WO2020203670A1 - Solution de traitement et procédé de formation de motif - Google Patents

Solution de traitement et procédé de formation de motif Download PDF

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Publication number
WO2020203670A1
WO2020203670A1 PCT/JP2020/013751 JP2020013751W WO2020203670A1 WO 2020203670 A1 WO2020203670 A1 WO 2020203670A1 JP 2020013751 W JP2020013751 W JP 2020013751W WO 2020203670 A1 WO2020203670 A1 WO 2020203670A1
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group
organic solvent
solvent
preferable
treatment liquid
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PCT/JP2020/013751
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English (en)
Japanese (ja)
Inventor
智美 高橋
清水　哲也
徹 土橋
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富士フイルム株式会社
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Priority to JP2021511939A priority Critical patent/JP7292378B2/ja
Publication of WO2020203670A1 publication Critical patent/WO2020203670A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • H01L21/04—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 boards such as liquid crystal and thermal heads, and other photolithography lithography processes.
  • the present invention relates to a treatment liquid and a pattern forming method.
  • Patent Document 1 discloses that an organic treatment solution containing a mixture of a first organic solvent and a second organic solvent selected from a ketone solvent and an ester solvent is used as a developing solution.
  • a treatment liquid for patterning a resist film which is used to perform at least one of development and cleaning of a resist film obtained from a sensitive light beam or a radiation-sensitive composition, and contains an organic solvent. It contains a first organic solvent that satisfies the following condition A and a second organic solvent that satisfies the following condition B.
  • the content of the second organic solvent is 10% by mass or more with respect to the total content of the first organic solvent and the second organic solvent.
  • the treatment liquid in which the content of the second organic solvent is 10% by mass or more with respect to the total mass of the treatment liquid.
  • Solvent condition A An organic having an SP value of 18.7 MPa 1/2 or less, a ⁇ P represented by the following formula (1) of 15.0 or less, and a ⁇ D represented by the following formula (2) of more than 70.0.
  • Solvent condition B An organic solvent having an SP value of 18.7 MPa 1/2 or less, a ⁇ P represented by the following formula (1) of 15.0 or less, and a ⁇ D represented by the following formula (2) of 70.0 or less. ..
  • ⁇ d represents the dispersion term of the Hansen solubility parameter.
  • ⁇ p represents the polarity term of the Hansen solubility parameter.
  • ⁇ h represents the hydrogen bond term of the Hansen solubility parameter.
  • Condition A-1 The SP value is 18.7 MPa 1/2 or less, the ⁇ P represented by the following formula (1) is 15.0 or less, the ⁇ D represented by the following formula (2) is larger than 70.0, and Organic solvent with ClogP less than 4.5 [3] Further containing a third organic solvent
  • the second organic solvent is 1,5-cyclooctadiene, isobutyl isobutyrate, ethyl 2-methylvalerate, butyl butyrate, hexyl acetate, isobutyl butyrate, butyl isobutyrate, pentyl butyrate, butyl isovalerate.
  • the third organic solvent is 2,6-dimethyl-4-heptanol, 2-octanol, 3-ethyl-3-pentanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-.
  • the treatment solution according to [3] which contains at least one alcohol-based solvent selected from the group consisting of 1-hexanol and 3,7-dimethyl-3-octanol.
  • a resist film forming step of forming a resist film using a sensitive light beam or a radiation-sensitive composition and The exposure process for exposing the resist film and A pattern forming method comprising a treatment step of treating the exposed resist film with the treatment liquid according to any one of [1] to [8].
  • a resist film forming step of forming a resist film using an active ray or a radiation-sensitive composition and The exposure process for exposing the resist film and A pattern forming method comprising a treatment step of treating the exposed resist film.
  • the above processing process The development process of developing with a developer and Equipped with a rinsing process for cleaning with a rinsing solution
  • the pattern forming method wherein the rinsing solution is the treatment solution according to any one of [1] to [8].
  • the ester-based solvent is butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butanoate, butyl isobutate.
  • the pattern forming method according to [11] which comprises one or more selected from the group consisting of isobutyl isobutate and.
  • the present invention it is possible to provide a treatment liquid for resist film patterning, which can suppress pattern collapse and has a low resistivity. Further, according to the present invention, it is possible to provide a pattern forming method using the above-mentioned and the treatment liquid for patterning the resist film.
  • the present invention will be described in detail.
  • the description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • 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 (EB). : Electron Beam) and the like.
  • light means active light or radiation.
  • the term "exposure” as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams and It also includes drawing with particle beams such as ion beams.
  • "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified. For example, when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acrylic represents acrylic and methacrylic.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are determined by a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Toso).
  • the acid dissociation constant pKa in the present specification represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). Will be done.
  • the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution.
  • the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All pKa values described herein indicate values calculated using this software package.
  • Software Package 1 Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labors).
  • 1 ⁇ is 1 x 10-10 m.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the treatment liquid of the present invention is used for at least one of development and cleaning of a resist film obtained from a sensitive light ray or a radiation-sensitive composition (hereinafter, also referred to as “resist composition”), and is organic.
  • a treatment liquid for patterning a resist film containing a solvent contains a first organic solvent that satisfies the condition A described later and a second organic solvent that satisfies the condition B described later, and the content of the second organic solvent is the first. It is 10% by mass or more with respect to the total content of the organic solvent and the second organic solvent.
  • the content of the second organic solvent is 10% by mass or more with respect to the total mass of the treatment liquid.
  • the treatment liquid of the present invention contains the first organic solvent and the second organic solvent so as to have a predetermined ratio with respect to the first organic solvent, thereby contributing to the contribution of the first organic solvent.
  • the resistivity of the treatment liquid can be adjusted within an appropriate range without reducing the effect of suppressing the pattern collapse that is improved.
  • the treatment liquid of the present invention has both an effect of suppressing pattern collapse and a low resistivity.
  • the treatment liquid of the present invention contains a first organic solvent (hereinafter, also referred to as "solvent A") that satisfies the following condition A.
