WO2021182182A1 - 処理液、パターン形成方法 - Google Patents

処理液、パターン形成方法 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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English (en)
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/ja
Priority to JP2023213680A priority patent/JP7731414B2/ja

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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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