１種で使用してもよいし、複数併用してもよい。 In the resist composition, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.
The solid content is intended to be a component of the composition excluding the solvent, and any component other than the solvent is regarded as a solid content even if it is a liquid component.
Further, the resin (A) may be used alone or in combination of two or more.
＜活性光線又は放射線により酸を発生する化合物（光酸発生剤）＞
　化学増幅型レジスト組成物は、活性光線又は放射線により酸を発生する化合物（以下、「光酸発生剤（ＰＡＧ：Ｐｈｏｔｏ　Ａｃｉｄ　Ｇｅｎｅｒａｔｏｒ）」ともいう。）を含むことが好ましい。
　光酸発生剤は、低分子化合物の形態であってもよく、重合体の一部に組み込まれた形態あってもよい。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用してもよい。
　また、光酸発生剤が低分子化合物の形態である場合、光酸発生剤の分子量は、３０００以下が好ましく、２０００以下がより好ましく、１０００以下が更に好ましい。
　光酸発生剤が、重合体の一部に組み込まれた形態である場合、樹脂（Ａ）の一部に組み込まれてもよく、樹脂（Ａ）とは異なる樹脂に組み込まれてもよい。
　本発明において、光酸発生剤が、低分子化合物の形態であることが好ましい。
　光酸発生剤としては、公知のものであれば特に制限されないが、活性光線又は放射線、好ましくは電子線又は極紫外線の照射により、有機酸、例えば、スルホン酸、ビス（アルキルスルホニル）イミド、及び、トリス（アルキルスルホニル）メチドの少なくともいずれかを発生する化合物が好ましい。
　より好ましくは下記一般式（ＺＩ）で表される化合物、（ＺＩＩ）で表される化合物、及び、（ＺＩＩＩ）で表される化合物が挙げられる。 <Compounds that generate acid by active light or radiation (photoacid generator)>
The chemically amplified resist composition preferably contains a compound that generates an acid by active light or radiation (hereinafter, also referred to as "photoacid generator (PAG)").
The photoacid generator may be in the form of a small molecule compound or may be incorporated into a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator is in the form of a small molecule compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A).
In the present invention, the photoacid generator is preferably in the form of a small molecule compound.
The photoacid generator is not particularly limited as long as it is known, but organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and bis (alkylsulfonyl) imide can be obtained by irradiation with active light or radiation, preferably electron beam or extreme ultraviolet light. , A compound that produces at least one of tris (alkylsulfonyl) methides is preferred.
More preferably, the compound represented by the following general formula (ZI), the compound represented by (ZII), and the compound represented by (ZIII) can be mentioned.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　上記一般式（ＺＩ）において、Ｒ２０１、Ｒ２０２、及び、Ｒ２０３は、それぞれ独立に、有機基を表す。
　Ｒ２０１、Ｒ２０２、及び、Ｒ２０３としての有機基の炭素数は、１～３０が好ましく、１～２０がより好ましい。
　また、Ｒ２０１～Ｒ２０３のうち、２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、又は、カルボニル基を含んでいてもよい。Ｒ２０１～Ｒ２０３のうち、２つが結合して形成する基としては、アルキレン基（例えば、ブチレン基、及び、ペンチレン基）が挙げられる。
　Ｚ－は、非求核性アニオン（求核反応を起こす能力が著しく低いアニオン）を表す。 In the above general formula (ZI), R 201 , R 202, and R 203 each independently represent an organic group.
The carbon number of the organic group as R 201 , R 202 , and R 203 is preferably 1 to 30, and more preferably 1 to 20.
Further , two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (for example, a butylene group and a pentylene group).
Z - represents a non-nucleophilic anion (anion with a significantly lower ability to undergo a nucleophilic reaction).
　非求核性アニオンとしては、例えば、スルホン酸アニオン（脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、及び、カンファースルホン酸アニオン等）、カルボン酸アニオン（脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、及び、アラルキルカルボン酸アニオン等）、スルホニルイミドアニオン、ビス（アルキルスルホニル）イミドアニオン、及び、トリス（アルキルスルホニル）メチドアニオン等が挙げられる。 Examples of the non-nucleophilic anion include a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, and camphor sulfonic acid anion, etc.) and a carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion). , And aralkyl carboxylic acid anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
　脂肪族スルホン酸アニオン、及び、脂肪族カルボン酸アニオンにおける脂肪族部位は、アルキル基であってもシクロアルキル基であってもよく、好ましくは炭素数１～３０の直鎖状又は分岐鎖状アルキル基、及び、炭素数３～３０のシクロアルキル基が挙げられる。 The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and a linear or branched alkyl having 1 to 30 carbon atoms is preferable. Examples thereof include a group and a cycloalkyl group having 3 to 30 carbon atoms.
　芳香族スルホン酸アニオン、及び、芳香族カルボン酸アニオンにおける芳香族基としては、炭素数６～１４のアリール基が好ましい。例えば、フェニル基、トリル基、及び、ナフチル基等が挙げられる。 As the aromatic sulfonic acid anion and the aromatic group in the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferable. For example, a phenyl group, a tolyl group, a naphthyl group and the like can be mentioned.
　上記アルキル基、シクロアルキル基、及び、アリール基は、置換基を有していてもよい。具体例としては、ニトロ基、フッ素原子等のハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（好ましくは炭素数１～１５）、シクロアルキル基（好ましくは炭素数３～１５）、アリール基（好ましくは炭素数６～１４）、アルコキシカルボニル基（好ましくは炭素数２～７）、アシル基（好ましくは炭素数２～１２）、アルコキシカルボニルオキシ基（好ましくは炭素数２～７）、アルキルチオ基（好ましくは炭素数１～１５）、アルキルスルホニル基（好ましくは炭素数１～１５）、アルキルイミノスルホニル基（好ましくは炭素数１～１５）、アリールオキシスルホニル基（好ましくは炭素数６～２０）、アルキルアリールオキシスルホニル基（好ましくは炭素数７～２０）、シクロアルキルアリールオキシスルホニル基（好ましくは炭素数１０～２０）、アルキルオキシアルキルオキシ基（好ましくは炭素数５～２０）、及び、シクロアルキルアルキルオキシアルキルオキシ基（好ましくは炭素数８～２０）等が挙げられる。
　各基が有するアリール基及び環構造については、置換基として更にアルキル基（好ましくは炭素数１～１５）が挙げられる。 The alkyl group, cycloalkyl group, and aryl group may have a substituent. Specific examples include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably 1 to 15 carbon atoms), and cycloalkyl groups (preferably 3 to 15 carbon atoms). , Aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms). ), Alkoxythio group (preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), aryloxysulfonyl group (preferably having 1 to 15 carbon atoms). 6 to 20), alkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably 10 to 20 carbon atoms), alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms) , And a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms) and the like.
Regarding the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.
　アラルキルカルボン酸アニオンにおけるアラルキル基としては、炭素数７～１２のアラルキル基が好ましい。例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、及び、ナフチルブチル基等が挙げられる。 As the aralkyl group in the aralkyl carboxylic acid anion, an aralkyl group having 7 to 12 carbon atoms is preferable. For example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like can be mentioned.
　スルホニルイミドアニオンとしては、例えば、サッカリンアニオンが挙げられる。 Examples of the sulfonylimide anion include saccharin anion.
　ビス（アルキルスルホニル）イミドアニオン、又は、トリス（アルキルスルホニル）メチドアニオンにおけるアルキル基は、炭素数１～５のアルキル基が好ましい。これらのアルキル基の置換基としては、ハロゲン原子、ハロゲン原子で置換されたアルキル基、アルコキシ基、アルキルチオ基、アルキルオキシスルホニル基、アリールオキシスルホニル基、及び、シクロアルキルアリールオキシスルホニル基等が挙げられ、フッ素原子又はフッ素原子で置換されたアルキル基が好ましい。
　また、ビス（アルキルスルホニル）イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。 The alkyl group in the bis (alkylsulfonyl) imide anion or the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group and the like. , A fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
Further, the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
　その他の非求核性アニオンとしては、例えば、弗素化燐（例えば、ＰＦ６ －）、弗素化硼素（例えば、ＢＦ４ －）、及び、弗素化アンチモン（例えば、ＳｂＦ６ －）等が挙げられる。 As other non-nucleophilic anions, e.g., fluorinated phosphorus (e.g., PF 6 -), fluorinated boron (e.g., BF 4 -), and, fluorinated antimony (e.g., SbF 6 -) and the like is ..
　非求核性アニオンとしては、スルホン酸の少なくともα位がフッ素原子で置換された脂肪族スルホン酸アニオン、フッ素原子又はフッ素原子を有する基で置換された芳香族スルホン酸アニオン、アルキル基がフッ素原子で置換されたビス（アルキルスルホニル）イミドアニオン、及び、アルキル基がフッ素原子で置換されたトリス（アルキルスルホニル）メチドアニオンが好ましい。非求核性アニオンとして、パーフルオロ脂肪族スルホン酸アニオン（好ましくは炭素数４～８）、又は、フッ素原子を有するベンゼンスルホン酸アニオンがより好ましく、ノナフルオロブタンスルホン酸アニオン、パーフルオロオクタンスルホン酸アニオン、ペンタフルオロベンゼンスルホン酸アニオン、又は、３，５－ビス（トリフルオロメチル）ベンゼンスルホン酸アニオンが更に好ましい。 Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the fluorine atom or a group having a fluorine atom is substituted, and an alkyl group is a fluorine atom. Bis (alkylsulfonyl) imide anions substituted with, and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. As the non-nucleophilic anion, a perfluoroaliphatic sulfonic acid anion (preferably 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom is more preferable, and a nonafluorobutane sulfonic acid anion and a perfluorooctane sulfonic acid are used. Anions, pentafluorobenzene sulfonic acid anions, or 3,5-bis (trifluoromethyl) benzene sulfonic acid anions are more preferred.
　酸強度又は感度の観点から、発生酸のｐＫａは、－１以下が好ましい。 From the viewpoint of acid strength or sensitivity, the pKa of the generated acid is preferably -1 or less.
　また、非求核性アニオンとしては、以下の一般式（ＡＮ１）で表されるアニオンも好ましい態様として挙げられる。 Further, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) is also mentioned as a preferable embodiment.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　式中、Ｘｆは、それぞれ独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
　Ｒ１及びＲ２は、それぞれ独立に、水素原子、フッ素原子、又は、アルキル基を表し、複数存在する場合のＲ１及びＲ２は、それぞれ同一でも異なっていてもよい。
　Ｌは、２価の連結基を表し、複数存在する場合のＬは同一でも異なっていてもよい。
　Ａは、環状の有機基を表す。
　ｘは１～２０の整数を表し、ｙは０～１０の整数を表し、ｚは０～１０の整数を表す。 In the formula, Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R 1 and R 2 may be the same or different, respectively.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.
　一般式（ＡＮ１）について、更に詳細に説明する。
　Ｘｆのフッ素原子で置換されたアルキル基におけるアルキル基の炭素数としては、１～１０が好ましく、１～４がより好ましい。また、Ｘｆのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基が好ましい。
　Ｘｆとしては、フッ素原子又は炭素数１～４のパーフルオロアルキル基が好ましい。Ｘｆの具体例としては、フッ素原子、ＣＦ３、Ｃ２Ｆ５、Ｃ３Ｆ７、Ｃ４Ｆ９、ＣＨ２ＣＦ３、ＣＨ２ＣＨ２ＣＦ３、ＣＨ２Ｃ２Ｆ５、ＣＨ２ＣＨ２Ｃ２Ｆ５、ＣＨ２Ｃ３Ｆ７、ＣＨ２ＣＨ２Ｃ３Ｆ７、ＣＨ２Ｃ４Ｆ９、及び、ＣＨ２ＣＨ２Ｃ４Ｆ９が挙げられる。なかでも、フッ素原子又はＣＦ３が好ましい。
　特に、双方のＸｆがフッ素原子であることが好ましい。 The general formula (AN1) will be described in more detail.
The number of carbon atoms of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4. The alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferable. Specific examples of Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH. 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , and CH 2 CH 2 C 4 F 9 . Of these, a fluorine atom or CF 3 is preferable.
In particular, it is preferable that both Xfs are fluorine atoms.
　Ｒ１及びＲ２のアルキル基は、置換基（好ましくはフッ素原子）を有していてもよく、炭素数１～４が好ましい。なかでも、Ｒ１及びＲ２のアルキル基は、炭素数１～４のパーフルオロアルキル基が好ましい。Ｒ１及びＲ２の置換基を有するアルキル基の具体例としては、ＣＦ３、Ｃ２Ｆ５、Ｃ３Ｆ７、Ｃ４Ｆ９、Ｃ５Ｆ１１、Ｃ６Ｆ１３、Ｃ７Ｆ１５、Ｃ８Ｆ１７、ＣＨ２ＣＦ３、ＣＨ２ＣＨ２ＣＦ３、ＣＨ２Ｃ２Ｆ５、ＣＨ２ＣＨ２Ｃ２Ｆ５、ＣＨ２Ｃ３Ｆ７、ＣＨ２ＣＨ２Ｃ３Ｆ７、ＣＨ２Ｃ４Ｆ９、及び、ＣＨ２ＣＨ２Ｃ４Ｆ９が挙げられる。なかでも、ＣＦ３が好ましい。
　Ｒ１及びＲ２としては、フッ素原子又はＣＦ３が好ましい。 The alkyl groups of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably have 1 to 4 carbon atoms. Among them, the alkyl groups of R 1 and R 2 are preferably perfluoroalkyl groups having 1 to 4 carbon atoms. Specific examples of alkyl groups having substituents on R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 and C 7 F 15. , C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 and CH 2 CH 2 C 4 F 9 can be mentioned. Of these, CF 3 is preferable.
As R 1 and R 2 , a fluorine atom or CF 3 is preferable.
　ｘは１～１０が好ましく、１～５がより好ましい。
　ｙは０～４が好ましく、０がより好ましい。
　ｚは０～５が好ましく、０～３がより好ましい。
　Ｌの２価の連結基としては特に制限されず、―ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－Ｏ－、－Ｓ―、－ＳＯ―、―ＳＯ２－、アルキレン基、シクロアルキレン基、アルケニレン基、及び、これらの複数が連結した連結基等が挙げられる。なかでも、総炭素数１２以下の連結基が好ましい。また、―ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、又は、－Ｏ－が好ましく、―ＣＯＯ－、又は、－ＯＣＯ－がより好ましい。 x is preferably 1 to 10, more preferably 1 to 5.
y is preferably 0 to 4, more preferably 0.
z is preferably 0 to 5, more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene group, cycloalkylene group, Examples thereof include an alkaneylene group and a linking group in which a plurality of these groups are linked. Of these, a linking group having a total carbon number of 12 or less is preferable. Further, -COO-, -OCO-, -CO-, or -O- is preferable, and -COO- or -OCO- is more preferable.
　上記一般式（ＡＮ１）において、Ａ以外の部分構造の組み合わせとして、ＳＯ３－－ＣＦ２－ＣＨ２－ＯＣＯ－、ＳＯ３－－ＣＦ２－ＣＨＦ－ＣＨ２－ＯＣＯ－、ＳＯ３－－ＣＦ２－ＣＯＯ－、ＳＯ３－－ＣＦ２－ＣＦ２－ＣＨ２－、及び、ＳＯ３－－ＣＦ２－ＣＨ（ＣＦ３）－ＯＣＯ－が好ましい。 In formula (AN1), a combination of partial structures other than A, SO 3- -CF 2 -CH 2 -OCO-, SO 3- -CF 2 -CHF-CH 2 -OCO-, SO 3- -CF 2 -COO-, SO 3- -CF 2 -CF 2 -CH 2 -, and, SO 3- -CF 2 -CH (CF 3) -OCO- are preferred.
　Ａの環状の有機基としては、環状構造を有するものであれば特に制限されず、脂環基、アリール基、及び、複素環基（芳香族性を有するものだけでなく、芳香族性を有さないものも含む）等が挙げられる。
　脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、及び、シクロオクチル基等の単環のシクロアルキル基、又は、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の炭素数７以上の嵩高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、ＭＥＥＦ（ｍａｓｋ　ｅｒｒｏｒ　ｅｎｈａｎｃｅｍｅｎｔ　ｆａｃｔｏｒ）向上の観点から好ましい。
　アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、及び、アントラセン環が挙げられる。
　複素環基としては、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及び、ピリジン環由来のものが挙げられる。なかでも、フラン環、チオフェン環、又は、ピリジン環由来のものが好ましい。 The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and has an alicyclic group, an aryl group, and a heterocyclic group (not only those having aromaticity but also aromaticity). (Including those that do not), etc.
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, or a norbornyl group, a tricyclodecanyl group, or a tetracyclodecanyl group. , Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable. Among them, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are used in the post-exposure heating step. It is preferable from the viewpoint of improving MEEF (maskeror enhancement factor) because it can suppress the diffusivity in the membrane.
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring, or a pyridine ring are preferable.