  • Condition A An organic having an SP value of 18.7 MPa 1/2 or less, a ⁇ P represented by the following formula (1) of 15.0 or less, and a ⁇ D represented by the following formula (2) of more than 70.0.
  • ⁇ d represents the dispersion term of the Hansen solubility parameter.
  • ⁇ p represents the polarity term of the Hansen solubility parameter.
  • ⁇ h represents the hydrogen bond term of the Hansen solubility parameter.
  • condition A-1 the treatment liquid has a lower resistivity.
  • Condition A-1 The SP value is 18.7 MPa 1/2 or less, the ⁇ P represented by the following formula (1) is 15.0 or less, the ⁇ D represented by the following formula (2) is larger than 70.0, and Organic solvent with ClogP less than 4.5
  • SP value is calculated based on the following formula using the Fedors method described in "PROPERTIES OF POLYMERS, 2nd Edition, 1976 Publishing".
  • the unit of the SP value is MPa 1/2 unless otherwise specified.
  • SP value (Fedors method) [(sum of aggregation energies of each substituent) / (sum of volume of each substituent)] 0.5
  • the parameters (aggregation energy and volume) of each substituent in addition to the respective values described in "PROPERTIES OF POLYMERS, 2nd Edition, 1976 Publishing", the description of literature values and the like can be adopted.
  • the smaller the SP value of the solvent the lower the polarity. That is, the smaller the SP value, the lower the affinity with the resist film, and the excessive penetration into the resist film can be suppressed, that is, the swelling can be suppressed.
  • the Hansen solubility parameter ( ⁇ ) is defined by the three-dimensional parameter ( ⁇ d, ⁇ p, ⁇ h) and is represented by the following formula (3).
  • ⁇ d the three-dimensional parameter
  • ⁇ p the Hansen solubility parameter
  • ⁇ h the three-dimensional parameter
  • ⁇ d a dispersion term (also referred to as a London dispersion force term).
  • ⁇ p represents a polar term (also referred to as a molecular polarization term).
  • ⁇ h represents a hydrogen bond term.
  • ⁇ d, ⁇ p, and ⁇ h can be calculated using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameter.
  • ⁇ d, ⁇ p, and ⁇ h in this specification are values calculated using Ver.5.1.04.
  • ⁇ d, ⁇ p, and ⁇ h in the above formula (1) and the formula (2) described later are synonymous with ⁇ d, ⁇ p, and ⁇ h in the above formula (3), respectively.
  • the ClogP of the solvent is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
  • Known methods and software can be used for the calculation of the ClogP value, but unless otherwise specified, the ClogP program incorporated in the ChemBioDrow Ultra 13.0 of Cambridge soft is used in the present specification. To do.
  • the high ClogP indicates that the affinity with the hydrophobic molecule (1-octanol as an index) is higher than that with the water molecule.
  • Solvent A is an organic solvent having an SP value of 18.7 MPa 1/2 or less, a ⁇ P of 15.0 or less, and a ⁇ D of more than 70.0.
  • the lower limit of the SP value is, for example, 15.0 MPa 1/2 or more
  • the lower limit of ⁇ P is, for example, 0.0 or more
  • the upper limit of ⁇ D is, for example, 100.0. It is as follows.
  • ClogP is smaller than 4.5. That is, the solvent A preferably satisfies the above condition A-1.
  • the lower limit of ClogP is, for example, 2.5 or more, and preferably 3.5 or more.
  • the hydrocarbon solvent may be either an aliphatic hydrocarbon solvent or an unsaturated aliphatic hydrocarbon solvent.
  • 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 in the hydrocarbon chain. Further, when the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.
  • the number of carbon atoms in the hydrocarbon solvent is preferably 7 or more in that pattern collapse can be further suppressed.
  • the upper limit is not particularly limited, but for example, 16 or less is mentioned, 14 or less is preferable, and 12 or less is more preferable.
  • the ether solvent is intended to be a solvent having at least one ether bond in the molecule. Therefore, for example, when the solvent has a functional group other than the ether bond and the ether bond, it is regarded as an ether solvent.
  • ethylcyclohexane (SP value: 16.4, ⁇ P: 0.0, ⁇ D: 100.0, ClogP: 4.4) and mesitylene (SP value: 18.6, ⁇ P: 3. 1, ⁇ D: 93.8, ClogP: 3.6), diisoamyl ether (SP value: 15.6, ⁇ P: 12.1, ⁇ D: 76.8, ClogP: 3.8), and diisobutyl ether (SP).
  • a value selected from the group consisting of 15.2, ⁇ D: 75.6, ⁇ P: 12.2, CRogP: 2.7) is preferable.
  • the treatment liquid of the present invention contains a second organic solvent (hereinafter, also referred to as “solvent B”) that satisfies the following condition B.
  • solvent B An organic solvent having an SP value of 18.7 MPa 1/2 or less, a ⁇ P represented by the following formula (1) of 15.0 or less, and a ⁇ D represented by the following formula (2) of 70.0 or less.
  • Equation (1): ⁇ P ⁇ p / ( ⁇ d + ⁇ p + ⁇ h) ⁇ 100
  • ⁇ D ⁇ d / ( ⁇ d + ⁇ p + ⁇ h) ⁇ 100
  • ⁇ d represents the dispersion term of the Hansen solubility parameter.
  • ⁇ p represents the polarity term of the Hansen solubility parameter.
  • ⁇ h represents the hydrogen bond term of the Hansen solubility parameter.
  • Solvent B is an organic solvent having an SP value of 18.7 MPa 1/2 or less, ⁇ P of 15.0 or less, and ⁇ D of 70.0 or less.
  • the treatment liquid of the present invention can adjust the resistivity within an appropriate range without reducing the effect of suppressing pattern collapse, which is improved by the contribution of the solvent A.
  • the lower limit of the SP value is, for example, 14.0 MPa 1/2 or more
  • the lower limit of ⁇ P is, for example, 0.0 or more
  • the upper limit of ⁇ D is, for example, 100.0. It is as follows.
  • the hydrocarbon solvent may be either an aliphatic hydrocarbon solvent or an unsaturated aliphatic hydrocarbon solvent.
  • 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 in the hydrocarbon chain. Further, when the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.
  • the number of carbon atoms in the hydrocarbon solvent is preferably 7 or more in that pattern collapse can be further suppressed.
  • the upper limit is not particularly limited, but for example, 16 or less is mentioned, 14 or less is preferable, and 12 or less is more preferable.
  • hydrocarbon solvent is preferably cyclic.
  • cyclic hydrocarbon solvent include 1,5-cyclooctadiene and the like.
  • the ester solvent is intended to be a solvent having at least one ester bond in the molecule.
  • the solvent has a functional group other than the ester bond and the ester bond, it is regarded as an ester solvent.
  • the ester solvent preferably has 8 or more carbon atoms, and more preferably 8 or 9 carbon atoms.
  • 1,5-cyclooctadiene (SP value: 14.3, ⁇ P: 12.9, ⁇ D: 67.8) and isobutyl isobutyrate (SP value: 17.1, ⁇ P: 14) .2, ⁇ D: 68.0), ethyl 2-methylvalerate (SP value: 17.4, ⁇ P: 14.8, ⁇ D: 66.2), butyl butyrate (SP value: 17.8, ⁇ P: 12) .0, ⁇ D: 64.7), hexyl acetate (SP value: 17.8, ⁇ P: 11.8, ⁇ D: 64.2), isobutyl butyrate (SP value: 16.8, ⁇ P: 14.3, ⁇ D) : 67.1), and butyl isobutyrate (SP value: 16.8, ⁇ P: 14.5, ⁇ D: 66.2) are preferably selected from the group.
  • the content of the first organic solvent is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total mass of the treatment liquid.
  • the upper limit is not particularly limited, but for example, 95% by mass or less is preferable, 90% by mass or less is more preferable, and 80% by mass or less is further preferable.
  • the content of the second organic solvent is 10% by mass or more, preferably 20% by mass or more, and more preferably 40% by mass or more, based on the total mass of the treatment liquid.
  • the upper limit thereof is not particularly limited, but is, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less.
  • the content of the second organic solvent is 10% by mass or more, more preferably 20% by mass or more, and further 30% by mass or more, based on the total content of the first organic solvent and the second organic solvent. preferable. Further, as the upper limit value, 80% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass or less is further preferable. In particular, in that the resistivity of the treatment liquid is smaller, the content of the second organic solvent in the treatment liquid is 30% by mass or more with respect to the total content of the first organic solvent and the second organic solvent. Is preferable. In addition, the content of the second organic solvent in the treatment liquid is the total content of the first organic solvent and the second organic solvent in that the formed pattern has little influence on the LWR (line width roughness) performance.
  • the content of the first organic solvent in the treatment liquid is higher than the total content of the first organic solvent and the second organic solvent in that pattern collapse can be suppressed regardless of the solvent type and the compounding ratio. It is preferably 30% by mass or more.
  • the treatment liquid of the present invention contains the first organic solvent and the second organic solvent and does not contain the third organic solvent described later, the first organic solvent and the second organic solvent
  • the total content of the above is preferably 95.0% by mass or more, more preferably 98.0% by mass or more, further preferably 99.0% by mass or more, and 99.5% by mass or more, based on the total mass of the treatment liquid. Is particularly preferable, and 99.9% by mass or more is most preferable.
  • the upper limit value is, for example, 100% by mass or less.
  • the treatment liquid of the present invention contains the first organic solvent, the second organic solvent, and the third organic solvent described later
  • the total content of the three organic solvents with respect to the total mass of the treatment liquid is preferably 90.0% by mass or more, more preferably 98.0% by mass or more, further preferably 99.0% by mass or more, and 99. 5.5% by mass or more is particularly preferable, and 99.9% by mass or more is most preferable.
  • the upper limit value is, for example, 100% by mass or less.
  • the treatment liquid of the present invention may contain at least one of the first organic solvent and the second organic solvent, and other components other than the first organic solvent and the second organic solvent. May include.
  • an alcohol solvent having an SP value of 19.0 to 21.0 MPa 1/2 (hereinafter, also referred to as “solvent C”) is preferable. Since the alcohol-based solvent has strong hydrogen bonds and is difficult to dry, the capillary force works for a long time, so that the volatileness of the solvent can greatly affect the resolution (suppression of pattern collapse). On the other hand, when the treatment liquid contains an alcohol-based solvent (solvent C) having an SP value in the above numerical range, various effects are exhibited without excessively reducing the effect of suppressing pattern collapse, which is improved by the contribution of solvent A. obtain.
  • the effects of the solvent C include, for example, the fact that the resistivity of the treatment liquid can be adjusted to a more appropriate range, and / or defects (particularly bridge defects) caused by highly polar residue components such as highly polar polymer residues. There is a point that can be further suppressed.
  • the alcohol solvent is intended to be a solvent having at least one alcohol group in the molecule.
  • the solvent has an alcohol group and a functional group other than the alcohol group, it is regarded as an alcohol-based solvent.
  • an acyclic alcohol solvent is preferable because it has a more excellent effect of suppressing pattern collapse.
  • 2,6-dimethyl-4-heptanol (SP value: 19.9), 2-octanol (SP value: 20.7), 3-ethyl is more excellent in the effect of suppressing pattern collapse. It is preferably selected from the group consisting of -3-pentanol (SP value: 20.8) and 2-ethyl-1-hexanol (SP value: 20.7).
  • the content of the third organic solvent is preferably 2% by mass or more, more preferably 5% by mass or more, based on the total mass of the treatment liquid.
  • the upper limit is not particularly limited, but for example, it is preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the treatment liquid of the present invention may contain the following ionic liquids.
  • the ionic liquid is not contained in the first organic solvent, the second organic solvent, and the third organic solvent.
  • the ionic liquid includes, for example, aromatic ions such as pyridinium ion or imidazolium ion, or aliphatic amine ions such as trimethylhexyl ammonium ion as cations, and NO 3 ⁇ as an anion.