　また、環状の有機基としては、ラクトン構造も挙げられ、具体例としては、下記一般式（ＬＣ１－１）～（ＬＣ１－１７）で表されるラクトン構造が挙げられる。 Further, examples of the cyclic organic group include a lactone structure, and specific examples thereof include lactone structures represented by the following general formulas (LC1-1) to (LC1-17).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　上記環状の有機基は、置換基を有していてもよく、上記置換基としては、アルキル基（直鎖状、分岐鎖状、及び、環状のいずれであってもよく、炭素数１～１２が好ましい）、シクロアルキル基（単環、多環、及び、スピロ環のいずれであってもよく、炭素数３～２０が好ましい）、アリール基（炭素数６～１４が好ましい）、ヒドロキシ基、アルコキシ基、エステル基、アミド基、ウレタン基、ウレイド基、チオエーテル基、スルホンアミド基、及び、スルホン酸エステル基等が挙げられる。なお、環状の有機基を構成する炭素（環形成に寄与する炭素）はカルボニル炭素であってもよい。
　なお、上記置換基は、上記一般式（ＬＣ１－１）～（ＬＣ１－１７）においてはＲｂ２に相当する。また、上記一般式（ＬＣ１－１）～（ＬＣ１－１７）において、ｎ２は０～４の整数を表す。ｎ２が２以上の時、複数存在するＲｂ２は、同一でも異なっていてもよく、また、複数存在するＲｂ２同士が結合して環を形成してもよい。 The cyclic organic group may have a substituent, and the substituent may be any of an alkyl group (linear, branched, or cyclic, and has 1 to 12 carbon atoms. (Preferably), cycloalkyl group (which may be monocyclic, polycyclic, or spiro ring, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, Examples thereof include an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be carbonyl carbon.
The substituent corresponds to Rb 2 in the general formulas (LC1-1) to (LC1-17). Further, in the above general formulas (LC1-1) to (LC1-17), n2 represents an integer of 0 to 4. When n2 is 2 or more, Rb 2 existing in plural numbers may be the same or different or may be bonded to form a ring Rb 2 between the plurality of.
　一般式（ＺＩ）において、Ｒ２０１、Ｒ２０２、及び、Ｒ２０３の有機基としては、アリール基、アルキル基、及び、シクロアルキル基等が挙げられる。
　Ｒ２０１、Ｒ２０２、及び、Ｒ２０３のうち、少なくとも１つがアリール基であることが好ましく、３つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基等の他に、インドール残基、及び、ピロール残基等のヘテロアリール基も可能である。Ｒ２０１～Ｒ２０３のアルキル基及びシクロアルキル基としては、炭素数１～１０の直鎖状又は分岐鎖状アルキル基、又は、炭素数３～１０のシクロアルキル基が好ましい。アルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、又は、ｎ－ブチル基等が好ましい。シクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、又は、シクロへプチル基等が好ましい。これらの基は、更に置換基を有していてもよい。更に有していてもよい置換基としては、ニトロ基、フッ素原子等のハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（好ましくは炭素数１～１５）、シクロアルキル基（好ましくは炭素数３～１５）、アリール基（好ましくは炭素数６～１４）、アルコキシカルボニル基（好ましくは炭素数２～７）、アシル基（好ましくは炭素数２～１２）、及び、アルコキシカルボニルオキシ基（好ましくは炭素数２～７）等が挙げられるが、これらに制限されるものではない。 In the general formula (ZI), examples of the organic group of R 201 , R 202 , and R 203 include an aryl group, an alkyl group, a cycloalkyl group, and the like.
Of R 201 , R 202 , and R 203 , it is preferable that at least one is an aryl group, and it is more preferable that all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group and the like, a heteroaryl group such as an indole residue and a pyrrole residue can also be used. As the alkyl group and cycloalkyl group of R 201 to R 203, a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms is preferable. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like are preferable. As the cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like are preferable. These groups may further have a substituent. Further, as the substituent which may be possessed, a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms) and a cycloalkyl group (preferably having 1 to 15 carbon atoms). 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), and an alkoxycarbonyloxy. Groups (preferably 2 to 7 carbon atoms) and the like can be mentioned, but the group is not limited thereto.
　次に、一般式（ＺＩＩ）、及び、（ＺＩＩＩ）について説明する。
　一般式（ＺＩＩ）、及び、（ＺＩＩＩ）中、Ｒ２０４～Ｒ２０７は、それぞれ独立に、アリール基、アルキル基、又は、シクロアルキル基を表す。
　Ｒ２０４～Ｒ２０７のアリール基としてはフェニル基、又は、ナフチル基が好ましく、フェニル基がより好ましい。Ｒ２０４～Ｒ２０７のアリール基は、酸素原子、窒素原子、及び、硫黄原子等を有する複素環構造を有するアリール基であってもよい。複素環構造を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、及び、ベンゾチオフェン等が挙げられる。
　Ｒ２０４～Ｒ２０７におけるアルキル基及びシクロアルキル基としては、炭素数１～１０の直鎖状若しくは分岐鎖状アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、及び、ペンチル基）、又は、炭素数３～１０のシクロアルキル基（シクロペンチル基、シクロヘキシル基、ノルボルニル基）が好ましい。 Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R 204 to R 207 independently represent an aryl group, an alkyl group, or a cycloalkyl group, respectively.
As the aryl group of R 204 to R 207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R 204 to R 207 include a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group). , Or a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group) is preferable.
　Ｒ２０４～Ｒ２０７のアリール基、アルキル基、及び、シクロアルキル基は、置換基を有していてもよい。Ｒ２０４～Ｒ２０７のアリール基、アルキル基、及び、シクロアルキル基が有していてもよい置換基としては、例えば、アルキル基（例えば炭素数１～１５）、シクロアルキル基（例えば炭素数３～１５）、アリール基（例えば炭素数６～１５）、アルコキシ基（例えば炭素数１～１５）、ハロゲン原子、水酸基、及び、フェニルチオ基等が挙げられる。 The aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). ~ 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.
　また、一般式（ＺＩＩ）において、Ｚ－は非求核性アニオンを表す。具体的には、一般式（ＺＩ）においてＺ－として説明したものと同じであり、好ましい形態も同じである。 Further, in the general formula (ZII), Z − represents a non-nucleophilic anion. Specifically, it is the same as that described as Z − in the general formula (ZI), and the preferred form is also the same.
　以下、一般式（ＺＩ）～（ＺＩＩＩ）の具体例を示すが、これに制限されない。 Hereinafter, specific examples of the general formulas (ZI) to (ZIII) will be shown, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　本発明においては、上記光酸発生剤は、露光で発生した酸の非露光部への拡散を抑制し解像性を良好にする観点から、電子線又は極紫外線の照射により、体積１３０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であって、体積１９０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることがより好ましく、体積２７０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることが更に好ましく、体積４００Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることが特に好ましい。ただし、感度や塗布溶剤溶解性の観点から、上記体積は、２０００Å３以下であることが好ましく、１５００Å３以下であることが更に好ましい。上記体積の値は、富士通株式会社製の「ＷｉｎＭＯＰＡＣ」を使用して求めた。まず、各例に係る酸の化学構造を入力し、次に、この構造を初期構造としてＭＭ３法を用いた分子力場計算により、各酸の最安定立体配座を決定し、その後、これら最安定立体配座についてＰＭ３法を用いた分子軌道計算を行うことにより、各酸の「ａｃｃｅｓｓｉｂｌｅ　ｖｏｌｕｍｅ」を計算することができる。なお、１Åは、０．１ｎｍを意味する。
　本発明においては、活性光線又は放射線の照射により以下に例示する酸を発生する光酸発生剤が好ましい。なお、例の一部には、体積の計算値を付記している（単位Å３）。なお、ここで求めた計算値は、アニオン部にプロトンが結合した酸の体積値である。 In the present invention, the photoacid generator has a volume of 130 Å 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. (more preferably sulfonic acid) in the size of the acid is a compound which generates, more preferably (more preferably sulfonic acid) acid volume 190 Å 3 or more in size is a compound that generates a volume 270 Å 3 It is more preferably a compound that generates an acid having a size of the above size (more preferably a sulfonic acid), and particularly preferably a compound that generates an acid (more preferably a sulfonic acid) having a volume of 400 Å 3 or more. .. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is more preferably preferably 2000 Å 3 or less, is 1500 Å 3 or less. The above volume value was determined using "WinMOPAC" manufactured by Fujitsu Limited. First, the chemical structure of the acid according to each example is input, then the most stable conformation of each acid is determined by the molecular mechanics field calculation using the MM3 method with this structure as the initial structure, and then the most stable conformation of each acid is determined. The "accessible volume" of each acid can be calculated by calculating the molecular orbital of the stable conformation using the PM3 method. In addition, 1 Å means 0.1 nm.
In the present invention, a photoacid generator that generates the acids exemplified below by irradiation with active light or radiation is preferable. In addition, the calculated value of the volume is added to a part of the example (unit: Å 3 ). The calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion portion.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　光酸発生剤としては、特開２０１４－４１３２８号公報の段落［０３６８］～［０３７７］、特開２０１３－２２８６８１号公報の段落［０２４０］～［０２６２］（対応する米国特許出願公開第２０１５／００４５３３号公報の段落［０３３９］）が援用でき、これらの内容は本明細書に組み込まれる。また、好ましい具体例として以下の化合物が挙げられるが、これらに制限されるものではない。 Examples of the photoacid generator include paragraphs [0368] to [0377] of JP2014-41328, and paragraphs [0240] to [0262] of JP2013-228681 (corresponding US Patent Application Publication No. 2015 / Paragraph [0339]) of Gazette No. 004533 can be incorporated, the contents of which are incorporated herein by reference. In addition, the following compounds can be mentioned as preferable specific examples, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　光酸発生剤は、１種類単独で又は２種類以上を組み合わせて使用することができる。
　光酸発生剤のレジスト組成物中の含有量は、組成物の全固形分を基準として、０．１～５０質量％が好ましく、５～５０質量％がより好ましく、８～４０質量％が更に好ましい。特に、電子線や極紫外線露光の際に高感度化及び高解像性を両立するには光酸発生剤の含有率は高い方が好ましい。上記観点からは、１０～４０質量％が好ましく、１０～３５質量％がより好ましい。 The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the resist composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and further 8 to 40% by mass, based on the total solid content of the composition. preferable. In particular, it is preferable that the content of the photoacid generator is high in order to achieve both high sensitivity and high resolution when exposed to electron beams or extreme ultraviolet rays. From the above viewpoint, 10 to 40% by mass is preferable, and 10 to 35% by mass is more preferable.
＜溶剤＞
　上述した各成分を溶解させてレジスト組成物を調製する際には、溶剤を使用できる。使用できる溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、炭素数４～１０の環状ラクトン、炭素数４～１０の、環を含んでいてもよいモノケトン化合物、アルキレンカーボネート、アルコキシ酢酸アルキル、及び、ピルビン酸アルキル等の有機溶剤が挙げられる。 <Solvent>
A solvent can be used when preparing the resist composition by dissolving each of the above-mentioned components. Examples of the solvent that can be used include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and a ring having 4 to 10 carbon atoms. Examples thereof include organic solvents such as monoketone compounds, alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvate which may be used.
　アルキレングリコールモノアルキルエーテルカルボキシレートとしては、例えば、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノメチルエーテルアセテート、及び、エチレングリコールモノエチルエーテルアセテートが挙げられる。
　アルキレングリコールモノアルキルエーテルとしては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、及び、エチレングリコールモノエチルエーテルが挙げられる。 Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl. Examples thereof include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
　乳酸アルキルエステルとしては、例えば、乳酸メチル、乳酸エチル、乳酸プロピル、及び、乳酸ブチルが挙げられる。
　アルコキシプロピオン酸アルキルとしては、例えば、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチル、及び、３－メトキシプロピオン酸エチルが挙げられる。 Examples of the lactate alkyl ester include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.
Examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
　炭素数４～１０の環状ラクトンとしては、例えば、β－プロピオラクトン、β－ブチロラクトン、γ－ブチロラクトン、α－メチル－γ－ブチロラクトン、β－メチル－γ－ブチロラクトン、γ－バレロラクトン、γ－カプロラクトン、γ－オクタノイックラクトン、及び、α－ヒドロキシ－γ－ブチロラクトンが挙げられる。 Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, and γ-. Caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone can be mentioned.
　炭素数４～１０の、環を含んでいてもよいモノケトン化合物としては、例えば、２－ブタノン、３－メチルブタノン、ピナコロン、２－ペンタノン、３－ペンタノン、３－メチル－２－ペンタノン、４－メチル－２－ペンタノン、２－メチル－３－ペンタノン、４，４－ジメチル－２－ペンタノン、２，４－ジメチル－３－ペンタノン、２，２，４，４－テトラメチル－３－ペンタノン、２－ヘキサノン、３－ヘキサノン、５－メチル－３－ヘキサノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、２－メチル－３－ヘプタノン、５－メチル－３－ヘプタノン、２，６－ジメチル－４－ヘプタノン、２－オクタノン、３－オクタノン、２－ノナノン、３－ノナノン、５－ノナノン、２－デカノン、３－デカノン、４－デカノン、５－ヘキセン－２－オン、３－ペンテン－２－オン、シクロペンタノン、２－メチルシクロペンタノン、３－メチルシクロペンタノン、２，２－ジメチルシクロペンタノン、２，４，４－トリメチルシクロペンタノン、シクロヘキサノン、３－メチルシクロヘキサノン、４－メチルシクロヘキサノン、４－エチルシクロヘキサノン、２，２－ジメチルシクロヘキサノン、２，６－ジメチルシクロヘキサノン、２，２，６－トリメチルシクロヘキサノン、シクロヘプタノン、２－メチルシクロヘプタノン、及び、３－メチルシクロヘプタノンが挙げられる。 Examples of the monoketone compound having 4 to 10 carbon atoms and which may contain a ring include 2-butanone, 3-methylbutanone, pinacone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone and 4-. Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4 -Heptanone, 2-octanone, 3-octanone, 2-nonanonone, 3-nonanonone, 5-nonanonone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one , Cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone , 4-Ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcyclohexanone, and 3-methylcycloheptanone. Be done.
　アルキレンカーボネートとしては、例えば、プロピレンカーボネート、ビニレンカーボネート、エチレンカーボネート、及び、ブチレンカーボネートが挙げられる。
　アルコキシ酢酸アルキルとしては、例えば、酢酸－２－メトキシエチル、酢酸－２－エトキシエチル、酢酸－２－（２－エトキシエトキシ）エチル、酢酸－３－メトキシ－３－メチルブチル、及び、酢酸－１－メトキシ－２－プロピルが挙げられる。
　ピルビン酸アルキルとしては、例えば、ピルビン酸メチル、ピルビン酸エチル、及び、ピルビン酸プロピルが挙げられる。
　なかでも、溶剤としては、常温常圧下で、沸点１３０℃以上の溶剤が好ましい。具体的には、シクロペンタノン、γ－ブチロラクトン、シクロヘキサノン、乳酸エチル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル、ピルビン酸エチル、酢酸－２－エトキシエチル、酢酸－２－（２－エトキシエトキシ）エチル、及び、プロピレンカーボネートが挙げられる。 Examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkoxyalkyl acetate include -2-methoxyethyl acetate, -2-ethoxyethyl acetate, -2- (2-ethoxyethoxy) ethyl acetate, -3-methoxy-3-methylbutyl acetate, and -1-acetic acid. Examples include methoxy-2-propyl.
Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
Among them, as the solvent, a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure is preferable. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, ethyl acetate-2-ethoxyethyl, acetate -2- (2-ethoxyethoxy) ethyl and propylene carbonate can be mentioned.
　上記溶剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The above solvent may be used alone or in combination of two or more.
　本発明においては、有機溶剤としては、構造中に水酸基を含む溶剤と、水酸基を含まない溶剤とを混合した混合溶剤を使用してもよい。
　水酸基を含む溶剤としては、例えば、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、及び、乳酸エチル等が挙げられる。なかでも、プロピレングリコールモノメチルエーテル、又は、乳酸エチルが好ましい。
　水酸基を含まない溶剤としては、例えば、プロピレングリコールモノメチルエーテルアセテート、エチルエトキシプロピオネート、２－ヘプタノン、γ－ブチロラクトン、シクロヘキサノン、酢酸ブチル、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、及び、ジメチルスルホキシド等が挙げられる。なかでも、プロピレングリコールモノメチルエーテルアセテート、エチルエトキシプロピオネート、２－ヘプタノン、γ－ブチロラクトン、シクロヘキサノン、又は、酢酸ブチルが好ましく、プロピレングリコールモノメチルエーテルアセテート、エチルエトキシプロピオネート、又は、２－ヘプタノンがより好ましい。
　水酸基を含まない溶剤に対する、水酸基を含む溶剤の含有量の質量比［水酸基を含む溶剤の含有質量／水酸基を含まない溶剤の含有質量］は、１／９９～９９／１が好ましく、１０／９０～９０／１０がより好ましく、２０／８０～６０／４０が更に好ましい。また、塗布均一性の点で、混合溶剤中の水酸基を含まない溶剤の質量は、５０質量％以上が好ましい。 In the present invention, as the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used may be used.
Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Of these, propylene glycol monomethyl ether or ethyl lactate is preferable.
Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, and dimethyl. Examples thereof include sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, or butyl acetate is preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, or 2-heptanone is preferable. More preferred.
The mass ratio of the content of the solvent containing hydroxyl groups to the solvent containing no hydroxyl groups [mass content of solvent containing hydroxyl groups / mass content of solvent not containing hydroxyl groups] is preferably 1/99 to 99/1, and is preferably 10/90. ~ 90/10 is more preferable, and 20/80 to 60/40 is even more preferable. Further, from the viewpoint of coating uniformity, the mass of the solvent containing no hydroxyl group in the mixed solvent is preferably 50% by mass or more.
　上記溶剤は、プロピレングリコールモノメチルエーテルアセテートを含む２種類以上の混合溶剤であることが好ましく、γ―ブチルラクトンと酢酸ブチルの組み合わせがより好ましい。 The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate, and more preferably a combination of γ-butyl lactone and butyl acetate.
　溶剤としては、例えば、特開２０１４－２１９６６４号公報の段落［００１３］～［００２９］に記載の溶剤も使用できる。 As the solvent, for example, the solvents described in paragraphs [0013] to [0029] of JP2014-219664A can also be used.
＜酸拡散制御剤＞
　レジスト組成物は、露光から加熱までの経時による性能変化を低減するために、酸拡散制御剤を含むことが好ましい。 <Acid diffusion control agent>
The resist composition preferably contains an acid diffusion control agent in order to reduce the change in performance with time from exposure to heating.
　酸拡散制御剤としては、例えば、塩基性化合物が挙げられる。
　塩基性化合物としては、例えば、下記式（Ａ１）～（Ｅ１）で示される構造を有する化合物が挙げられる。 Examples of the acid diffusion control agent include basic compounds.
Examples of the basic compound include compounds having a structure represented by the following formulas (A1) to (E1).
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　一般式（Ａ１）及び（Ｅ１）中のＲ２００、Ｒ２０１、及び、Ｒ２０２は、同一でも異なってもよく、水素原子、アルキル基（好ましくは炭素数１～２０）、シクロアルキル基（好ましくは炭素数３～２０）、又は、アリール基（好ましくは炭素数６～２０）を表す。なお、Ｒ２０１及びＲ２０２は、互いに結合して環を形成してもよい。 R 200 , R 201 , and R 202 in the general formulas (A1) and (E1) may be the same or different, and may be the same or different, and are a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), and a cycloalkyl group (preferably 1 to 20 carbon atoms). Represents 3 to 20 carbon atoms) or an aryl group (preferably 6 to 20 carbon atoms). R 201 and R 202 may be combined with each other to form a ring.
　上記置換基を有するアルキル基としては、炭素数１～２０のアミノアルキル基、炭素数１～２０のヒドロキシアルキル基、又は、炭素数１～２０のシアノアルキル基が好ましい。
　Ｒ２０３、Ｒ２０４、Ｒ２０５、及び、Ｒ２０６は、同一でも異なってもよく、炭素数１～２０のアルキル基を表す。
　一般式（Ａ１）及び（Ｅ１）中のアルキル基は、無置換であることが好ましい。 As the alkyl group having the above substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
R 203 , R 204 , R 205 , and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A1) and (E1) are preferably unsubstituted.
　一般式（Ａ１）～（Ｅ１）で示される構造を有する化合物として、グアニジン、アミノピロリジン、ピラゾール、ピラゾリン、ピペラジン、アミノモルホリン、アミノアルキルモルフォリン、ピペリジンの他、イミダゾール構造、ジアザビシクロ構造、オニウムヒドロキシド構造、オニウムカルボキシレート構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び／又はエーテル結合を有するアルキルアミン誘導体、及び、水酸基及び／又はエーテル結合を有するアニリン誘導体等が挙げられる。 Compounds having structures represented by the general formulas (A1) to (E1) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin, piperidine, imidazole structure, diazabicyclo structure, and onium hydroxide. Examples thereof include compounds having a structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
　イミダゾール構造を有する化合物としては、イミダゾール、２，４，５－トリフェニルイミダゾール、及び、ベンズイミダゾール等が挙げられる。ジアザビシクロ構造を有する化合物としては、１，４－ジアザビシクロ［２，２，２］オクタン、１，５－ジアザビシクロ［４，３，０］ノナ－５－エン、及び、１，８－ジアザビシクロ［５，４，０］ウンデカ－７－エン等が挙げられる。オニウムヒドロキシド構造を有する化合物としてはトリアリールスルホニウムヒドロキシド、フェナシルスルホニウムヒドロキシド、及び、２－オキソアルキル基を有するスルホニウムヒドロキシドが挙げられる。具体的には、トリフェニルスルホニウムヒドロキシド、トリス（ｔ－ブチルフェニル）スルホニウムヒドロキシド、ビス（ｔ－ブチルフェニル）ヨードニウムヒドロキシド、フェナシルチオフェニウムヒドロキシド、及び、２－オキソプロピルチオフェニウムヒドロキシド等が挙げられる。
　オニウムカルボキシレート構造を有する化合物としては、オニウムヒドロキシド構造を有する化合物のアニオン部がカルボキシレートになったものであり、例えば、アセテート、アダマンタン－１－カルボキシレート、及び、パーフルオロアルキルカルボキシレート等が挙げられる。トリアルキルアミン構造を有する化合物としては、トリ（ｎ－ブチル）アミン、及び、トリ（ｎ－オクチル）アミン等が挙げられる。
　アニリン化合物としては、２，６－ジイソプロピルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジブチルアニリン、及び、Ｎ，Ｎ－ジヘキシルアニリン等が挙げられる。
　水酸基及び／又はエーテル結合を有するアルキルアミン誘導体としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、及び、トリス（メトキシエトキシエチル）アミン等が挙げられる。
　水酸基及び／又はエーテル結合を有するアニリン誘導体としては、Ｎ，Ｎ－ビス（ヒドロキシエチル）アニリン等が挙げられる。 Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [5, 4,0] Undeca-7-en and the like. Examples of the compound having an onium hydroxide structure include a triarylsulfonium hydroxide, a phenacylsulfonium hydroxide, and a sulfonium hydroxide having a 2-oxoalkyl group. Specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium. Hydroxyldo and the like can be mentioned.
Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Can be mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like.
Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
　塩基性化合物としては、更に、フェノキシ基を有するアミン化合物、及び、フェノキシ基を有するアンモニウム塩化合物も挙げられる。 Further, examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
　アミン化合物は、１級、２級、及び、３級のアミン化合物を使用することができ、少なくとも１つのアルキル基が窒素原子に結合しているアミン化合物が好ましい。アミン化合物は、３級アミン化合物であることがより好ましい。アミン化合物は、少なくとも１つのアルキル基（好ましくは炭素数１～２０）が窒素原子に結合していれば、アルキル基の他に、シクロアルキル基（好ましくは炭素数３～２０）、又は、アリール基（好ましくは炭素数６～１２）が窒素原子に結合していてもよい。
　また、アミン化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に１つ以上であり、３～９個が好ましく、４～６個がより好ましい。
　なかでも、オキシアルキレン基としては、オキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）、又は、オキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくは－ＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、オキシエチレン基がより好ましい。 As the amine compound, primary, secondary and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. The amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. The group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
Further, it is preferable that the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
Among them, the oxyalkylene group includes an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-). Preferably, an oxyethylene group is more preferred.
　アンモニウム塩化合物は、１級、２級、３級、又は、４級のアンモニウム塩化合物を使用することができ、少なくとも１つのアルキル基が窒素原子に結合しているアンモニウム塩化合物が好ましい。アンモニウム塩化合物は、少なくとも１つのアルキル基（好ましくは炭素数１～２０）が窒素原子に結合していれば、アルキル基の他に、シクロアルキル基（好ましくは炭素数３～２０）、又は、アリール基（好ましくは炭素数６～１２）が窒素原子に結合していてもよい。
　アンモニウム塩化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に１つ以上であり、３～９個が好ましく、４～６個がより好ましい。なかでも、オキシアルキレン基としては、基（－ＣＨ２ＣＨ２Ｏ－）、又は、オキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくはＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、オキシエチレン基がより好ましい。
　アンモニウム塩化合物のアニオンとしては、ハロゲン原子、スルホネート、ボレート、及び、フォスフェート等が挙げられる。なかでも、ハロゲン原子又はスルホネートが好ましい。ハロゲン原子としては、クロライド、ブロマイド、及び、アイオダイドが好ましい。スルホネートとしては、炭素数１～２０の有機スルホネートが好ましい。有機スルホネートとしては、炭素数１～２０のアルキルスルホネート、及び、アリールスルホネートが好ましい。アルキルスルホネートのアルキル基は、置換基を有していてもよく、置換基としては、例えば、フッ素、塩素、臭素、アルコキシ基、アシル基、及び、アリール基等が挙げられる。アルキルスルホネートとして、メタンスルホネート、エタンスルホネート、ブタンスルホネート、ヘキサンスルホネート、オクタンスルホネート、ベンジルスルホネート、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、及び、ノナフルオロブタンスルホネート等が挙げられる。アリールスルホネートのアリール基としては、ベンゼン環、ナフタレン環、及び、アントラセン環が挙げられる。ベンゼン環、ナフタレン環、及び、アントラセン環は、置換基を有していてもよく、置換基としては炭素数１～６の直鎖状若しくは分岐鎖状アルキル基、又は、炭素数３～６のシクロアルキル基が好ましい。直鎖状若しくは分岐鎖状アルキル基、及び、シクロアルキル基として、具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ヘキシル基、及び、シクロヘキシル基等が挙げられる。他の置換基としては炭素数１～６のアルコキシ基、ハロゲン原子、シアノ基、ニトロ基、アシル基、及び、アシルオキシ基等が挙げられる。 As the ammonium salt compound, a primary, secondary, tertiary or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The ammonium salt compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or a cycloalkyl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. The aryl group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
The ammonium salt compound preferably has an oxygen atom in the alkyl chain and has an oxyalkylene group formed therein. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among them, as the oxyalkylene group, a group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or CH 2 CH 2 CH 2 O-) is preferable, and oxy Ethylene groups are more preferred.
Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Of these, a halogen atom or a sulfonate is preferable. Chloride, bromide, and iodide are preferable as the halogen atom. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is preferable. As the organic sulfonate, alkyl sulfonate having 1 to 20 carbon atoms and aryl sulfonate are preferable. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy group, acyl group, aryl group and the like. Examples of the alkyl sulphonate include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring, and anthracene ring may have a substituent, and the substituent may be a linear or branched alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. Cycloalkyl groups are preferred. As linear or branched alkyl group and cycloalkyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n. -Hexyl group, cyclohexyl group and the like can be mentioned. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group and the like.
　フェノキシ基を有するアミン化合物、又は、フェノキシ基を有するアンモニウム塩化合物とは、アミン化合物又はアンモニウム塩化合物のアルキル基の窒素原子と反対側の末端にフェノキシ基を有するものである。フェノキシ基は、置換基を有していてもよい。フェノキシ基の置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、カルボン酸エステル基、スルホン酸エステル基、アリール基、アラルキル基、アシルオキシ基、及び、アリールオキシ基等が挙げられる。置換基の置換位は、２～６位のいずれであってもよい。置換基の数は、１～５の範囲でいずれであってもよい。 The amine compound having a phenoxy group or the ammonium salt compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryl. Examples include oxy groups. The substituent of the substituent may be any of 2 to 6 positions. The number of substituents may be in the range of 1 to 5.
　フェノキシ基と窒素原子との間に、少なくとも１つのオキシアルキレン基を有することが好ましい。オキシアルキレン基の数は、分子内に１つ以上であり、３～９個が好ましく、４～６個がより好ましい。なかでも、オキシアルキレン基としては、オキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）、又は、オキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくは－ＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、オキシエチレン基がより好ましい。 It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among them, the oxyalkylene group includes an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-). Preferably, an oxyethylene group is more preferred.
　フェノキシ基を有するアミン化合物は、フェノキシ基を有する１級又は２級アミンと、ハロアルキルエーテルとを加熱して反応させた後、水酸化ナトリウム、水酸化カリウム、及び、テトラアルキルアンモニウム等の強塩基の水溶液を添加した後、酢酸エチル及びクロロホルム等の有機溶剤で抽出によって得られる。または、１級又は２級アミンと、末端にフェノキシ基を有するハロアルキルエーテルとを加熱して反応させた後、水酸化ナトリウム、水酸化カリウム、及び、テトラアルキルアンモニウム等の強塩基の水溶液を添加した後、酢酸エチル及びクロロホルム等の有機溶剤で抽出によって得られる。 The amine compound having a phenoxy group is prepared by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, and then using a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium. After adding the aqueous solution, it is obtained by extraction with an organic solvent such as ethyl acetate and chloroform. Alternatively, a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal are heated and reacted, and then an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium is added. Then, it is obtained by extraction with an organic solvent such as ethyl acetate and chloroform.
（プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又は、プロトンアクセプター性から酸性に変化した化合物を発生する化合物（ＰＡ））
　本発明に係る組成物は、酸拡散制御剤として、プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又は、プロトンアクセプター性から酸性に変化した化合物を発生する化合物〔以下、化合物（ＰＡ）ともいう。〕を更に含んでいてもよい。 (A compound that has a proton-accepting functional group and is decomposed by irradiation with active light or radiation to reduce or eliminate the proton-accepting property, or to generate a compound that has changed from proton-accepting property to acidic (PA). )))
The composition according to the present invention has a proton-accepting functional group as an acid diffusion control agent, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have a proton acceptor property. A compound that produces a compound that has changed from sex to acid [hereinafter, also referred to as compound (PA). ] May be further included.
　プロトンアクセプター性官能基とは、プロトンと静電的に相互作用し得る基、又は、電子を有する官能基であって、例えば、環状ポリエーテル等のマクロサイクリック構造を有する官能基や、π共役に寄与しない非共有電子対をもった窒素原子を有する官能基を意味する。π共役に寄与しない非共有電子対を有する窒素原子とは、例えば、下記一般式に示す部分構造を有する窒素原子である。 The proton-accepting functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or π. It means a functional group having a nitrogen atom having an unshared electron pair that does not contribute to conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
　プロトンアクセプター性官能基の好ましい部分構造として、例えば、クラウンエーテル構造、アザクラウンエーテル構造、１～３級アミン構造、ピリジン構造、イミダゾール構造、及び、ピラジン構造等が挙げられる。 Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.
　化合物（ＰＡ）は、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又は、プロトンアクセプター性から酸性に変化した化合物を発生する。ここで、プロトンアクセプター性の低下、消失、又は、プロトンアクセプター性から酸性への変化とは、プロトンアクセプター性官能基にプロトンが付加することに起因するプロトンアクセプター性の変化であり、具体的には、プロトンアクセプター性官能基を有する化合物（ＰＡ）とプロトンからプロトン付加体が生成する時、その化学平衡における平衡定数が減少することを意味する。 Compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
　化合物（ＰＡ）の具体例としては、例えば、下記化合物が挙げられる。更に、化合物（ＰＡ）の具体例としては、例えば、特開２０１４－０４１３２８号公報の段落［０４２１］～［０４２８］、及び、特開２０１４－１３４６８６号公報の段落［０１０８］～［０１１６］に記載されたものを援用することができ、これらの内容は本明細書に組み込まれる。 Specific examples of the compound (PA) include the following compounds. Further, specific examples of the compound (PA) include, for example, paragraphs [0421] to [0428] of JP-A-2014-014328 and paragraphs [0108]-[0116] of JP-A-2014-134686. The ones described may be incorporated and these contents are incorporated herein by reference.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
　酸拡散制御剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　酸拡散制御剤の含有量は、レジスト組成物の全固形分に対して、０．００１～１０質量％が好ましく、０．００５～５質量％がより好ましい。 The acid diffusion control agent may be used alone or in combination of two or more.
The content of the acid diffusion control agent is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, based on the total solid content of the resist composition.
　レジスト組成物中での光酸発生剤および酸拡散制御剤の使用割合は、光酸発生剤／酸拡散制御剤（モル比）＝２．５～３００であることが好ましい。本発明の効果がより優れる点で、モル比が２．５以上が好ましく、露光後加熱処理までの経時でのレジストパターンの太りによる解像度の低下抑制の観点から３００以下が好ましい。光酸発生剤／酸拡散制御剤（モル比）は、５．０～２００がより好ましく、７．０～１５０が更に好ましい。 The ratio of the photoacid generator and the acid diffusion control agent used in the resist composition is preferably photoacid generator / acid diffusion control agent (molar ratio) = 2.5 to 300. In terms of more excellent effects of the present invention, the molar ratio is preferably 2.5 or more, and preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time from exposure to heat treatment. The photoacid generator / acid diffusion control agent (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.
　酸拡散制御剤としては、例えば、特開２０１３－０１１８３３号公報の段落［０１４０］～［０１４４］に記載の化合物（アミン化合物、アミド基含有化合物、ウレア化合物、及び、含窒素複素環化合物等）を使用できる。 Examples of the acid diffusion control agent include the compounds described in paragraphs [0140] to [0144] of JP2013-011833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). Can be used.
＜疎水性樹脂＞
　レジスト組成物は、上記樹脂（Ａ）とは別に疎水性樹脂を含んでいてもよい。
　疎水性樹脂はレジスト膜の表面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性／非極性物質を均一に混合することに寄与しなくてもよい。
　疎水性樹脂を添加することの効果として、水に対するレジスト膜表面の静的／動的な接触角の制御、及び、アウトガスの抑制等が挙げられる。 <Hydrophobic resin>
The resist composition may contain a hydrophobic resin in addition to the resin (A).
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule and polar / non-polar substances are uniformly mixed. It does not have to contribute to.
The effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgas, and the like.
　疎水性樹脂は、膜表層への偏在化の観点から、フッ素原子、珪素原子、及び、樹脂の側鎖部分に含有されたＣＨ３部分構造のいずれか１種以上を有することが好ましく、２種以上を有することがより好ましい。また、上記疎水性樹脂は、炭素数５以上の炭化水素基を含むことが好ましい。これらの基は樹脂の主鎖中に有していても、側鎖に置換していてもよい。 From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of fluorine atoms, silicon atoms, and a CH 3-part structure contained in the side chain portion of the resin. It is more preferable to have the above. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.