  • ionic liquids include, for example, IL-P14 and IL-A2 (manufactured by Koei Chemical Industry Co., Ltd.); Elegan SS-100 (manufactured by Nippon Oil & Fats Co., Ltd.), which is a quaternary ammonium salt-based ionic liquid. And so on.
  • IL-P14 and IL-A2 manufactured by Koei Chemical Industry Co., Ltd.
  • Elegan SS-100 manufactured by Nippon Oil & Fats Co., Ltd.
  • One type of ionic liquid 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 to 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 usually 0.001 to 5% by mass, 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.
  • an amine-based antioxidant or a phenol-based antioxidant is preferable.
  • 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.
  • One type of basic compound 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, preferably 0.5 to 5% by mass, based on the total amount 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.
  • the treatment liquid of the present invention may contain other solvents.
  • the treatment solution of the present invention contains the first organic solvent, the second organic solvent, and other organic solvents other than the third organic solvent. You may be.
  • the other organic solvent 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 treatment liquid of the present invention is used as a rinsing liquid, the treatment liquid of the present invention contains the first organic solvent, the second organic solvent, and other organic solvents other than the third organic solvent. You may be.
  • the other organic solvent is not particularly limited, and examples thereof include solvents such as hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
  • the present invention also relates to a pattern forming method using the above-mentioned treatment liquid.
  • the pattern forming method of the present invention (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) A treatment step of treating the exposed resist film with the above-mentioned treatment liquid is included.
  • the resist film forming step is a step of forming a resist film using a resist composition, and can be performed by, for example, the following method.
  • each component described later is dissolved in a solvent to prepare a resist composition, and if necessary, filtered through a filter and then applied onto the substrate.
  • the pore size of the filter is preferably 0.1 micron or less, more preferably 0.05 micron or less, and further preferably 0.03 micron or less.
  • As the material of the filter polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • the resist composition is applied onto a substrate (eg, silicon, silicon dioxide coating) such as that used in the manufacture of integrated circuit elements by an appropriate coating method such as a spinner. Then, it dries to form a resist film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the resist film.
  • a substrate eg, silicon, silicon dioxide coating
  • an appropriate coating method such as a spinner.
  • various undercoat films inorganic film, organic film, antireflection film
  • the heating temperature is preferably 80 to 180 ° C, more preferably 80 to 150 ° C, even more 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 45 nm, preferably 15 to 40 nm, in that it is more excellent in etching resistance and resolution.
  • the exposure method in the (ii) exposure step may be immersion exposure.
  • the pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
  • the pattern forming method of the present invention preferably includes (v) post-exposure Bake (PEB) step after (ii) exposure step and before (iii) development step.
  • the pattern forming method of the present invention may include (ii) exposure steps a plurality of times.
  • the pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
  • the pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.
  • the above-mentioned (i) film forming step, (ii) exposure step, and (iii) processing step can be performed by a generally known method.
  • a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film
  • SOG Spin On Glass
  • SOC Spin On Carbon
  • antireflection film As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
  • a protective film (top coat) may be formed on the upper layer of the resist film.
  • a known material can be appropriately used.
  • composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used.
  • the composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
  • 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 support that forms the resist film is not particularly limited, and is used in 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.
  • a commonly used substrate can be used.
  • Specific examples of the support include an inorganic substrate such as silicon, SiO 2 , and SiN.
  • 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, polar ultraviolet light (EUV), X-ray, and electron beam.
  • far-ultraviolet light is preferable, and the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, and 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), or 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 processing solution of the present invention may be used as a developing solution in a developing step or may be used as a rinsing solution in a rinsing step. Of these, it is preferably used as a rinsing solution in the rinsing process.
  • the treatment liquid of the present invention is used as a rinse liquid in the rinsing step, it is preferable to use a treatment liquid other than the treatment liquid of the present invention as the development liquid in the development 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.
  • Examples include a method of spraying the developer on the surface (spray method) or a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method). Be done.
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the developing time is usually 10 to 300 seconds, 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 another developing solution may be used, but it is preferable to use another developing solution.
  • development using a treatment solution 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 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, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), and 2 acetate.
  • butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, or butyl butanoate are preferable, and isoamyl acetate is more preferable.
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, and the like.
  • alcohol 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,
  • 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 monophenyl.
  • Glycol ether-based solvents containing hydroxyl groups such as ether; and the like are mentioned, and glycol ether-based solvents are preferable.
  • the ether-based solvent examples include the above-mentioned glycol ether-based solvent containing a hydroxyl group, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and a hydroxyl group-free glycol ether-based solvent such as diethylene glycol diethyl ether; anisole and phenitol.
  • Aromatic ether solvents such as dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyl tetrahydrofuran, perfluorotetratetra, 1,4-dioxane, isopropyl ether and the like. Of these, glycol ether solvents and 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. Can be mentioned.
  • Hydrocarbon solvents include, for example, pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoro.
  • Alibo hydrocarbon solvents such as heptane; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropyl
  • Aromatic hydrocarbon solvents such as benzene;
  • an unsaturated hydrocarbon solvent can also be used, and examples thereof include unsaturated hydrocarbon 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 in the hydrocarbon chain. Further, when the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.
  • the aliphatic hydrocarbon solvent which is a hydrocarbon solvent, may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as an aliphatic hydrocarbon-based solvent, compounds having the same carbon number and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, are aliphatic hydrocarbon-based compounds. It may be contained in a 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 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, pentyl propionate, and propionic acid. It is preferably selected from the group consisting of hexyl, heptyl propionate, butyl butanoate, butyl isobutate, and isobutyl isobutate, and isoamyl acetate or butyl isobutate is more preferable.
  • the above-mentioned ester having 6 or more carbon atoms and 2 or less heteroatoms is used in terms of further suppressing the suppression of swelling of the resist film.
  • 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.
  • 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, propylene carbonate and the like, 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 may be mixed with a solvent other than the above or water.
  • 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 amount of the developer. % Is particularly preferable.