　疎水性樹脂が、フッ素原子及び／又は珪素原子を含む場合、疎水性樹脂における上記フッ素原子及び／又は珪素原子は、樹脂の主鎖中に含まれていてもよく、側鎖中に含まれていてもよい。 When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.
　疎水性樹脂がフッ素原子を含む場合、フッ素原子を有する部分構造として、フッ素原子を有するアルキル基、フッ素原子を有するシクロアルキル基、又は、フッ素原子を有するアリール基を有する樹脂であることが好ましい。
　フッ素原子を有するアルキル基（好ましくは炭素数１～１０、より好ましくは炭素数１～４）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又は分岐鎖状アルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
　フッ素原子を有するシクロアルキル基は、少なくとも１つの水素原子がフッ素原子で置換された単環又は多環のシクロアルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
　フッ素原子を有するアリール基としては、フェニル基、及び、ナフチル基等のアリール基の少なくとも１つの水素原子がフッ素原子で置換されたものが挙げられ、更にフッ素原子以外の置換基を有していてもよい。
　フッ素原子又は珪素原子を有する繰り返し単位の例としては、ＵＳ２０１２／０２５１９４８Ａ１の段落［０５１９］に例示されたものを挙げることができる。 When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Further, it may have a substituent other than a fluorine atom.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.
Examples of the aryl group having a fluorine atom include a phenyl group and a group in which at least one hydrogen atom of an aryl group such as a naphthyl group is substituted with a fluorine atom, and further has a substituent other than the fluorine atom. May be good.
Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph [0519] of US2012 / 0251948A1.
　また、上記したように、疎水性樹脂は、側鎖部分にＣＨ３部分構造を含むことも好ましい。
　ここで、疎水性樹脂中の側鎖部分が有するＣＨ３部分構造には、エチル基、及び、プロピル基等が有するＣＨ３部分構造を包含するものである。
　一方、疎水性樹脂の主鎖に直接結合しているメチル基（例えば、メタクリル酸構造を有する繰り返し単位のα－メチル基）は、主鎖の影響により疎水性樹脂の表面偏在化への寄与が小さいため、本発明におけるＣＨ３部分構造に包含されないものとする。 Further, as described above, the hydrophobic resin may also preferably comprise a CH 3 partial structure side chain moiety.
Here, the CH 3 partial structure contained in the side chain portion of the hydrophobic resin, an ethyl group, and is intended to encompass CH 3 partial structure a propyl group has.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) contributes to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. small order, and it shall not be included in the CH 3 partial structures in the present invention.
　疎水性樹脂に関しては、特開２０１４－０１０２４５号公報の段落［０３４８］～［０４１５］の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Regarding the hydrophobic resin, the description in paragraphs [0348] to [0415] of JP2014-010245A can be referred to, and these contents are incorporated in the present specification.
　なお、疎水性樹脂としてはこの他にも特開２０１１－２４８０１９号公報、特開２０１０－１７５８５９号公報、及び／又は、特開２０１２－０３２５４４号公報に記載の樹脂も好ましく使用できる。 As the hydrophobic resin, the resins described in JP-A-2011-24801, JP-A-2010-175859, and / or JP-A-2012-032544 can also be preferably used.
＜界面活性剤＞
　レジスト組成物は、界面活性剤を更に含んでいてもよい。界面活性剤を含むことにより、波長が２５０ｎｍ以下、特には２２０ｎｍ以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
　界面活性剤としては、フッ素系及び／又はシリコン系界面活性剤を用いることが特に好ましい。
　フッ素系及び／又はシリコン系界面活性剤としては、例えば、米国特許出願公開第２００８／０２４８４２５号の段落［０２７６］に記載の界面活性剤が挙げられる。また、エフトップＥＦ３０１若しくはＥＦ３０３（新秋田化成（株）製）；フロラードＦＣ４３０、４３１若しくは４４３０（住友スリーエム（株）製）；メガファックＦ１７１、Ｆ１７３、Ｆ１７６、Ｆ１８９、Ｆ１１３、Ｆ１１０、Ｆ１７７、Ｆ１２０若しくはＲ０８（ＤＩＣ（株）製）；サーフロンＳ－３８２、ＳＣ１０１、１０２、１０３、１０４、１０５若しくは１０６（旭硝子（株）製）；トロイゾルＳ－３６６（トロイケミカル（株）製）；ＧＦ－３００若しくはＧＦ－１５０（東亜合成化学（株）製）、サーフロンＳ－３９３（セイミケミカル（株）製）；エフトップＥＦ１２１、ＥＦ１２２Ａ、ＥＦ１２２Ｂ、ＲＦ１２２Ｃ、ＥＦ１２５Ｍ、ＥＦ１３５Ｍ、ＥＦ３５１、ＥＦ３５２、ＥＦ８０１、ＥＦ８０２若しくはＥＦ６０１（（株）ジェムコ製）；ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０若しくはＰＦ６５２０（ＯＭＮＯＶＡ社製）；又は、ＦＴＸ－２０４Ｇ、２０８Ｇ、２１８Ｇ、２３０Ｇ、２０４Ｄ、２０８Ｄ、２１２Ｄ、２１８Ｄ若しくは２２２Ｄ（（株）ネオス製）を使用してもよい。なお、ポリシロキサンポリマーＫＰ－３４１（信越化学工業（株）製）も、シリコン系界面活性剤として使用できる。 <Surfactant>
The resist composition may further contain a surfactant. The inclusion of a surfactant makes it possible to form a pattern with less adhesion and less development defects with good sensitivity and resolution when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less. ..
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425. In addition, Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Co., Ltd.) You may. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.
　また、界面活性剤は、上記に示す公知のものの他に、テロメリゼーション法（テロマー法ともいわれる）、又は、オリゴメリゼーション法（オリゴマー法ともいわれる）により製造されたフルオロ脂肪族化合物を使用して合成してもよい。具体的には、このフルオロ脂肪族化合物から導かれたフルオロ脂肪族基を備えた重合体を、界面活性剤として使用してもよい。このフルオロ脂肪族化合物は、例えば、特開２００２－０９０９９１号公報に記載された方法によって合成することができる。
　また、米国特許出願公開第２００８／０２４８４２５号の段落［０２８０］に記載されているフッ素系及び／又はシリコン系以外の界面活性剤を使用してもよい。 In addition to the known surfactants shown above, fluoroaliphatic compounds produced by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method) are used as the surfactant. May be synthesized. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991.
In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.
　界面活性剤は、１種単独で使用してもよく、２種以上を使用してもよい。 The surfactant may be used alone or in combination of two or more.
　レジスト組成物が界面活性剤を含む場合、その含有量は、組成物の全固形分に対して、０～２質量％が好ましく、０．０００１～２質量％がより好ましく、０．０００５～１質量％が更に好ましい。 When the resist composition contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and 0.0005 to 1 with respect to the total solid content of the composition. Mass% is more preferred.
＜その他の添加剤＞
　化学増幅型レジスト組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び／又は、現像液に対する溶解性を促進させる化合物（例えば、分子量１０００以下のフェノール化合物、又は、カルボキシル基を含んだ脂環族若しくは脂肪族化合物）を更に含んでいてもよい。 <Other additives>
The chemically amplified resist composition is a dissolution-inhibiting compound, a dye, a plasticizing agent, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1000 or less, or a compound. , An alicyclic or aliphatic compound containing a carboxyl group) may be further contained.
　レジスト組成物は、溶解阻止化合物を更に含んでいてもよい。
　ここで「溶解阻止化合物」とは、酸の作用により分解して有機系現像液中での溶解度が減少する、分子量３０００以下の化合物である。 The resist composition may further contain a dissolution inhibitory compound.
Here, the "dissolution-inhibiting compound" is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
〔処理液の製造方法〕
　本発明の処理液は、金属成分、及び、沸点３００℃以上の有機物等の含有量を所望の範囲内にするために、以下の精製工程を実施することが好ましい。 [Manufacturing method of treatment liquid]
The treatment liquid of the present invention preferably carries out the following purification steps in order to keep the content of metal components and organic substances having a boiling point of 300 ° C. or higher within a desired range.
＜精製工程＞
　精製工程は、いずれのタイミングで実施されてもよい。精製工程としては、例えば、以下の精製処理Ｉ～ＩＶが挙げられる。
　すなわち、精製処理Ｉは、処理液に含まれる有機溶剤の製造前において、上記有機溶剤の製造に用いられる原材料に対して精製を行う処理である。
　また、精製処理ＩＩは、処理液に含まれる有機溶剤の製造時及び／又は製造後に、これの精製を行う処理である。
　また、精製処理ＩＩＩは、処理液の製造時において、２種以上の有機溶剤を混合する前に、成分毎に精製を行う処理である。
　また、精製処理ＩＶは、処理液の製造時において、２種以上の有機溶剤を混合した後に、混合物の精製を行う処理である。
　上述した通り、目的の処理液を得るには精製を行うことが好ましい。精製は個々の有機溶剤を精製した後に混合してもよいし、各有機溶剤を混合した後に精製してもよい。特に精製した有機溶剤をブレンドする方法が、有機溶剤のブレンド比を一定に製造できる点で好ましい。
　精製処理Ｉ～ＩＶは、それぞれ、１回のみ実施されてもよいし、２回以上実施されてもよい。
　また、使用する有機溶剤は、高純度グレード品（特に、上述した有機不純物、金属不純物、及び、水等の含有量が少ないもの）を購入し、更に、それらに対して後述する精製処理を行って使用することができる。 <Refining process>
The purification step may be carried out at any timing. Examples of the purification step include the following purification treatments I to IV.
That is, the purification treatment I is a treatment for purifying the raw material used for the production of the organic solvent before the production of the organic solvent contained in the treatment liquid.
Further, the purification treatment II is a treatment for purifying the organic solvent contained in the treatment liquid at the time of production and / or after production.
Further, the purification treatment III is a treatment in which each component is purified before mixing two or more kinds of organic solvents at the time of producing the treatment liquid.
Further, the purification treatment IV is a treatment for purifying the mixture after mixing two or more kinds of organic solvents at the time of producing the treatment liquid.
As described above, it is preferable to carry out purification in order to obtain the desired treatment liquid. Purification may be performed after purifying the individual organic solvents, or may be performed after mixing the respective organic solvents. In particular, a method of blending a purified organic solvent is preferable in that the blend ratio of the organic solvent can be produced to be constant.
Each of the purification treatments I to IV may be carried out only once or twice or more.
As the organic solvent to be used, high-purity grade products (particularly those having a small content of the above-mentioned organic impurities, metal impurities, water, etc.) are purchased, and further, the purification treatment described later is performed on them. Can be used.
　以下において、精製工程の一例を示す。以下の説明においては、精製工程における精製対象を、単に「被精製液」と総称する。
　精製工程として、例えば、被精製液のイオン交換処理を行う第一イオン交換処理、第一イオン交換処理後の被精製液の脱水を行う脱水処理、脱水処理後の被精製液の蒸留を行う蒸留処理、蒸留処理後の被精製液のイオン交換処理を行う第二イオン交換処理、及び、第二イオン交換処理後の被精製液の有機不純物除去を行う有機不純物除去処理、をこの順に実施する態様が挙げられる。なお、以下においては、上記の精製工程を一例として説明するが、本発明の処理液を調製する際の精製方法はこれに制限されない。例えば、まず、被精製液の脱水を行う脱水処理を実施し、脱水処理後の被精製液の蒸留を行う蒸留処理、被精製液のイオン交換処理を行う第一イオン交換処理、及び、第二イオン交換処理後の被精製液の有機不純物除去を行う有機不純物除去処理、をこの順に実施する態様であってもよい。 An example of the purification process is shown below. In the following description, the purification target in the purification step is simply collectively referred to as "the liquid to be purified".
As the purification step, for example, a first ion exchange treatment for performing an ion exchange treatment of the liquid to be purified, a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and a distillation for distilling the liquid to be purified after the dehydration treatment. An embodiment in which the second ion exchange treatment for performing the ion exchange treatment of the liquid to be purified after the treatment and the distillation treatment and the organic impurity removal treatment for removing the organic impurities of the liquid to be purified after the second ion exchange treatment are carried out in this order. Can be mentioned. In the following, the above purification step will be described as an example, but the purification method for preparing the treatment liquid of the present invention is not limited thereto. For example, first, a dehydration treatment for dehydrating the liquid to be purified is performed, a distillation treatment for distilling the liquid to be purified after the dehydration treatment, a first ion exchange treatment for ion exchange treatment of the liquid to be purified, and a second. The organic impurity removing treatment for removing the organic impurities in the liquid to be purified after the ion exchange treatment may be carried out in this order.
　第一イオン交換処理によれば、被精製液中のイオン成分（例えば、金属成分等）を除去することができる。
　第一イオン交換処理では、イオン交換樹脂等の第一イオン交換手段が用いられる。イオン交換樹脂としては、カチオン交換樹脂又はアニオン交換樹脂を単床で設けたもの、カチオン交換樹脂とアニオン交換樹脂とを複床で設けたもの、及び、カチオン交換樹脂とアニオン交換樹脂とを混床で設けたもの、のいずれであってもよい。
　また、イオン交換樹脂としては、イオン交換樹脂からの水分溶出を低減させるために、極力水分を含まない乾燥樹脂を使用することが好ましい。このような乾燥樹脂としては、市販品を使用でき、オルガノ社製の１５ＪＳ－ＨＧ・ＤＲＹ（商品名、乾燥カチオン交換樹脂、水分２％以下）、及び、ＭＳＰＳ２－１・ＤＲＹ（商品名、混床樹脂、水分１０％以下）等が挙げられる。 According to the first ion exchange treatment, an ionic component (for example, a metal component) in the liquid to be purified can be removed.
In the first ion exchange treatment, a first ion exchange means such as an ion exchange resin is used. As the ion exchange resin, a cation exchange resin or an anion exchange resin is provided on a single bed, a cation exchange resin and an anion exchange resin are provided on a double bed, and a cation exchange resin and an anion exchange resin are mixed. It may be any of those provided in.
Further, as the ion exchange resin, it is preferable to use a dry resin containing as little water as possible in order to reduce the elution of water from the ion exchange resin. As such a dry resin, a commercially available product can be used, and 15JS-HG / DRY (trade name, dry cation exchange resin, moisture content of 2% or less) manufactured by Organo Corporation and MSPS2-1 / DRY (trade name, mixed). Floor resin, moisture content of 10% or less) and the like.
　脱水処理によれば、被精製液中の水を除去できる。また、脱水処理において後述するゼオライト（特に、ユニオン昭和社製のモレキュラーシーブ（商品名）等）を使用した場合には、オレフィン類も除去可能である。
　脱水処理に用いられる脱水手段としては、脱水膜、被精製液に不溶である水吸着剤、乾燥した不活性ガスを用いた曝気置換装置、及び、加熱又は真空加熱装置等が挙げられる。
　脱水膜を用いる場合には、浸透気化（ＰＶ）又は蒸気透過（ＶＰ）による膜脱水を行う。脱水膜は、例えば、透水性膜モジュールとして構成されるものである。脱水膜としては、ポリイミド系、セルロース系、ポリビニルアルコール系等の高分子系、又は、ゼオライト等の無機系の素材からなる膜を使用できる。
　水吸着剤は、被精製液に添加して用いられる。水吸着剤としては、ゼオライト、五酸化二リン、シリカゲル、塩化カルシウム、硫酸ナトリウム、硫酸マグネシウム、無水塩化亜鉛、発煙硫酸、及び、ソーダ石灰等が挙げられる。 According to the dehydration treatment, water in the liquid to be purified can be removed. Further, when zeolite described later (particularly, molecular sieve (trade name) manufactured by Union Showa Co., Ltd.) is used in the dehydration treatment, olefins can also be removed.
Examples of the dehydrating means used for the dehydration treatment include a dehydration film, a water adsorbent insoluble in the liquid to be purified, an aeration replacement device using a dry inert gas, and a heating or vacuum heating device.
When a dehydrated membrane is used, membrane dehydration is performed by osmotic vaporization (PV) or vapor permeation (VP). The dehydrated membrane is configured as, for example, a permeable membrane module. As the dehydration film, a film made of a polymer-based material such as polyimide-based, cellulosic-based, or polyvinyl alcohol-based, or an inorganic-based material such as zeolite can be used.
The water adsorbent is used by adding it to the liquid to be purified. Examples of the water adsorbent include zeolite, diphosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, anhydrous zinc chloride, fuming sulfuric acid, soda lime and the like.
　蒸留処理によれば、脱水膜から溶出した不純物、第一イオン交換処理では除去しにくい被精製液中の金属成分、微粒子（金属成分が微粒子である場合には、これも含む）、及び、被精製液中の水を除去できる。
　蒸留手段は、例えば、単段の蒸留装置によって構成される。蒸留処理によって蒸留装置内等で不純物が濃縮するが、この濃縮された不純物の一部が流出することを防ぐために、蒸留手段には、不純物が濃縮されている液の一部を定期的に、又は、定常的に外部に排出する手段を設けることが好ましい。 According to the distillation treatment, impurities eluted from the dehydration membrane, metal components in the liquid to be purified that are difficult to remove by the first ion exchange treatment, fine particles (including fine particles if the metal components are fine particles), and a subject. Water in the purified liquid can be removed.
The distillation means is composed of, for example, a single-stage distillation apparatus. Impurities are concentrated in a distillation apparatus or the like by the distillation treatment, but in order to prevent a part of the concentrated impurities from flowing out, a part of the liquid in which the impurities are concentrated is periodically used in the distillation means. Alternatively, it is preferable to provide means for constantly discharging to the outside.