  • the system 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.
  • an ester solvent represented by the following general formula (S1) or the following general formula (S2) is also preferable.
  • the ester solvent the ester 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, and 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 acetate, 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 being separated, and an ester solvent, a ketone solvent, and 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 solvents.
  • the combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
  • the mixing ratio of the solvent represented by the general formula (S1) and the combined solvent is usually a mass ratio. It is 20:80 to 99: 1, preferably 50:50 to 97: 3, more preferably 60:40 to 95: 5, and even more preferably 60:40 to 90:10.
  • 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, respectively. Or represents a halogen atom. R'' and R'''' may be combined with each other to form a ring. As R'' and R''', a hydrogen atom or an alkyl group is preferable.
  • the alkyl group represented by R'' and R'''', the alkoxyl group, and the alkoxycarbonyl group preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
  • R ′ ′′ represents an alkylene group or a cycloalkylene group, and an alkylene group is preferable.
  • the carbon number of the alkylene group represented by R'' is preferably 1 to 10, and the carbon number of the cycloalkylene group represented by R'''' is preferably 3 to 10.
  • the alkylene group represented by R ′′ may have an ether bond in the alkylene chain.
  • Alkyl group, cycloalkyl group, alkoxyl group and alkoxycarbonyl group represented by R'' and R'''', alkylene group and cycloalkylene group represented by R''', and R'' and R Rings formed by bonding'''' to each other may have substituents.
  • 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
  • R'' and R'''' are unsubstituted alkyl groups
  • R'''' is an unsubstituted alkylene group
  • R'' and R'''' are methyl. It is more preferably either a group or an ethyl group, and even more preferably R ′′ and R'''' are methyl groups.
  • the developing solution 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 (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 solvents.
  • the combined solvent may be one type or two or more types, but one type is preferable in order to obtain stable performance.
  • the mixing ratio of the solvent represented by the general formula (S2) and the combined solvent is usually a mass ratio. It is 20:80 to 99: 1, preferably 50:50 to 97: 3, more preferably 60:40 to 95: 5, and even more preferably 60:40 to 90:10.
  • 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 the number of carbon atoms is preferably 1 to 4, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
  • the rinsing step is a step of washing (rinsing) with a rinsing solution after the above-mentioned developing step.
  • the developed substrate is washed with the above rinsing solution.
  • the cleaning treatment method is not particularly limited, and for example, a method of continuously discharging the rinse liquid onto the 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 solution on the surface of the substrate (spray method), etc. can be applied.
  • the cleaning process is performed by the rotary discharge method, and the substrate is rotated at 2000 rpm to 4000 rpm after cleaning. It is preferable to remove the rinse liquid from the substrate by rotating with.
  • the rinsing time is usually 10 seconds to 300 seconds, preferably 10 seconds to 180 seconds, and more preferably 20 seconds to 120 seconds.
  • the temperature of the rinsing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • 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 usually 40 to 160 ° C, preferably 50 to 150 ° C, more preferably 50 to 110 ° C.
  • the drying time is usually 15 to 300 seconds, 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 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 composition ratio to a ratio at which 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.
  • an organic solvent having a higher SP value than the first organic solvent contained in the treatment liquid of the present invention is continuously supplied to the back surface of the wafer. Then, there is a method of suppressing the precipitation / precipitation of the resist in the waste liquid which is flowed to the waste liquid tank through the pipe 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.
  • the developer and the rinse liquid are stored in separate waste liquid tanks after use.
  • the inside of the treatment chamber may be washed with a solvent having a higher SP value than the first organic 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. preferable.
  • resist composition Next, a resist composition that is preferably used in combination with the treatment liquid of the present invention will be described in detail.
  • the resist composition preferably contains a resin (hereinafter, also referred to as "acid-decomposable resin” or “resin (A)”) whose polarity is increased by decomposition due to the action of an acid. That is, in the pattern forming method of the present invention, 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 positive pattern is preferably formed. , A negative 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 produce 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 that decomposes 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 alkyl groups (linear or branched chain), cycloalkyl groups (monocyclic or polycyclic), and alkenyl groups (straight chain). (Orchid 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. Is more preferable.
  • Rx 1 to Rx 3 may be combined to form a monocyclic or polycyclic ring.
  • an alkyl group of Rx 1 to Rx 3 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 is 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 polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Cycloalkyl group is preferred.
  • an aryl group of Rx 1 to Rx 3 an aryl group having 6 to 10 carbon atoms is preferable, 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 cycloalkyl group is preferable as the ring formed by bonding 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 tetracyclododecanyl.
  • a polycyclic cycloalkyl group such as a 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, a hetero atom such as a carbonyl group, or vinylidene. It may be replaced by a base. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. It may be replaced with.
  • 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.
  • cycloalkyl group, aryl group, and aralkyl group for example, one or more methylene groups are replaced with a group having a hetero atom such as an oxygen atom and / or a hetero atom such as a carbonyl group. May be good.
  • 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 each 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 hetero atom such as an oxygen atom or a group having a hetero atom 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 adamantan group.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may be combined with each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • 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 is an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, 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 a linking group may divalent have a iodine atom, -CO -, - O -, - S -, - SO -, - SO 2 -, have a fluorine atom or an iodine atom Examples thereof include a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene 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 chain.
  • 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 an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or 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 chain.
  • 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 fluorine atoms or iodine atoms, respectively. It has a cycloalkyl group (monocyclic or polycyclic) that may have a fluorine atom or an alkenyl group that may have a fluorine atom or an iodine atom (linear or branched chain), or a fluorine atom or an iodine atom. Represents an aryl group (monocyclic or polycyclic) which may be used.
  • 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.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may be replaced with, for example, one of the methylene groups being replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
  • 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 may independently have a hydrogen atom; a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; a fluorine atom, an iodine atom and an alkyl group.
  • a cycloalkyl group which may have a hetero atom selected from the group consisting of oxygen atoms; an aryl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; or It represents a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined, which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
  • M 1 represents a single bond or a divalent linking group.