　第二イオン交換処理によれば、蒸留装置内で蓄積した不純物が流出した場合にこれを除去できる。また、送液ラインとして利用されるステンレス鋼（ＳＵＳ）等の配管からの溶出物を除去できる。
　第二イオン交換手段としては、塔状の容器内にイオン交換樹脂を充填したもの、及び、イオン吸着膜が挙げられる。なかでも、高流速での処理が可能である観点からイオン吸着膜が好ましい。
　イオン吸着膜としては、ネオセプタ（商品名、アストム社製）が挙げられる。 According to the second ion exchange treatment, when impurities accumulated in the distillation apparatus flow out, they can be removed. In addition, eluate from pipes such as stainless steel (SUS) used as a liquid feeding line can be removed.
Examples of the second ion exchange means include a column-shaped container filled with an ion exchange resin and an ion adsorption membrane. Of these, an ion adsorption membrane is preferable from the viewpoint of being able to process at a high flow velocity.
Examples of the ion adsorption membrane include Neocepta (trade name, manufactured by Astom Co., Ltd.).
　上述した各処理は、密閉状態で、かつ、被精製液に水の混入する可能性が低い不活性ガス雰囲気下で行われることが好ましい。
　また、各処理は、水分の混入を極力抑えるために、露点温度が－７０℃以下の不活性ガス雰囲気下で行うことが好ましい。－７０℃以下の不活性ガス雰囲気下では、気相中の水分濃度が２質量ｐｐｍ以下であるため、被精製液中に水分が混入する可能性が低くなるためである。 It is preferable that each of the above-mentioned treatments is carried out in a hermetically sealed state and in an atmosphere of an inert gas in which water is unlikely to be mixed in the liquid to be purified.
Further, each treatment is preferably performed in an inert gas atmosphere having a dew point temperature of −70 ° C. or lower in order to suppress the mixing of water as much as possible. This is because in an inert gas atmosphere of −70 ° C. or lower, the water concentration in the gas phase is 2 mass ppm or less, so that the possibility of water being mixed in the liquid to be purified is reduced.
　精製工程としては、上記の処理の他に、国際公開第ＷＯ２０１２／０４３４９６号に記載されている、炭化ケイ素を用いた金属成分の吸着精製処理等が挙げられる。 Examples of the purification step include, in addition to the above treatment, an adsorption purification treatment of a metal component using silicon carbide, which is described in International Publication No. WO2012 / 043496.
　有機不純物除去処理によれば、蒸留処理後の被精製液中に含まれ、蒸留処理では除去しにくい高沸点有機不純物等（沸点３００℃以上の有機物も含む）を除去できる。
　有機不純物除去手段としては、例えば、有機不純物を吸着可能な有機不純物吸着フィルタを備えた有機不純物吸着部材により実施することができる。なお、有機不純物吸着部材は、通常、上記有機不純物吸着フィルタと上記不純物吸着フィルタを固定する基材とを備えて構成される。
　有機不純物吸着フィルタは、有機不純物の吸着性能が向上するという観点から、有機不純物と相互作用可能な有機物骨格を表面に有すること（換言すると、有機不純物と相互作用可能な有機物骨格によって表面が修飾されていること）が好ましい。なお、有機不純物と相互作用可能な有機物骨格を表面に有する、とは、後述する有機不純物吸着フィルタを構成する基材の表面に上記有機不純物と相互作用可能な有機物骨格が付与されている形態が一例として挙げられる。
　有機不純物と相互作用可能な有機物骨格としては、例えば、有機不純物と反応して有機不純物を有機不純物吸着フィルタに捕捉できるような化学構造が挙げられる。より具体的には、有機不純物として、フタル酸ジオクチル、フタル酸ジイソノニル、アジピン酸ジオクチル、又は、フタル酸ジブチルを含む場合には、有機物骨格としては、ベンゼン環骨格が挙げられる。また、有機不純物としてエチレンプロピレンゴムを含む場合には、有機物骨格としては、アルキレン骨格が挙げられる。また、有機不純物としてｎ－長鎖アルキルアルコール（溶剤として１－長鎖アルキルアルコールを用いた場合の構造異性体）を含む場合には、有機物骨格としては、アルキル基が挙げられる。
　有機不純物吸着フィルタを構成する基材（材質）としては、活性炭を担持したセルロース、ケイソウ土、ナイロン、ポリエチレン、ポリプロピレン、ポリスチレン、及び、フッ素樹脂等が挙げられる。
　また、有機不純物除去フィルタには、特開２００２－２７３１２３号公報及び特開２０１３－１５０９７９号公報に記載の活性炭を不織布に固着したフィルタも使用できる。 According to the organic impurity removing treatment, high boiling point organic impurities and the like (including organic substances having a boiling point of 300 ° C. or higher) that are contained in the liquid to be purified after the distillation treatment and are difficult to remove by the distillation treatment can be removed.
As the organic impurity removing means, for example, it can be carried out by an organic impurity adsorbing member provided with an organic impurity adsorbing filter capable of adsorbing organic impurities. The organic impurity adsorption member is usually configured to include the organic impurity adsorption filter and a base material for fixing the impurity adsorption filter.
The organic impurity adsorption filter has an organic substance skeleton capable of interacting with organic impurities on the surface from the viewpoint of improving the adsorption performance of organic impurities (in other words, the surface is modified by the organic substance skeleton capable of interacting with organic impurities. It is preferable. In addition, having an organic substance skeleton capable of interacting with organic impurities on the surface means that the surface of the base material constituting the organic impurity adsorption filter described later is provided with the organic substance skeleton capable of interacting with the organic impurities. Take as an example.
Examples of the organic substance skeleton capable of interacting with organic impurities include a chemical structure capable of reacting with organic impurities and capturing the organic impurities in an organic impurity adsorption filter. More specifically, when the organic impurity contains dioctyl phthalate, diisononyl phthalate, dioctyl adipate, or dibutyl phthalate, the organic skeleton includes a benzene ring skeleton. When ethylene propylene rubber is contained as the organic impurity, the organic skeleton includes an alkylene skeleton. When n-long-chain alkyl alcohol (structural isomer when 1-long-chain alkyl alcohol is used as the solvent) is contained as the organic impurity, the organic skeleton includes an alkyl group.
Examples of the base material (material) constituting the organic impurity adsorption filter include cellulose carrying activated carbon, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.
Further, as the organic impurity removing filter, a filter in which activated carbon described in JP-A-2002-273123 and JP-A-2013-150979 is fixed to a non-woven fabric can also be used.
　また、上記有機不純物除去処理は、上述したような有機不純物を吸着可能な有機不純物吸着フィルタを用いた態様に制限されず、例えば有機不純物を物理的に補足する態様であってもよい。２５０℃以上の比較的高い沸点を有する有機不純物は粗大である場合が多く（例えば、炭素数８以上の化合物）、このため孔径が１ｎｍ程度のフィルタを用いることで物理的に補足することも可能である。
　例えば、有機不純物としてフタル酸ジオクチルを含む場合、フタル酸ジオクチルの構造は１０Å（＝１ｎｍ）よりも大きい。そのため、孔径が１ｎｍの有機不純物除去フィルタを用いることで、フタル酸ジオクチルはフィルタの孔を通過できない。つまり、フタル酸ジオクチルは、フィルタによって物理的に捕捉されるので、被精製液中から除去される。
　このように、有機不純物の除去は、化学的な相互作用だけでなく物理的な除去方法を適用することでも可能である。ただし、この場合には、３ｎｍ以上の孔径のフィルタが後述する「ろ過部材」として用いられ、３ｎｍ未満の孔径のフィルタが「有機不純物除去フィルタ」として用いられる。 Further, the organic impurity removing treatment is not limited to the mode using the organic impurity adsorption filter capable of adsorbing the organic impurities as described above, and may be, for example, a mode of physically supplementing the organic impurities. Organic impurities having a relatively high boiling point of 250 ° C. or higher are often coarse (for example, compounds having 8 or more carbon atoms), and therefore can be physically supplemented by using a filter having a pore size of about 1 nm. Is.
For example, when dioctyl phthalate is contained as an organic impurity, the structure of dioctyl phthalate is larger than 10 Å (= 1 nm). Therefore, by using an organic impurity removing filter having a pore diameter of 1 nm, dioctyl phthalate cannot pass through the pores of the filter. That is, dioctyl phthalate is physically trapped by the filter and is therefore removed from the liquid to be purified.
As described above, the removal of organic impurities can be achieved not only by chemical interaction but also by applying a physical removal method. However, in this case, a filter having a pore diameter of 3 nm or more is used as a “filter member” described later, and a filter having a pore diameter of less than 3 nm is used as an “organic impurity removing filter”.
　また、精製工程は、更に、例えば、後述する精製処理Ｖ及び精製処理ＶＩを有していてもよい。精製処理Ｖ及び精製処理ＶＩは、いずれのタイミングで実施されてもよく、例えば、精製処理ＩＶを実施した後等が挙げられる。
　精製処理Ｖは、金属イオンを除去する目的で金属イオン吸着部材を用いたフィルタリング処理である。
　また、精製処理ＶＩは、粗大な粒子を除去するためのろ過処理である。
　以下、精製処理Ｖ及び精製処理ＶＩについて説明する。 Further, the purification step may further include, for example, a purification process V and a purification process VI described later. The purification treatment V and the purification treatment VI may be carried out at any timing, and examples thereof include after the purification treatment IV is carried out.
The purification process V is a filtering process using a metal ion adsorbing member for the purpose of removing metal ions.
Further, the purification treatment VI is a filtration treatment for removing coarse particles.
Hereinafter, the purification treatment V and the purification treatment VI will be described.
　精製処理ＶＩにおいて、金属イオンの除去手段としては、金属イオン吸着フィルタを備えた金属イオン吸着部材を用いたフィルタリングがその一例として挙げられる。
　金属イオン吸着部材は、金属イオン吸着フィルタを少なくとも１つ備えた構成であり、また、目的とする精製レベルに応じて金属イオン吸着フィルタを複数重ねた構成であってもよい。金属イオン吸着部材は、通常、上記金属イオン吸着フィルタと上記金属イオン吸着フィルタを固定する基材とを備えて構成される。
　金属イオン吸着フィルタは、被精製液中の金属イオンを吸着する機能を備える。また、金属イオン吸着フィルタは、イオン交換可能なフィルタであることが好ましい。
　ここで、吸着対象となる金属イオンとしては、特に制限されないが、半導体デバイスの欠陥の原因になりやすいという観点から、Ｆｅ、Ｃｒ、Ｎｉ、及び、Ｐｂであることが好ましい。
　金属イオン吸着フィルタは、金属イオンの吸着性能が向上するという観点から、表面に酸基を有することが好ましい。酸基としては、スルホ基及びカルボキシル基等が挙げられる。
　金属イオン吸着フィルタを構成する基材（材質）としては、セルロース、ケイソウ土、ナイロン、ポリエチレン、ポリプロピレン、ポリスチレン、及び、フッ素樹脂等が挙げられる。 In the purification treatment VI, as an example of the means for removing metal ions, filtering using a metal ion adsorption member provided with a metal ion adsorption filter can be mentioned as an example.
The metal ion adsorption member has a configuration including at least one metal ion adsorption filter, and may have a configuration in which a plurality of metal ion adsorption filters are stacked according to a target purification level. The metal ion adsorption member is usually configured to include the metal ion adsorption filter and a base material for fixing the metal ion adsorption filter.
The metal ion adsorption filter has a function of adsorbing metal ions in the liquid to be purified. Further, the metal ion adsorption filter is preferably a filter capable of ion exchange.
Here, the metal ion to be adsorbed is not particularly limited, but Fe, Cr, Ni, and Pb are preferable from the viewpoint of easily causing defects in the semiconductor device.
The metal ion adsorption filter preferably has an acid group on its surface from the viewpoint of improving the adsorption performance of metal ions. Examples of the acid group include a sulfo group and a carboxyl group.
Examples of the base material (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.
　精製処理ＶＩにおいて、ろ過手段としては、除粒子径が２０ｎｍ以下であるフィルタを備えたろ過部材を使用して実施する態様が一例として挙げられる。被精製液が、上記フィルタを追加することにより、被精製液から粒子状の不純物を除去できる。ここで、「粒子状の不純物」としては、被精製液の製造時に使用される原料に不純物として含まれる塵、埃、有機固形物、及び、無機固形物等の粒子、並びに、被精製液の精製時に汚染物として持ち込まれる塵、埃、有機固形物、及び、無機固形物の粒子等が挙げられ、最終的に被精製液中で溶解せずに粒子として存在するものが該当する。
　また、「粒子状の不純物」には、金属原子を含むコロイド化した不純物も含まれる。金属原子としては、特に制限されないが、Ｎａ、Ｋ、Ｃａ、Ｆｅ、Ｃｕ、Ｍｇ、Ｍｎ、Ｌｉ、Ａｌ、Ｃｒ、Ｎｉ、Ｚｎ、及び、Ｐｂ（好ましくは、Ｆｅ、Ｃｒ、Ｎｉ、及び、Ｐｂ）からなる群から選択される少なくとも１種の金属原子の含有量が特に低い場合（例えば、被精製液中の上記金属原子の含有量がそれぞれ１０００質量ｐｐｔ以下の場合）、これらの金属原子を含む不純物がコロイド化しやすい。上記金属イオン吸着部材では、コロイド化した不純物の除去が困難になりやすい。従って、除粒子径が２０ｎｍ以下であるフィルタ（例えば、孔径が２０ｎｍ以下の精密ろ過膜）を用いることにより、コロイド化した不純物の除去が効果的に行われる。
　粒子状の不純物は、除粒子径が２０ｎｍ以下であるフィルタで除去されるサイズを有し、具体的にはその直径が２０ｎｍ以上の粒子である。なお、本明細書において、粒子状の不純物を「粗大粒子」ということがある。
　なかでも、上記フィルタの除粒子径は、１～１５ｎｍが好ましく、１～１２ｎｍがより好ましい。除粒子径が１５ｎｍ以下であることで、より微細な粒子状の不純物を除去でき、除粒子径が１ｎｍ以上であることで、被精製液のろ過効率が向上する。
　ここで、除粒子径とは、フィルタが除去可能な粒子の最小サイズを意味する。例えば、フィルタの除粒子径が２０ｎｍである場合には、直径２０ｎｍ以上の粒子を除去可能である。
　上記フィルタの材質としては、例えば、６－ナイロン、６，６－ナイロン、ポリエチレン、ポリプロピレン、ポリスチレン、及び、フッ素樹脂等が挙げられる。 An example of the purification treatment VI is an embodiment in which a filtration member provided with a filter having a particle size removal diameter of 20 nm or less is used as the filtration means. By adding the above filter, the liquid to be purified can remove particulate impurities from the liquid to be purified. Here, the "particulate impurities" include particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw materials used in the production of the liquid to be purified, and the liquid to be purified. Examples include particles of dust, dust, organic solids, and inorganic solids that are brought in as contaminants during purification, and those that finally exist as particles without being dissolved in the liquid to be purified fall under this category.
The "particulate impurities" also include colloidal impurities containing metal atoms. The metal atom is not particularly limited, but Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, and Pb (preferably Fe, Cr, Ni, and Pb). ), When the content of at least one metal atom selected from the group is particularly low (for example, when the content of the metal atoms in the liquid to be purified is 1000 mass ppt or less, respectively), these metal atoms are used. Impurities contained are likely to colloid. With the metal ion adsorption member, it tends to be difficult to remove colloidal impurities. Therefore, by using a filter having a particle size removal diameter of 20 nm or less (for example, a microfiltration membrane having a pore size of 20 nm or less), colloidal impurities can be effectively removed.
The particulate impurities have a size that can be removed by a filter having a particle size removal diameter of 20 nm or less, and specifically, particles having a diameter of 20 nm or more. In the present specification, particulate impurities may be referred to as "coarse particles".
Among them, the particle size of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm. When the particle size is 15 nm or less, finer particulate impurities can be removed, and when the particle size is 1 nm or more, the filtration efficiency of the liquid to be purified is improved.
Here, the particle size removal means the minimum size of particles that can be removed by the filter. For example, when the removal particle diameter of the filter is 20 nm, particles having a diameter of 20 nm or more can be removed.
Examples of the material of the filter include 6-nylon, 6,6-nylon, polyethylene, polypropylene, polystyrene, fluororesin and the like.
　ろ過部材は、更に、除粒子径が５０ｎｍ以上のフィルタ（例えば、孔径が５０ｎｍ以上の微粒子除去用の精密ろ過膜）を備えていてもよい。被精製液中に、コロイド化した不純物、特に鉄又はアルミニウムのような金属原子を含むコロイド化した不純物以外にも微粒子が存在する場合には、除粒子径が２０ｎｍ以下であるフィルタ（例えば、孔径が２０ｎｍ以下の精密ろ過膜）を使用してろ過する前に、除粒子径が５０ｎｍ以上のフィルタ（例えば、孔径が５０ｎｍ以上の微粒子除去用の精密ろ過膜）を使用して被精製液のろ過を実施することで、除粒子径が２０ｎｍ以下であるフィルタ（例えば、孔径が２０ｎｍ以下の精密ろ過膜）のろ過効率が向上し、粗大粒子の除去性能がより向上する。 The filtration member may further include a filter having a particle size removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles having a pore size of 50 nm or more). When fine particles other than colloidal impurities, particularly colloidal impurities containing metal atoms such as iron or aluminum, are present in the liquid to be purified, a filter having a particle removal diameter of 20 nm or less (for example, pore size). Filtering of the liquid to be purified using a filter with a particle removal diameter of 50 nm or more (for example, a precision filtration film for removing fine particles with a pore size of 50 nm or more) before filtering using a precision filtration membrane with a particle size of 20 nm or less. By carrying out the above, the filtration efficiency of a filter having a particle removal diameter of 20 nm or less (for example, a precision filtration film having a pore size of 20 nm or less) is improved, and the removal performance of coarse particles is further improved.