  • Q 1 represents a fluorine atom, an alkyl group which may have a hetero atom selected from the group consisting of iodine atoms and an oxygen atom; Yes fluorine atom, a hetero atom selected from the group consisting of iodine atoms and an oxygen atom May be cycloalkyl group; aryl group selected from the group consisting of fluorine atom, iodine atom and oxygen atom; amino group; ammonium group; mercapto group; cyano group; aldehyde group; or a group combining these (for example).
  • Ar 1 represents an aromatic ring group which may have a fluorine atom or an iodine atom.
  • Rn 1 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, or an aryl group 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 chain), cycloalkyl groups (monocyclic or polycyclic), alkenyl groups (linear or branched chain), or aryl (linear or branched chain). 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.).
  • xa 1 Represented by xa 1, as the alkyl group which may have a substituent group, include groups represented by methyl group or -CH 2 -R 11.
  • R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group.
  • the halogen atom may be substituted, an alkyl group having 5 or less carbon atoms, or a halogen atom may be 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, and an -O-Rt- group.
  • 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- group. Is more preferable.
  • 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 is 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 polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Cycloalkyl group is preferred.
  • an aryl group of Rx 1 to Rx 3 an aryl group having 6 to 10 carbon atoms is preferable, 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.
  • cycloalkyl group formed by bonding two of Rx 1 to Rx 3 a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferable, and in addition, a norbornyl group, a tetracyclodecanyl group, and the like.
  • Polycyclic cycloalkyl groups such as a tetracyclododecanyl group and an adamantyl group are preferable. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or vinylidene. It may be replaced by a base. 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 (1 to 4 carbon atoms). Examples thereof include carbon numbers 2 to 6). 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, and further preferably 30 mol, based on all the repeating units in the resin (A). % Or more 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 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. May be good.
  • Group A A group consisting of the following repeating units (20) to (29).
  • Repetitive unit showing no acid decomposition property (32)
  • the resin (A) When the resist composition is used for EUV applications, 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 applications, 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 does not contain either a fluorine atom or a silicon atom. Further, when the resist 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 includes 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. Is preferably a different repeating 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 an 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, 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 an (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 group.
  • An alkyl group having 20 or less carbon atoms such as an octyl group and a dodecyl group is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is 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, a pyrrole ring, and the like.
  • a divalent aromatic ring group containing a heterocycle such as a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiaziazole 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 in the general formula (I). Examples thereof include 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 described in 43 ; 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, a butylene group, an alkylene group having 1 to 8 carbon atoms such as hexylene, and 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. That is, Ar 4 is preferably a benzene ring group.
  • the repeating unit represented by the general formula (I) 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, and there are a plurality of them. In some cases, they may be the same or different. When it has 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).
  • 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 thereof is not particularly limited, but is preferably 50 mol% or less, more preferably 45 mol% or less, and further 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., which will be described later. It is preferably different from other types of repeating units belonging to 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 thereof 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 an iodine atom does not include ⁇ repeating unit having an acid-degradable group >> and ⁇ repeating unit having an acid group >>, the above-mentioned fluorine atom or iodine
  • the content of the repeating unit having an 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 >>.
  • 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.
  • repeating unit containing at least one of a fluorine atom and an iodine atom 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 Repeating units having an acid group and repeating units having a fluorine atom or an iodine atom can be mentioned.
  • 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 referred to as "a repeating unit having a lactone group, a sultone group, or a carbonate group". It may also have). 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 sultone in the form of a bicyclo structure or a spiro structure.
  • a 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 a table represented by 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 a ring member atom having a 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.
  • It has a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulas (SL1-1) to (SL1-3).
  • Examples of the repeating unit 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 combining these. Represent. Of these, a single bond or a linking group represented by -Ab 1- CO 2- is preferable.
  • 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 general formulas (SL1-1) to (SL1-1). It represents a group formed by extracting one hydrogen atom from a ring member atom having a sultone structure represented by any 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.
  • R A 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 divalent combination thereof. 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 (also referred to as “photoacid generator”) that generates an acid by irradiation with active light or radiation described later.
  • 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 thereof 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 independently have a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR or -COOR:
  • R is the number of carbon atoms. 1 to 6 alkyl groups or fluorinated alkyl groups), or carboxyl groups.
  • 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.
  • 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 a "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 Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of them is used as the Tg (° C.) of the polymer.
  • the Bicerano method is described in the Precision of developers, Marcel Dekker Inc, New York (1993) and the like. Further, the calculation of Tg by the Bicerano method can be performed using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
  • 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 interaction 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 groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, hydroxyl groups, alkoxy groups, asyloxy groups, cyano groups, nitro groups, amino groups, halogen atoms, 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 alkenylene group, and a plurality of these.
  • Examples thereof include linked linking groups.
  • 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 have three or more constituent atoms excluding hydrogen atoms. It is a substituent.
  • 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 organic groups 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 is an alkyl group having 1 to 20 carbon atoms. Alternatively, an alkyl fluorinated group) and the like can be mentioned.
  • R' represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
  • 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, respectively.
  • An ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
  • R' is independently 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 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.
  • 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 atom.
  • Esther 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 thereof 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.
  • 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 of R 2c to R 4c are hydroxyl groups and the rest are hydrogen atoms. More preferably, two of R 2c to R 4c 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 thereof 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). Is preferable.
  • the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased.
  • the repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or an alkali on the main chain of the resin via a linking group. Repeat units to which soluble groups are 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 .
  • repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group is preferable.
  • 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 low molecular weight components from the resist film into the immersion liquid during immersion exposure.
  • a repeating unit include a repeating unit derived from 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclohexyl (meth) acrylate and the like.
  • 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.
  • crosslinked cyclic hydrocarbon group a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo [5, 2, 1, 0 2,6 ] decanyl group is preferable, and a norbonyl group or an adamantyl group is more preferable.
  • 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.
  • 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) has a repeating unit selected from the group consisting of a repeating unit having an oxatian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantin ring group. You may be doing it. Such repeating units are illustrated below.
  • the resin (A) has 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 be doing it.
  • all the repeating units are composed of (meth) acrylate-based repeating units.
  • all the repeating units are methacrylate-based repeating units
  • all the repeating units are acrylate-based repeating units
  • all 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 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000.
  • the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000.
  • 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 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 in 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 resist composition preferably contains a compound that generates an acid by active light or radiation (hereinafter, also referred to as “photoacid generator ⁇ PAG: Photo Acid Generator >>”).
  • the photoacid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight 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 low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and further 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 low molecular weight compound.
  • the photoacid generator is not particularly limited as long as it is known, but it is exposed to an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or by irradiation with active light or radiation, preferably electron beam or extreme ultraviolet light. Compounds that generate at least one of the tris (alkylsulfonyl) methides are preferred. More preferably, the compounds represented by the following general formulas (ZI), (ZII) and (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 generally 1 to 30, 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, and 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 anions examples include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, 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 preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of carbon atoms. Included are 3 to 30 cycloalkyl groups.
  • the aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion preferably includes an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.
  • the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples of this include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), and cycloalkyl groups (preferably having 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 12 carbon atoms).
  • Alkoxythio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), aryloxysulfonyl group (preferably carbon number 1 to 15).
  • Number 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) ), Cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms) and the like.
  • an alkyl group (preferably 1 to 15 carbon atoms) can be further mentioned as a substituent.
  • Examples of the aralkyl group in the aralkyl carboxylic acid anion include an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion and 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 -), fluorinated antimony (e.g., SbF 6 -) and the like .
  • 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 a fluorine atom or a group having a fluorine atom is substituted, and an alkyl group having 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 preferable.
  • non-nucleophilic anion a perfluoroaliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, and even more preferably a nonafluorobutane sulfonic acid anion, perfluoro Octane sulfonic acid anion, pentafluorobenzene sulfonic acid anion, 3,5-bis (trifluoromethyl) benzene sulfonic acid anion.
  • the pKa of the generated acid is -1 or less in order to improve the sensitivity.
  • 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 from each other.
  • L represents a divalent linking group, and when a plurality of L are present, 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 alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
  • the Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • 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.
  • both Xfs are fluorine atoms.
  • the alkyl groups of R 1 and R 2 may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferable. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms.
  • substituents 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.
  • R 1 and R 2 are preferably a fluorine atom or CF 3 .
  • 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 alkenylene group or a linking group in which a plurality of these groups are linked, and a linking group having a total carbon number of 12 or less is preferable. Of these, -COO-, -OCO-, -CO-, and -O- are preferable, and -COO- and -OCO- are more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to an alicyclic group, an aryl group, or a heterocyclic group (not only those having aromaticity but also not having aromaticity). (Including those), 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, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group or a tetracyclododeca.
  • Polycyclic cycloalkyl groups such as nyl group and 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 membranes in the post-exposure heating step.
  • Medium diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF (mask error 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.
  • a lactone structure can also be mentioned, and as a specific example, a lactone structure represented by the following general formulas (LC1-1) to (LC1-17) can be mentioned.
  • the cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms) or cyclo.
  • Alkyl 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, alkoxy group, ester group, amide. Examples thereof include a group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonic acid ester group and the like.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • the above-mentioned substituent corresponds to Rb 2 in the above-mentioned (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 and a cycloalkyl group.
  • R 201 , R 202 and R 203 at least one is preferably an aryl group, and more preferably 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.
  • the alkyl group and cycloalkyl group of R 201 to R 203 preferably, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms can be mentioned. More preferably, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like. More preferably, the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like.
  • 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).
  • 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 12 carbon atoms
  • Preferred examples thereof include 2 to 7) carbon atoms, but the present invention is not limited thereto.
  • R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • 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, benzothiophene and the like.
  • the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon.
  • the number 3 to 10 cycloalkyl groups (cyclopentyl group, cyclohexyl group, norbornyl group) can be mentioned.
  • 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 to 15 carbon atoms). ), Aryl group (for example, 6 to 15 carbon atoms), alkoxy group (for example, 1 to 15 carbon atoms), halogen atom, hydroxyl group, 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 (more preferably a sulfonic acid) having a size of the above, 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 at 2000 ⁇ 3 or less, and 1500 ⁇ 3 or less.
  • the above volume value was determined using "WinMOPAC" manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, then the most stable conformation of each acid is determined by the molecular force field calculation using the MM3 method with this structure as the initial structure, and then.
  • the "accessible volume" of each acid can be calculated by calculating the molecular orbital of these most stable conformations using the PM3 method. Note that 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. 2015/004533). ⁇ 0339>) of the specification can be incorporated, and these contents are incorporated in the specification of the present application. In addition, 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 pyruvates 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.
  • Preferable examples 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 for example, methyl lactate, ethyl lactate, propyl lactate and butyl lactate are preferably mentioned.
  • Preferred examples of the alkyl alkoxypropionate 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 are preferred.
  • Examples of the monoketone compound having 4 to 10 carbon atoms and which may contain a ring include 2-butanone, 3-methylbutanone, pinacol, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone and 4-.
  • alkylene carbonate for example, propylene carbonate, vinylene carbonate, ethylene carbonate and butylene carbonate are preferable.
  • Alkoxy alkyl acetates include, for example, -2-methoxyethyl acetate, -2-ethoxyethyl acetate, -2- (2-ethoxyethoxy) ethyl acetate, -3-methoxy-3-methylbutyl acetate, -1-methoxy-acetate. 2-propyl is preferably mentioned.
  • Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
  • Examples of the solvent that can be preferably used include a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure.
  • a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure examples include 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 two or more kinds may be used in combination.
  • a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed may be used as the organic solvent.
  • 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, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are particularly 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, dimethyl sulfoxide and the like.
  • propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate and ethyl ethoxypropionate are particularly preferable.
  • 2-Heptanone is most preferred.
  • the mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and further preferably 20/80 to 60/40. Is.
  • a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.