　このような各処理を得て得られた被精製液を、本発明の処理液の調製に使用したり、本発明の処理液そのものとして使用できる。
　なお、上述した精製工程の一例として、各処理が全て行われる場合を示したが、これに制限されず、上記各処理を単独で行ってもよいし、上記処理を複数組み合わせて行ってもよい。また、上記各処理は、１回行われてもよいし、複数回行われてもよい。 The liquid to be purified obtained by obtaining each of these treatments can be used for preparing the treatment liquid of the present invention, or can be used as the treatment liquid itself of the present invention.
As an example of the above-mentioned purification step, the case where all the treatments are performed is shown, but the present invention is not limited to this, and each of the above treatments may be performed alone or in combination of a plurality of the above treatments. .. Further, each of the above processes may be performed once or a plurality of times.
　上記精製工程以外に、処理液に含まれる、沸点３００℃以上の有機物、金属成分及び水の含有量を所望の範囲内にする方法としては、処理液を組成する有機溶剤の原材料、又は、処理液そのものを不純物の溶出が少ない容器に収容することも挙げられる。また、処理液の製造時の「配管」等からメタル分が溶出しないように、上記配管内壁にフッ素系樹脂のライニングを施す等の方法も挙げられる。 In addition to the above purification step, as a method for keeping the contents of organic substances, metal components and water having a boiling point of 300 ° C. or higher contained in the treatment liquid within a desired range, the raw material of the organic solvent constituting the treatment liquid or the treatment It is also possible to store the liquid itself in a container in which impurities are less likely to elute. Further, there is also a method of lining the inner wall of the pipe with a fluororesin so that the metal component does not elute from the “pipe” or the like during the production of the treatment liquid.
〔容器（収容容器）〕
　本発明の処理液は、腐食性等が問題とならない限り、任意の容器に充填して保管、運搬、そして使用することができる。
　容器としては、半導体用途向けに、容器内のクリーン度が高く、不純物の溶出が少ないものが好ましい。
　使用可能な容器としては、具体的には、アイセロ化学（株）製の「クリーンボトル」シリーズ、及び、コダマ樹脂工業製の「ピュアボトル」等が挙げられるが、これらに制限されない。この容器の内壁（容器内の溶液と接触する接液部）は、非金属材料により形成されたものであることが好ましい。
　非金属材料としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリエチレン－ポリプロピレン樹脂、四フッ化エチレン樹脂（ＰＴＦＥ）、四フッ化エチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、四フッ化エチレン－六フッ化プロピレン共重合樹脂（ＦＥＰ）、四フッ化エチレン－エチレン共重合樹脂（ＥＴＦＥ）、三フッ化塩化エチレン－エチレン共重合樹脂（ＥＣＴＦＥ）、フッ化ビニリデン樹脂（ＰＶＤＦ）、三フッ化塩化エチレン共重合樹脂（ＰＣＴＦＥ）、及び、フッ化ビニル樹脂（ＰＶＦ）からなる群から選ばれる少なくとも１種がより好ましい。
　特に、上記のなかでも、内壁がフッ素系樹脂である容器を用いる場合、内壁がポリエチレン樹脂、ポリプロピレン樹脂、又は、ポリエチレン－ポリプロピレン樹脂である容器を用いる場合と比べて、エチレン又はプロピレンのオリゴマーの溶出という不具合の発生を抑制できる。
　このような内壁がフッ素系樹脂である容器の具体例としては、例えば、Ｅｎｔｅｇｒｉｓ社製　ＦｌｕｏｒｏＰｕｒｅＰＦＡ複合ドラム等が挙げられる。また、特表平３－５０２６７７号公報の第４頁等、国際公開第２００４／０１６５２６号パンフレットの第３頁等、及び、国際公開第９９／０４６３０９号パンフレットの第９頁及び１６頁等に記載の容器も使用できる。
　なお、非金属材料の内壁とする場合、非金属材料中の有機成分の処理液への溶出が抑制されていることが好ましい。 [Container (container)]
The treatment liquid of the present invention can be filled in an arbitrary container, stored, transported, and used as long as corrosiveness does not become a problem.
As the container, it is preferable that the container has a high degree of cleanliness and less elution of impurities for semiconductor applications.
Specific examples of the containers that can be used include, but are not limited to, the "clean bottle" series manufactured by Aicello Chemical Co., Ltd. and the "pure bottle" manufactured by Kodama Resin Industry. The inner wall of the container (the wetted portion in contact with the solution in the container) is preferably formed of a non-metallic material.
Non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, ethylene tetrafluoride resin (PTFE), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (PFA), ethylene tetrafluoride-hexfluoride. Propropylene copolymer resin (FEP), ethylene tetrafluoride-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride copolymer At least one selected from the group consisting of a resin (PCTFE) and a vinyl fluoride resin (PVF) is more preferable.
In particular, among the above, when a container having an inner wall made of a fluororesin is used, an ethylene or propylene oligomer is eluted as compared with a case where a container having an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin is used. It is possible to suppress the occurrence of such a problem.
Specific examples of such a container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris. In addition, it is described on pages 4 of the special table No. 3-502677, page 3 of the pamphlet of International Publication No. 2004/016526, and pages 9 and 16 of the pamphlet of International Publication No. 99/046309. Containers can also be used.
When the inner wall of the non-metal material is used, it is preferable that the elution of the organic component in the non-metal material into the treatment liquid is suppressed.
　また、容器の内壁には、上述した非金属材料の他に、石英又は金属材料（より好ましくは、電解研磨された金属材料。換言すると、電解研磨済みの金属材料）も好ましく用いられる。
　上記金属材料（特に、電解研磨された金属材料の製造に用いられる金属材料）は、クロムを金属材料全質量に対して２５質量％超で含むものが好ましく、例えばステンレス鋼が挙げられる。
　金属材料におけるクロムの含有量は、金属材料全質量に対して３０質量％以上がより好ましい。また、その上限値としては特に制限されないが、一般的に９０質量％以下が好ましい。 Further, in addition to the above-mentioned non-metal material, quartz or a metal material (more preferably, an electropolished metal material, in other words, an electropolished metal material) is preferably used for the inner wall of the container.
The metal material (particularly, the metal material used for producing the electropolished metal material) preferably contains chromium in an amount of more than 25% by mass with respect to the total mass of the metal material, and examples thereof include stainless steel.
The chromium content in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material. The upper limit is not particularly limited, but is generally preferably 90% by mass or less.
　ステンレス鋼としては、特に制限されず、公知のステンレス鋼を使用できる。
　なかでも、ニッケルを８質量％以上含む合金が好ましく、ニッケルを８質量％以上含むオーステナイト系ステンレス鋼がより好ましい。オーステナイト系ステンレス鋼としては、例えばＳＵＳ（Ｓｔｅｅｌ　Ｕｓｅ　Ｓｔａｉｎｌｅｓｓ）３０４（Ｎｉ含有量８質量％、Ｃｒ含有量１８質量％）、ＳＵＳ３０４Ｌ（Ｎｉ含有量９質量％、Ｃｒ含有量１８質量％）、ＳＵＳ３１６（Ｎｉ含有量１０質量％、Ｃｒ含有量１６質量％）、及び、ＳＵＳ３１６Ｌ（Ｎｉ含有量１２質量％、Ｃｒ含有量１６質量％）等が挙げられる。 The stainless steel is not particularly limited, and known stainless steel can be used.
Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.
　金属材料を電解研磨する方法としては特に制限されず、公知の方法を使用できる。例えば、特開２０１５－２２７５０１号公報の段落［００１１］～［００１４］、及び、特開２００８－２６４９２９号公報の段落［００３６］～［００４２］等に記載された方法を使用できる。 The method for electrolytically polishing a metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs [0011] to [0014] of JP2015-227501 and paragraphs [0036] to [0042] of JP2008-264929 can be used.
　金属材料は、電解研磨されることにより表面の不動態層におけるクロムの含有量が、母相のクロムの含有量よりも多くなっているものと推測される。そのため、電解研磨された金属材料で被覆された内壁からは、溶液中に金属成分が流出しにくいため、金属成分（金属不純物）が低減された溶液を得ることができるものと推測される。
　なお、金属材料はバフ研磨されていることが好ましい。バフ研磨の方法は特に制限されず、公知の方法を使用できる。バフ研磨の仕上げに用いられる研磨砥粒のサイズは特に制限されないが、金属材料の表面の凹凸がより小さくなりやすい点で、＃４００以下が好ましい。
　なお、バフ研磨は、電解研磨の前に行われることが好ましい。
　また、金属材料は、研磨砥粒のサイズ等の番手を変えて行われる複数段階のバフ研磨、酸洗浄、及び、磁性流体研磨等を、１又は２以上組み合わせて処理されたものであってもよい。 It is presumed that the content of chromium in the passivation layer on the surface of the metal material is higher than the content of chromium in the matrix by electropolishing. Therefore, it is presumed that a solution having a reduced metal component (metal impurities) can be obtained because the metal component does not easily flow out into the solution from the inner wall coated with the electropolished metal material.
The metal material is preferably buffed. The method of buffing is not particularly limited, and a known method can be used. The size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
The buffing is preferably performed before the electrolytic polishing.
Further, even if the metal material is processed by combining one or two or more of a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of the abrasive grains. good.
　本発明においては、上記容器と、この容器内に収容された上記処理液と、を有するものを、溶液収容体ともいう。 In the present invention, a container having the above-mentioned container and the above-mentioned treatment liquid contained in the container is also referred to as a solution container.
　これらの容器は、処理液を充填する前にその内部が洗浄されることが好ましい。洗浄に用いる液体としては、本発明の処理液自体、又は、本発明の処理液に含まれる有機溶剤である場合、本発明の効果が顕著に得られる。本発明の処理液は、製造後にガロン瓶又はコート瓶等の容器にボトリングし、輸送及び保管されてもよい。ガロン瓶はガラス材料を使用したものであってもそれ以外であってもよい。 It is preferable that the inside of these containers is cleaned before filling with the treatment liquid. When the liquid used for cleaning is the treatment liquid of the present invention itself or an organic solvent contained in the treatment liquid of the present invention, the effect of the present invention can be remarkably obtained. The treatment liquid of the present invention may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production. The gallon bottle may or may not be made of glass material.
　保管における処理液中の成分の変化を防ぐ目的で、容器内を純度９９．９９９９５体積％以上の不活性ガス（チッソ、又はアルゴン等）で置換しておいてもよい。特に、含水率が少ないガスが好ましい。また、輸送及び保管に際しては、常温でもよいが、変質を防ぐため、－２０℃～２０℃の範囲に温度制御してもよい。 The inside of the container may be replaced with an inert gas (chisso, argon, etc.) having a purity of 99.99995% by volume or more for the purpose of preventing changes in the components in the treatment liquid during storage. In particular, a gas having a low water content is preferable. Further, during transportation and storage, the temperature may be at room temperature, but in order to prevent deterioration, the temperature may be controlled in the range of −20 ° C. to 20 ° C.
〔クリーンルーム〕
　本発明の処理液の製造、収容容器の開封及び／又は洗浄、処理液の充填等を含めた取り扱い、処理分析、及び、測定は、全てクリーンルームで行うことが好ましい。クリーンルームは、ＩＳＯ１４６４４－１のクリーンルーム基準を満たすことが好ましい。ＩＳＯ（国際標準化機構）クラス１、ＩＳＯクラス２、ＩＳＯクラス３、及び、ＩＳＯクラス４のいずれかを満たすことが好ましく、ＩＳＯクラス１又はＩＳＯクラス２を満たすことがより好ましく、ＩＳＯクラス１を満たすことが更に好ましい。後述する実施例での処理液の製造、収容容器の開封及び／又は洗浄、処理液の充填等を含めた取り扱い、処理分析、及び、測定は、クラス２のクリーンルームにて行った。 [Clean room]
It is preferable that the production of the treatment liquid of the present invention, the opening and / or cleaning of the storage container, the handling including the filling of the treatment liquid, the treatment analysis, and the measurement are all performed in a clean room. The clean room preferably meets the ISO 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and satisfy ISO class 1. Is even more preferable. The handling, treatment analysis, and measurement including the production of the treatment liquid, opening and / or cleaning of the storage container, filling of the treatment liquid, etc. in the examples described later were performed in a class 2 clean room.
〔除電工程〕
　本発明の処理液若しくは処理液に含まれる有機溶剤の調製、及び、精製においては、更に除電工程を有していてもよい。除電工程は、原料、反応物、及び、精製物からなる群から選択される少なくとも１種（以下「精製物等」という。）を除電することで、精製物等の帯電電位を低減させる工程である。
　除電方法としては特に制限されず、公知の除電方法を使用できる。除電方法としては、例えば、上記精製液等を導電性材料に接触させる方法が挙げられる。
　上記精製液等を導電性材料に接触させる接触時間は、０．００１～６０秒が好ましく、０．００１～１秒がより好ましく、０．０１～０．１秒が更に好ましい。導電性材料としては、ステンレス鋼、金、白金、ダイヤモンド、及び、グラッシーカーボン等が挙げられる。
　精製液等を導電性材料に接触させる方法としては、例えば、導電性材料からなる接地されたメッシュを管路内部に配置し、ここに精製液等を通す方法等が挙げられる。 [Static elimination process]
The treatment liquid of the present invention or the organic solvent contained in the treatment liquid may further have a static elimination step in the preparation and purification. The static elimination step is a step of reducing the charging potential of a purified product or the like by removing static electricity from at least one selected from the group consisting of a raw material, a reactant, and a purified product (hereinafter referred to as "refined product or the like"). be.
The static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the static elimination method include a method in which the purified liquid or the like is brought into contact with the conductive material.
The contact time for bringing the purified liquid or the like into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 seconds. Examples of the conductive material include stainless steel, gold, platinum, diamond, glassy carbon and the like.
Examples of the method of bringing the purified liquid or the like into contact with the conductive material include a method of arranging a grounded mesh made of the conductive material inside the conduit and passing the purified liquid or the like through the grounded mesh.
　上記除電工程は、原料供給から精製物の充填までのいずれの時点で実施されてもよく、例えば、原料供給工程、反応工程、調液工程、精製工程、ろ過工程、及び、充填工程からなる群から選択される少なくとも１種の工程の前に含まれることが好ましく、上記各工程において使用する容器に精製物等を注入する前に、除電工程を行うことがより好ましい。これにより、容器等に由来する不純物が、精製物等に混入するのを抑制することができる。 The static elimination step may be carried out at any time from the supply of the raw material to the filling of the purified product. For example, the group consisting of the raw material supply step, the reaction step, the liquid preparation step, the purification step, the filtration step, and the filling step. It is preferable that it is contained before at least one step selected from the above steps, and it is more preferable to carry out a static elimination step before injecting the purified product or the like into the container used in each of the above steps. This makes it possible to prevent impurities derived from the container or the like from being mixed into the purified product or the like.
　以下、実施例により本発明を説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.
〔感活性光線又は感放射線性組成物（レジスト組成物）〕
　以下に示す材料を使用して感活性光線又は感放射線性組成物（レジスト組成物）を調製した。 [Sensitive ray or radiation sensitive composition (resist composition)]
A light-sensitive or radiation-sensitive composition (resist composition) was prepared using the materials shown below.
＜樹脂（Ａ）＞
（合成例１）：樹脂（Ａ－１）の合成
　２Ｌフラスコに、シクロヘキサノン（６００ｇ）を入れ、上記シクロヘキサノンに対して、１００ｍＬ／ｍｉｎの流量で一時間窒素置換した。その後、重合開始剤Ｖ－６０１（和光純薬工業（株）製）（４．６０ｇ（０．０２ｍｏｌ））を、上記フラスコに加え、上記フラスコの内容物の内温が８０℃になるまで昇温した。
　次に、４－アセトキシスチレン（４８．６６ｇ（０．３ｍｏｌ））と、１－エチルシクロペンチルメタクリレート（１０９．４ｇ（０．６ｍｏｌ））と、モノマー１（２２．２ｇ（０．１ｍｏｌ））と、重合開始剤Ｖ－６０１（和光純薬工業（株）製）（４．６０ｇ（０．０２ｍｏｌ））とを、シクロヘキサノン（２００ｇ）に溶解し、モノマー溶液を調製した。
　上記モノマー溶液を、上述の通り内温８０℃に加熱した上記フラスコ中に６時間かけて滴下した。滴下終了後、更に内温８０℃で２時間反応させた。 <Resin (A)>
(Synthesis Example 1): Synthesis of resin (A-1) Cyclohexanone (600 g) was placed in a 2 L flask, and the cyclohexanone was replaced with nitrogen at a flow rate of 100 mL / min for 1 hour. Then, the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (4.60 g (0.02 mol)) was added to the flask, and the temperature of the contents of the flask was raised to 80 ° C. It was warm.
Next, 4-acetoxystyrene (48.66 g (0.3 mol)), 1-ethylcyclopentyl methacrylate (109.4 g (0.6 mol)), and monomer 1 (22.2 g (0.1 mol)) were added. The polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (4.60 g (0.02 mol)) was dissolved in cyclohexanone (200 g) to prepare a monomer solution.
The monomer solution was added dropwise to the flask heated to an internal temperature of 80 ° C. over 6 hours as described above. After completion of the dropping, the reaction was further carried out at an internal temperature of 80 ° C. for 2 hours.
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
　反応溶液（上記フラスコの内容物）を室温まで冷却してから、ヘキサン（３Ｌ）中に滴下し、ポリマーを沈殿させた混合液を得た。上記混合液をろ過して、固体（ろ物）を得た。得られた固体（ろ物）をアセトン（５００ｍｌ）に溶解し、再度ヘキサン（３Ｌ）中に滴下し、上述したのと同様にして再び固体（ろ物）を得た。得られた固体を減圧乾燥して、４－アセトキシスチレン／１－エチルシクロペンチルメタクリレート／モノマー１共重合体（Ａ－１ａ）（１６０ｇ）を得た。 The reaction solution (contents of the above flask) was cooled to room temperature and then added dropwise to hexane (3 L) to obtain a mixed solution in which the polymer was precipitated. The above mixed solution was filtered to obtain a solid (filter). The obtained solid (filter) was dissolved in acetone (500 ml) and added dropwise to hexane (3 L) again to obtain a solid (filter) again in the same manner as described above. The obtained solid was dried under reduced pressure to obtain 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1a) (160 g).
　反応容器中に上記で得られた共重合体（Ａ－１ａ）（１０ｇ）、メタノール（４０ｍｌ）、１－メトキシ－２－プロパノール（２００ｍｌ）、及び、濃塩酸（１．５ｍｌ）を中身が空のフラスコに加え、反応溶液（上記フラスコの内容物）を８０℃に加熱して５時間攪拌した。反応溶液を室温まで放冷してから、蒸留水（３Ｌ）中に滴下して混合液を得た。上記混合液をろ過して、固体（ろ物）を得た。得られた固体（ろ物）をアセトン（２００ｍｌ）に溶解し、再度蒸留水（３Ｌ）中に滴下し、上述したのと同様にして再び固体（ろ物）を得た。得られた固体を減圧乾燥して樹脂（Ａ－１）（８．５ｇ）を得た。樹脂（Ａ－１）の重量平均分子量は１０８００であり、分子量分散度（Ｍｗ／Ｍｎ）は１．５５であった。 The copolymer (A-1a) (10 g), methanol (40 ml), 1-methoxy-2-propanol (200 ml), and concentrated hydrochloric acid (1.5 ml) obtained above are emptied in the reaction vessel. The reaction solution (contents of the above flask) was heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and then added dropwise to distilled water (3 L) to obtain a mixed solution. The above mixed solution was filtered to obtain a solid (filter). The obtained solid (filter) was dissolved in acetone (200 ml) and added dropwise to distilled water (3 L) again to obtain a solid (filter) again in the same manner as described above. The obtained solid was dried under reduced pressure to obtain a resin (A-1) (8.5 g). The weight average molecular weight of the resin (A-1) was 10800, and the molecular weight dispersion (Mw / Mn) was 1.55.
（合成例２）：樹脂（Ａ－２）の合成
　用いるモノマーを変更する以外は、上記合成例１と同様の方法で、更に、樹脂（Ａ－２）を合成した。樹脂中の各繰り返し単位の組成比（モル比）は、１Ｈ－ＮＭＲ（Ｎｕｃｌｅａｒ　Ｍａｇｎｅｔｉｃ　Ｒｅｓｏｎａｎｃｅ）測定により算出した。 (Synthesis Example 2): Synthesis of Resin (A-2) A resin (A-2) was further synthesized by the same method as in Synthesis Example 1 above, except that the monomer used was changed. The composition ratio (molar ratio) of each repeating unit in the resin was calculated by 1 H-NMR (Nuclear Magnetic Resonance) measurement.
　下記表に、レジスト組成物に使用した樹脂を示す。
　表中、「組成比（モル比）」欄は、各樹脂を構成する各繰り返し単位の含有量（組成比（モル比））を示す。「構造」欄に示した各繰り返し単位の含有量が、「組成比（モル比）」欄に示した値と、左から順に対応する。 The table below shows the resins used in the resist composition.
In the table, the "composition ratio (molar ratio)" column indicates the content (composition ratio (molar ratio)) of each repeating unit constituting each resin. The content of each repeating unit shown in the "Structure" column corresponds to the value shown in the "Composition ratio (molar ratio)" column in order from the left.
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000069
＜光酸発生剤＞
　光酸発生剤として、下記成分を使用した。 <Photoacid generator>
The following components were used as the photoacid generator.
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
＜塩基性化合物（酸拡散制御剤）＞
　塩基性化合物として、下記成分を使用した。 <Basic compound (acid diffusion control agent)>
The following components were used as the basic compound.
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
＜溶剤＞
　溶剤として、下記成分を使用した。
　Ｃ－１：プロピレングリコールモノメチルエーテルアセテート
　Ｃ－２：プロピレングリコール
　Ｃ－３：乳酸エチル <Solvent>
The following components were used as the solvent.
C-1: Propylene glycol monomethyl ether acetate C-2: Propylene glycol C-3: Ethyl lactate
＜レジスト組成物の調製＞
　下記表２に示す各成分を、同表に示す配合で、同表に示す溶剤に溶解させた。得られた混合液を０．０３μｍのポアサイズを有するポリエチレンフィルターを使用してろ過して、レジスト組成物１～２を得た。 <Preparation of resist composition>
Each component shown in Table 2 below was dissolved in the solvent shown in the same table in the formulation shown in the same table. The obtained mixed solution was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain resist compositions 1 and 2.
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
［試験］
〔簡易解像性能評価：ＥＢ露光評価：実施例Ａ～Ｅ及び比較例Ａ～Ｅ〕
　表２に記載のレジスト組成物１を用い、以下の操作により、レジストパターンを形成した。レジストパターン形成条件の詳細は表３及び４に示す。
　ＥＢ露光とＥＵＶ露光はいずれも露光によりレジスト膜がイオン化して二次電子が発生し、発生した二次電子によって光酸発生剤が分解して酸を発生する。そのため、ＥＵＶ露光の代わりに、簡易露光評価としてＥＢ露光を評価として用いても、ＥＵＶ露光と同様の結果を再現することができる。 [test]
[Simple resolution performance evaluation: EB exposure evaluation: Examples A to E and Comparative Examples A to E]
Using the resist composition 1 shown in Table 2, a resist pattern was formed by the following operations. Details of the resist pattern formation conditions are shown in Tables 3 and 4.
In both EB exposure and EUV exposure, the resist film is ionized by exposure to generate secondary electrons, and the generated secondary electrons decompose the photoacid generator to generate acid. Therefore, even if EB exposure is used as an evaluation as a simple exposure evaluation instead of EUV exposure, the same result as EUV exposure can be reproduced.
＜パターンの作製＞
（レジスト組成物の塗布及び塗布後ベーク）
　６インチシリコンウエハ上に有機膜形成用組成物（製品名：ＡＬ４１２、Ｂｒｅｗｅｒ　Ｓｃｉｅｎｃｅ社製）を塗布し、２０５℃で６０秒間ベークして、膜厚２０ｎｍの有機膜を形成した。その上に表２に記載のレジスト組成物１を塗布し、温度１２０℃、６０秒間の条件でベーク（塗布後ベーク）し、膜厚６０ｎｍのレジスト膜を形成した。 <Making a pattern>
(Applying resist composition and baking after application)
A composition for forming an organic film (product name: AL412, manufactured by Brewer Science) was applied onto a 6-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an organic film having a film thickness of 20 nm. The resist composition 1 shown in Table 2 was applied onto the resist composition 1 and baked at a temperature of 120 ° C. for 60 seconds to form a resist film having a film thickness of 60 nm.
（露光）
　上述のようにレジスト膜を形成したウエハ（レジスト膜付きウエハ）におけるレジスト膜に、電子線照射装置（（株）エリオニクス製　Ｇ１００；加速電圧１００ｋｅＶ、ビーム電流１００ｐＡ）を使用して、ハーフピッチ２２ｎｍのラインアンドスペースパターン（長さ方向０．２ｍｍ、描画本数４５本）を、表３に記載の各露光量で露光した。具体的には、以下に示す表３中の、それぞれのショット番号に対応する露光量で、それぞれ露光を行った。
　レジスト膜に対して、各露光量で露光（ショット）して、各露光量で露光したレジスト膜をそれぞれ以降の工程に供した。
　なお、表３における各露光量は、ショット番号順に、それぞれ対数的に等間隔となるように設定している。
　評価に用いたレジスト膜の感度が異なるような場合でも、最終的に問題なく解像できたショット数（問題なく解像できた露光量の数）を比較することで、解像性能の比較が可能である。 (exposure)
An electron beam irradiation device (G100 manufactured by Elionix Inc.; acceleration voltage 100 keV, beam current 100 pA) was used on the resist film in the wafer on which the resist film was formed as described above (wafer with a resist film), and the half pitch was 22 nm. A line-and-space pattern (0.2 mm in the length direction, 45 drawn lines) was exposed at each exposure amount shown in Table 3. Specifically, each exposure was performed with the exposure amount corresponding to each shot number in Table 3 shown below.
The resist film was exposed (shot) at each exposure amount, and the resist film exposed at each exposure amount was subjected to the subsequent steps.
The exposure amounts in Table 3 are set to be logarithmicly evenly spaced in the order of shot numbers.
Even if the sensitivity of the resist film used for evaluation is different, the resolution performance can be compared by comparing the number of shots that could be finally resolved without problems (the number of exposures that could be resolved without problems). It is possible.
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
（露光後ベーク）
　露光後、上記ウエハを電子線照射装置から取り出して、ただちに、温度１１０℃、６０秒間の条件でホットプレート上にて加熱（露光後ベーク）した。 (Bake after exposure)
After the exposure, the wafer was taken out from the electron beam irradiator and immediately heated (baked after exposure) on a hot plate at a temperature of 110 ° C. for 60 seconds.
（現像工程）
　シャワー型現像装置（ＡＣＴＥＳ（株）製ＡＤＥ３０００Ｓ）を使用して、５０ｒｐｍで上記ウエハを回転しながら、現像液としての酢酸ブチル（２３℃）を、２００ｍＬ／分の流量で上記ウエハ上に１０秒間吐出して現像を行った。 (Development process)
Using a shower-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 rpm, butyl acetate (23 ° C.) as a developing solution was applied onto the wafer at a flow rate of 200 mL / min for 10 seconds. It was discharged and developed.
（リンス工程）
　その後、５０ｒｐｍで上記ウエハを回転しながら表４～８に記載の処理液（２３℃）を、２００ｍＬ／分の流量で、上記ウエハ上に５秒間吐出してリンス処理を行った。最後に、２０００ｒｐｍで６０秒間高速回転して上記ウエハを乾燥させた。 (Rinse process)
Then, while rotating the wafer at 50 rpm, the treatment liquid (23 ° C.) shown in Tables 4 to 8 was discharged onto the wafer at a flow rate of 200 mL / min for 5 seconds for rinsing. Finally, the wafer was dried at a high speed of 2000 rpm for 60 seconds.
＜評価＞
　以下の項目について、得られたパターンの評価を行った。結果の詳細は表４～８に示す。 <Evaluation>
The obtained patterns were evaluated for the following items. Details of the results are shown in Tables 4-8.
（解像性）
　２２ｎｍラインアンドスペースパターンの各露光量での解像状況を、走査型電子顕微鏡（（株）日立製作所製Ｓ－９２６０）を使用して観察した。各露光量で問題なく解像しているショット数をカウントして、解像性を評価した。
　図１に、実施例Ａ－１及び比較例Ａ－１における、ショット番号３～１０の露光量で露光して形成したパターンの顕微鏡写真を示す。
　比較例Ａ－１ではショット番号４の露光量で露光した場合のみ、問題なく解像していると判断した。つまり、比較例Ａ－１では、問題なく解像できたショット数（解像コマ数）は１であった。
　対して、実施例１ではショット番号４～８の露光量で露光した場合に、問題なく解像していると判断した。つまり、実施例Ａ－１では、問題なく解像できたショット数（解像コマ数）は５であった。同様の判断基準に基づいて、他の実施例及び比較例についても解像コマ数を求めた。以下の評価基準で評価した。
　Ａ：　５以上
　Ｂ：　４
　Ｃ：　３
　Ｄ：　２
　Ｅ：　１以下 (Resolution)
The resolution of the 22 nm line-and-space pattern at each exposure amount was observed using a scanning electron microscope (S-9260 manufactured by Hitachi, Ltd.). The resolution was evaluated by counting the number of shots that were resolved without any problem at each exposure amount.
FIG. 1 shows micrographs of patterns formed by exposure with exposure amounts of shot numbers 3 to 10 in Example A-1 and Comparative Example A-1.
In Comparative Example A-1, it was determined that the resolution was not a problem only when the exposure was performed with the exposure amount of shot number 4. That is, in Comparative Example A-1, the number of shots (number of resolution frames) that could be resolved without any problem was 1.
On the other hand, in Example 1, it was determined that the resolution was not a problem when the exposure was performed with the exposure amounts of shot numbers 4 to 8. That is, in Example A-1, the number of shots (number of resolution frames) that could be resolved without any problem was 5. Based on the same criteria, the number of resolution frames was calculated for other examples and comparative examples. It was evaluated according to the following evaluation criteria.
A: 5 or more B: 4
C: 3
D: 2
E: 1 or less
（形状（露光部膜減り））
　上記の感度を示す照射量における線幅２２ｎｍのパターンの形状を、走査型電子顕微鏡（（株）日立製作所製Ｓ－４８００）を使用して観察し、以下指標に従い、得られたパターンの形状を評価した。
　パターンの形状が矩形に近いほど膜減りを抑制できていると判断でき、パターンの形状の劣化が著しいほど膜減りが多いと判断できる。
　Ａ：矩形
　Ｂ：わずかに形状が劣化
　Ｃ：顕著に形状が劣化又は非解像 (Shape (reduced film on exposed part))
The shape of the pattern with a line width of 22 nm at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.), and the shape of the obtained pattern was determined according to the following index. evaluated.
It can be judged that the closer the pattern shape is to a rectangle, the more the film loss can be suppressed, and the more the pattern shape is significantly deteriorated, the more the film loss can be judged.
A: Rectangle B: Slightly deteriorated shape C: Significantly deteriorated shape or unresolution
（ブリッジ欠陥）
　２２ｎｍラインアンドスペースパターンの各露光量での解像状況を、走査型電子顕微鏡（（株）日立製作所製Ｓ－９２６０）を使用して観察した。パターン倒れがなく解像できている最大露光量での残渣欠陥の数をカウントし、以下の評価基準で評価した。
　Ａ：３個以下
　Ｂ：４～１０個
　Ｃ：１１～１５個
　Ｄ：１６～３０個
　Ｅ：３１個以上 (Bridge defect)
The resolution of the 22 nm line-and-space pattern at each exposure amount was observed using a scanning electron microscope (S-9260 manufactured by Hitachi, Ltd.). The number of residual defects at the maximum exposure that could be resolved without pattern collapse was counted and evaluated according to the following evaluation criteria.
A: 3 or less B: 4 to 10 C: 11 to 15 D: 16 to 30 E: 31 or more
（帯電性）
　ＰＦＡ配管（内径４ｍｍ、外径６ｍｍ、ニチアス製　ナフロン（Ｒ））の内部に、流速０．５Ｌ／ｍｉｎでリンス液を通液した。その際の配管表面の電位をデジタル静電電位測定器（ＫＳＤ－２０００、春日電機社製）で測定した。以下の評価基準で評価した。
（ＥＳＤリスク評価基準）
　Ａ：５００ｍＶ以下
　Ｂ：５００ｍＶ超１０００ｍＶ以下
　Ｃ：１０００ｍＶ超５０００ｍＶ以下
　Ｄ：５０００ｍＶ超７５００ｍＶ以下
　Ｅ：７５００ｍＶ超 (Chargeability)
A rinse solution was passed through a PFA pipe (inner diameter 4 mm, outer diameter 6 mm, Nichias Naflon (R) ) at a flow velocity of 0.5 L / min. The potential on the surface of the pipe at that time was measured with a digital electrostatic potential measuring device (KSD-2000, manufactured by Kasuga Denki Co., Ltd.). It was evaluated according to the following evaluation criteria.
(ESD risk assessment criteria)
A: 500 mV or less B: 500 mV or more and 1000 mV or less C: 1000 mV or more and 5000 mV or less D: 5000 mV or more and 7500 mV or less E: 7500 mV or less
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
　表中、「二溶剤の沸点差」は、下記式（Ｂｐ）で求められる値を意味する。
　式（Ｂｐ）　「二溶剤の沸点差（℃）」＝｜フッ素系溶剤の沸点（℃）－第二溶剤の沸点（℃）｜
　沸点は１気圧における沸点である。
　表４～８中、「骨格」欄は、第二溶剤が、直鎖状構造、分岐鎖状構造、又は、環状構造を有するか否かを表す。「環状」の記載は、第二溶剤が環状構造を有することを意味する。「分岐」の記載は、第二溶剤が、分岐鎖状アルキル基を有し、環状構造を有さないことを意味する。「直鎖」の記載は、第二の溶剤が、直鎖状のアルキル基を有し、環状構造及び分岐鎖状アルキル基を有さないことを意味する。 In the table, the "boiling point difference between the two solvents" means the value obtained by the following formula (Bp).
Formula (Bp) "Boiling point difference between two solvents (° C)" = | Boiling point of fluorine-based solvent (° C) -Boiling point of second solvent (° C) |
The boiling point is the boiling point at 1 atm.
In Tables 4 to 8, the "skeleton" column indicates whether or not the second solvent has a linear structure, a branched chain structure, or a cyclic structure. The description of "cyclic" means that the second solvent has a cyclic structure. The description of "branched" means that the second solvent has a branched chain alkyl group and does not have a cyclic structure. The description of "straight chain" means that the second solvent has a linear alkyl group and does not have a cyclic structure or a branched chain alkyl group.
＜結果＞
　表４～８に示す結果より、本発明の処理液をリンス液として使用した場合、所望の効果が得られるが確認された。 <Result>
From the results shown in Tables 4 to 8, it was confirmed that the desired effect was obtained when the treatment liquid of the present invention was used as a rinsing liquid.
　実施例Ａ－１～Ａ－３と、実施例Ａ－４～Ａ－５との比較等から、フッ素系溶剤の含有量が、処理液の全質量に対して、１０～８０質量％である場合、より効果が優れることが確認された。
　実施例Ｂ－１～Ｂ－５の比較、実施例Ｃ－１～Ｃ－５の比較、実施例Ｄ－１～Ｄ－５の比較、実施例Ｅ－１～Ｅ－５の比較からも、上記効果がわかる。 From the comparison between Examples A-1 to A-3 and Examples A-4 to A-5, the content of the fluorine-based solvent is 10 to 80% by mass with respect to the total mass of the treatment liquid. In that case, it was confirmed that the effect was superior.
Also from the comparison of Examples B-1 to B-5, the comparison of Examples C-1 to C-5, the comparison of Examples D-1 to D-5, and the comparison of Examples E-1 to E-5. The above effect can be seen.
　実施例Ａ－２及びＡ－２４と、実施例Ａ－２２及びＡ－４４との比較から、有機溶剤が、非環状エステル系溶剤の場合、より効果が優れることが確認された。
　また、実施例Ｂ－９及びＢ－１８と、実施例Ｂ－２及びＢ－１１との比較から、有機溶剤が、非環状エーテル系溶剤の場合、より効果が優れることが確認された。 From the comparison between Examples A-2 and A-24 and Examples A-22 and A-44, it was confirmed that the effect was more excellent when the organic solvent was an acyclic ester solvent.
Further, from the comparison between Examples B-9 and B-18 and Examples B-2 and B-11, it was confirmed that the effect was more excellent when the organic solvent was an acyclic ether solvent.
　実施例Ａ－１、Ｂ－１、Ｃ－１、Ｄ－１及びＥ－１の比較より、第二溶剤としてエステル系溶剤、エーテル系溶剤、アルコール系溶剤、又は、ケトン系溶剤を用いる場合、より効果が優れることが確認された。 From the comparison of Examples A-1, B-1, C-1, D-1 and E-1, when an ester solvent, an ether solvent, an alcohol solvent, or a ketone solvent is used as the second solvent, It was confirmed that the effect was superior.
　実施例Ａ－２、Ａ－６、Ａ－８、Ａ－１１、Ａ－１６、Ａ－２０、及び、Ａ－２１の比較より、エステル系溶剤の炭素数が８以下の場合、より効果が優れることが確認された。 From the comparison of Examples A-2, A-6, A-8, A-11, A-16, A-20, and A-21, the effect is more effective when the number of carbon atoms of the ester solvent is 8 or less. It was confirmed to be excellent.
〔実施例Ｆ－１〕
　レジスト組成物１のかわりにレジスト組成物２を用いた以外、実施例Ａ－１と同様の手順を実施してパターンの形成を行ったところ、解像性の評価はＣ、露光部膜減りの評価はＢ、ブリッジ欠陥の評価はＡ、帯電性の評価はＡであった。
　上記結果より、樹脂がヒドロキシスチレン系繰り返し単位を有する場合、より優れた効果が得られることが確認された。 [Example F-1]
When a pattern was formed by carrying out the same procedure as in Example A-1 except that the resist composition 2 was used instead of the resist composition 1, the resolution was evaluated as C, and the exposed film was reduced. The evaluation was B, the evaluation of bridge defects was A, and the evaluation of chargeability was A.
From the above results, it was confirmed that when the resin has a hydroxystyrene-based repeating unit, a more excellent effect can be obtained.
　本発明の処理液は、上記に記載したリンス液としての用途のみならず、現像液として用いても、所望の効果が得られる。
　具体的には、実施例１において、現像液を、酢酸ブチルと２Ｈ，３Ｈ－デカフルオロペンタンとの体積比が３：２（酢酸ブチル：２Ｈ，３Ｈ－デカフルオロペンタン）の混合液に変更して現像を行っても、同様にパターンが得られた。 The treatment liquid of the present invention can be used not only as a rinse liquid described above but also as a developing liquid to obtain a desired effect.
Specifically, in Example 1, the developer was changed to a mixed solution of butyl acetate and 2H, 3H-decafluoropentane in a volume ratio of 3: 2 (butyl acetate: 2H, 3H-decafluoropentane). A pattern was obtained in the same manner even when the development was carried out.

Claims (22)

  1. 　感活性光線又は感放射線性組成物から得られるレジスト膜に対して、露光後の現像及び洗浄の少なくとも一方を行うために使用される、レジスト膜パターニング用の処理液であって、
    　炭素数３～５のフッ素系溶剤と、前記炭素数３～５のフッ素系溶剤以外の有機溶剤とを含む、処理液。     A treatment liquid for patterning a resist film, which is used to perform at least one of development and cleaning after exposure on a resist film obtained from a sensitive light beam or a radiation-sensitive composition.
    A treatment liquid containing a fluorinated solvent having 3 to 5 carbon atoms and an organic solvent other than the fluorinated solvent having 3 to 5 carbon atoms.
  2. 　前記有機溶剤が、ヘテロ原子を有していてもよい炭化水素を含む、請求項１に記載の処理液。 The treatment liquid according to claim 1, wherein the organic solvent contains a hydrocarbon which may have a hetero atom.
  3. 　前記処理液がリンス液である、請求項１又は２に記載の処理液。 The treatment liquid according to claim 1 or 2, wherein the treatment liquid is a rinse liquid.
  4. 　前記フッ素系溶剤に含まれるフッ素原子数が、前記フッ素系溶剤に含まれる炭素数に対して、２倍以上である、請求項１～３のいずれか１項に記載の処理液。 The treatment liquid according to any one of claims 1 to 3, wherein the number of fluorine atoms contained in the fluorine-based solvent is twice or more the number of carbon atoms contained in the fluorine-based solvent.
  5. 　前記フッ素系溶剤の含有量が、処理液の全質量に対して、１０～８０質量％である、請求項１～４のいずれか１項に記載の処理液。 The treatment liquid according to any one of claims 1 to 4, wherein the content of the fluorine-based solvent is 10 to 80% by mass with respect to the total mass of the treatment liquid.
  6. 　前記フッ素系溶剤が、２Ｈ，３Ｈ－デカフルオロペンタン、及び、１Ｈ－ウンデカフルオロペンタンからなる群から選ばれる少なくとも１種を含む、請求項１～５のいずれか１項に記載の処理液。 The treatment liquid according to any one of claims 1 to 5, wherein the fluorinated solvent contains at least one selected from the group consisting of 2H, 3H-decafluoropentane, and 1H-undecafluoropentane.
  7. 　前記有機溶剤が、エステル系溶剤、エーテル系溶剤、アルコール系溶剤、ケトン系溶剤、及び、炭化水素系溶剤からなる群から選ばれる少なくとも１種を含む、請求項１～６のいずれか１項に記載の処理液。 The item according to any one of claims 1 to 6, wherein the organic solvent contains at least one selected from the group consisting of an ester solvent, an ether solvent, an alcohol solvent, a ketone solvent, and a hydrocarbon solvent. The treatment solution described.
  8. 　前記有機溶剤が非環状エステル系溶剤を含み、
    　前記非環状エステル系溶剤の炭素数が炭素数５以上であり、
    　前記非環状エステル系溶剤の沸点と、前記フッ素系溶剤の沸点との差の絶対値が５０℃以上である、請求項１～７のいずれか１項に記載の処理液。     The organic solvent contains a non-cyclic ester solvent and contains
    The acyclic ester solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
    The treatment liquid according to any one of claims 1 to 7, wherein the absolute value of the difference between the boiling point of the acyclic ester solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
  9. 　前記有機溶剤が、プロピオン酸イソプロピル、酢酸ｓｅｃ－ブチル、ギ酸イソアミル、酢酸ブチル、炭酸ジエチル、酪酸ブチル、酪酸アミル、酪酸イソブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸イソアミル、酢酸アミル、酢酸ヘキシル、酢酸－２－エチルブチル、ギ酸アミル、ギ酸ヘキシル、ギ酸イソヘキシル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸プロピル、プロピオン酸ヘキシル、酪酸エチル、イソ酪酸エチル、酪酸ヘキシル、イソ酪酸イソブチル、ヘキサン酸エチル、ｎ－オクタン酸メチル、及び、ｎ－オクタン酸エチルからなる群から選ばれる少なくとも１種を含む、請求項８に記載の処理液。 The organic solvent is isopropyl propionate, sec-butyl acetate, isoamyl formate, butyl acetate, diethyl carbonate, butyl butyrate, amyl butyrate, isobutyl butyrate, isobutyl acetate, tert-butyl acetate, isoamyl acetate, amyl acetate, hexyl acetate, acetic acid. -2-ethylbutyl, amyl formate, hexyl formate, isohexyl formate, butyl propionate, isobutyl propionate, propyl propionate, hexyl propionate, ethyl butyrate, ethyl isobutyrate, hexyl butyrate, isobutyl isobutyrate, ethyl hexanoate, n- The treatment solution according to claim 8, which comprises at least one selected from the group consisting of methyl octanate and ethyl n-octanoate.
  10. 　前記有機溶剤が非環状エーテル系溶剤を含み、
    　前記非環状エーテル系溶剤の炭素数５以上であり、
    　前記非環状エーテル系溶剤の沸点と、前記フッ素系溶剤の沸点との差の絶対値が５０℃以上である、請求項１～７のいずれか１項に記載の処理液。     The organic solvent contains an acyclic ether solvent and contains
    The acyclic ether solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
    The treatment liquid according to any one of claims 1 to 7, wherein the absolute value of the difference between the boiling point of the acyclic ether solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
  11. 　前記有機溶剤が、ジイソアミルエーテル、アミルエーテル、ジイソアミルエーテル、及び、アミルエーテルからなる群から選ばれる少なくとも１種を含む、請求項１０に記載の処理液。 The treatment solution according to claim 10, wherein the organic solvent contains at least one selected from the group consisting of diisoamyl ether, amyl ether, diisoamyl ether, and amyl ether.
  12. 　前記有機溶剤が非環状アルコール系溶剤を含み、
    　前記非環状アルコール系溶剤の炭素数７以上であり、
    　前記非環状アルコール系溶剤の沸点と、前記フッ素系溶剤の沸点との差の絶対値が１００℃以上である、請求項１～７のいずれか１項に記載の処理液。     The organic solvent contains a non-cyclic alcohol solvent and contains
    The acyclic alcohol solvent has 7 or more carbon atoms and has 7 or more carbon atoms.
    The treatment liquid according to any one of claims 1 to 7, wherein the absolute value of the difference between the boiling point of the acyclic alcohol solvent and the boiling point of the fluorine solvent is 100 ° C. or higher.
  13. 　前記有機溶剤が、２，６－ジメチル－４－ヘプタノール、３－オクタノール、２－エチルヘキサノール、１－オクタノール、２－オクタノール、３，５－ジメチル－１－ヘキシン－３－オール、１－オクチン－３－オール、３，７－ジメチル－３－オクタノール、３，５，５－トリメチル－１－ヘキサノール、３－エチル－３－ペンタノール－４－メチルペンタノール、及び、１－ヘプタノールからなる群から選ばれる少なくとも１種を含む、請求項１２に記載の処理液。 The organic solvent is 2,6-dimethyl-4-heptanol, 3-octanol, 2-ethylhexanol, 1-octanol, 2-octanol, 3,5-dimethyl-1-hexin-3-ol, 1-octin-. From the group consisting of 3-ol, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol-4-methylpentanol, and 1-heptanol. The treatment solution according to claim 12, which comprises at least one selected.
  14. 　前記有機溶剤が非環状ケトン系溶剤を含み、
    　前記非環状ケトン系溶剤の炭素数５以上であり、
    　前記非環状ケトン系溶剤の沸点と、前記フッ素系溶剤の沸点との差の絶対値が５０℃以上である、請求項１～７のいずれか１項に記載の処理液。     The organic solvent contains an acyclic ketone solvent and contains
    The acyclic ketone solvent has 5 or more carbon atoms and has 5 or more carbon atoms.
    The treatment liquid according to any one of claims 1 to 7, wherein the absolute value of the difference between the boiling point of the acyclic ketone solvent and the boiling point of the fluorine solvent is 50 ° C. or higher.
  15. 　前記有機溶剤が、ジイソブチルケトン、３－オクタノン、２，４－ジメチル－３－ペンタノン、２，６－ジメチル－４－ヘプタノン、５－ノナノン、及び、２，５－ジメチル－３－ヘキサノンからなる群から選ばれる少なくとも１種を含む、請求項１４に記載の処理液。 The group in which the organic solvent consists of diisobutyl ketone, 3-octanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 5-nonanonone, and 2,5-dimethyl-3-hexanone. The treatment liquid according to claim 14, which comprises at least one selected from.
  16. 　前記有機溶剤が炭素数７以上の炭化水素系溶剤を含む、請求項１～７のいずれか１項に記載の処理液。 The treatment liquid according to any one of claims 1 to 7, wherein the organic solvent contains a hydrocarbon solvent having 7 or more carbon atoms.
  17. 　前記有機溶剤が、デカン、メシチレン、ウンデカン、ノナノン、３－メチルノナノン、４－メチルノナノン、及び、５－メチルノナンからなる群から選ばれる少なくとも１種を含む、請求項１６に記載の処理液。 The treatment liquid according to claim 16, wherein the organic solvent contains at least one selected from the group consisting of decane, mesitylene, undecane, nonanone, 3-methylnonanone, 4-methylnonanone, and 5-methylnonanone.
  18. 　前記感活性光線又は感放射線性組成物が、ヒドロキシスチレン系繰り返し単位を有する樹脂を含む、請求項１～１７のいずれか１項に記載の処理液。 The treatment solution according to any one of claims 1 to 17, wherein the sensitive light ray or radiation sensitive composition contains a resin having a hydroxystyrene-based repeating unit.
  19. 　前記感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
    　前記レジスト膜を露光する露光工程と、
    　露光された前記レジスト膜を請求項１～１８のいずれか１項に記載の処理液によって処理する処理工程とを備える、パターン形成方法。     A resist film forming step of forming a resist film using the sensitive light beam or a radiation-sensitive composition, and
    An exposure step for exposing the resist film and
    A pattern forming method comprising a treatment step of treating the exposed resist film with the treatment liquid according to any one of claims 1 to 18.
  20. 　前記感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
    　前記レジスト膜を露光する露光工程と、
    　露光された前記レジスト膜を処理する処理工程とを備える、パターン形成方法であって、
    　前記処理工程は、
    　現像液によって現像する現像工程と、
    　リンス液によって洗浄するリンス工程とを備え、
    　前記リンス液が請求項１～１８のいずれか１項に記載の処理液である、パターン形成方法。     A resist film forming step of forming a resist film using the sensitive light beam or a radiation-sensitive composition, and
    An exposure step for exposing the resist film and
    A pattern forming method comprising a treatment step of treating the exposed resist film.
    The processing step is
    The development process of developing with a developer and
    Equipped with a rinsing process for cleaning with a rinsing liquid,
    The pattern forming method, wherein the rinsing liquid is the treatment liquid according to any one of claims 1 to 18.
  21. 　前記現像液が、エステル系溶剤を含む、請求項２０に記載のパターン形成方法。 The pattern forming method according to claim 20, wherein the developer contains an ester solvent.
  22. 　前記エステル系溶剤が、酢酸ブチル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチル、酢酸ｓｅｃ－ブチル、酢酸アミル、酢酸イソアミル、ギ酸アミル、ギ酸イソアミル、ギ酸ヘキシル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸イソプロピル、プロピオン酸プロピル、酪酸エチル、イソ酪酸エチル、炭酸ジエチル、炭酸ジブチル、ブタン酸ブチル、イソ酪酸イソブチル、イソ吉草酸エチル、イソ吉草酸ブチル、ヘプタン酸プロピル、ヘプタン酸エチル、ヘキサン酸ブチル、ヘキサン酸プロピル、及び、３－メチル吉草酸エチルからなる群から選ばれる少なくとも１種を含む、請求項２１に記載のパターン形成方法。 The ester-based solvent is butyl acetate, isobutyl acetate, tert-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, amyl formate, isoamyl formate, hexyl formate, amyl propionate, isoamyl propionate, isopropyl propionate, propion. Propyl acid, ethyl butyrate, ethyl isobutyrate, diethyl carbonate, dibutyl carbonate, butyl butanoate, isobutyl isobutyrate, ethyl isovalerate, butyl isovalerate, propyl heptate, ethyl heptate, butyl hexanoate, propyl hexanoate, The pattern forming method according to claim 21, further comprising at least one selected from the group consisting of ethyl 3-methylvalerate.
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