  • the solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate. Of these, the combination of ⁇ -butyl lactone and butyl acetate is particularly preferable.
  • the solvent for example, the solvent described in paragraphs 0013 to 0029 of JP2014-219664A can also be used.
  • the resist composition preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
  • a basic compound preferably, a compound having a structure represented by the following formulas (A1) to (E1) can be mentioned.
  • R200 , R201 and R202 may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), or a cycloalkyl group (preferably carbon). It represents a number 3 to 20) or an aryl group (preferably 6 to 20 carbon atoms), where R 201 and R 202 may be bonded to each other to form a ring.
  • alkyl group having a substituent an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl groups in these general formulas (A1) and (E1) are unsubstituted.
  • Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine, as well as imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure.
  • a compound having a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like can be mentioned.
  • 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, 1,8-diazabicyclo [5,4,0]. ] Undeca-7-en and the like can be mentioned.
  • Compounds having an onium hydroxide structure include triarylsulfonium hydroxides, phenacylsulfonium hydroxides, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxides and tris (t-butylphenyl) sulfoniums. Hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide 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.
  • 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.
  • alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like.
  • aniline derivative having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline and the like.
  • examples of the preferable basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
  • amine compound a primary, secondary or tertiary amine compound 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 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.
  • 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 1 or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule.
  • 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-) is preferable, and more preferably. It is an oxyethylene group.
  • 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 an aryl group 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. (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 an oxyalkylene group is formed.
  • the number of oxyalkylene groups is 1 or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule.
  • 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-) is preferable, and more preferably oxy. It is an ethylene group.
  • the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, a phosphate and the like, and among them, a halogen atom and a sulfonate are preferable.
  • Chloride, bromide, and iodide are particularly preferable as the halogen atom
  • organic sulfonate having 1 to 20 carbon atoms is particularly preferable as the sulfonate.
  • the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • 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 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
  • the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl and cyclohexyl.
  • substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano, a nitro, an acyl group, an acyloxy group and the like.
  • the amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those 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 aryloxy group. And so on.
  • the substituent of the substituent may be any of 2 to 6 positions.
  • the number of substituents may be any in the range of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups is 1 or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule.
  • 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-) is preferable, and more preferably. It is an oxyethylene group.
  • 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 adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium. It can be obtained by extracting with an organic solvent such as ethyl acetate or chloroform.
  • an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extracting with an organic solvent such as chloroform.
  • the composition according to the present invention has a proton-accepting functional group as a basic compound, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have proton-accepting properties.
  • a compound [hereinafter, also referred to as compound (PA)] that generates a compound changed to acidic may be further contained.
  • a proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
  • 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, crown ether, azacrown ether, 1st to tertiary amine, pyridine, imidazole, 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, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-413328A and paragraphs 0108 to 0116 of JP2014-134686 can be incorporated. , These contents are incorporated herein by reference.
  • the amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition.
  • the photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
  • the compounds described in paragraphs 0140 to 0144 of JP2013-11833A can be used (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.).
  • the resist composition may have a hydrophobic resin (A') 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 mixed uniformly. 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.
  • Hydrophobic resin from the viewpoint of uneven distribution in the film surface layer, "fluorine atom”, “silicon atom”, and has any one or more "CH 3 partial structure contained in the side chain portion of the resin" It is preferable, and it is more preferable to have two or more kinds. 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. It may be.
  • the partial structure having a fluorine atom may be 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, and further, a fluorine atom. It may have a substituent other than.
  • 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 those in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom. ..
  • 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 is intended to encompass CH 3 partial structure an ethyl group, and a propyl group having.
  • 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.
  • hydrophobic resin those described in JP-A-2011-24801, JP-A-2010-175859, and 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 surfactant described in ⁇ 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.); EFTOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351,
  • a fluoroaliphatic compound produced by a telomerization method also called a telomer method
  • an oligomerization method also called an 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.
  • a surfactant other than the fluorine-based and / or silicon-based surfactants described in ⁇ 0280> of US Patent Application Publication No. 2008/0248425 may be used.
  • One type of these surfactants may be used alone, or two or more types may be used in combination.
  • the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, still more preferably, based on the total solid content of the composition. It is 0.0005 to 1% by mass.
  • the resist composition contains a dissolution inhibitory compound, a dye, a plasticizer, 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 carboxy group. It may further contain an alicyclic group or an aliphatic compound).
  • the resist composition may further contain a dissolution-inhibiting compound.
  • a dissolution-inhibiting compound is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
  • an upper layer film may be formed on the upper layer of the resist film. It is preferable that the upper layer film is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
  • the upper layer film is not particularly limited, and a conventionally known upper layer film can be formed by a conventionally known method.
  • the upper layer film can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543.
  • the organic impurities having a boiling point of 300 ° C. or higher may be a resin component or a plasticizer contained in a plastic material (for example, an O-ring) used for a member of a manufacturing apparatus. It is presumed that it was eluted in the liquid at any point in the manufacturing process.
  • the content of the organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid is more preferably 0.001 to 30 mass ppm with respect to the total mass of the treatment liquid, and is 0.001 mass ppm to 15 mass ppm. This is even more preferable from the viewpoint of suppressing defects in the substrate when used in the semiconductor device manufacturing process, and even more preferably 0.001 mass ppm to 10 mass ppm, 0.001 mass ppm to 1 mass ppm. Is most preferable.
  • the content of organic impurities having a boiling point of 300 ° C. or higher is 30 mass ppm 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 from the viewpoint of suppressing that organic impurities do not volatilize and remain on the substrate surface, resulting in defective defects.
  • the content of organic impurities having a boiling point of 300 ° C. or higher is 5% 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.
  • organic impurities of 300 ° C. or higher include components such as diisononyl phthalate (DOP, boiling point 385 ° C.) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403 ° C.), and dioctyl adipate (DOA). , Boiling point 335 ° C.), Dibutyl phthalate (DBP, boiling point 340 ° C.), ethylene propylene rubber (EPDM, boiling point 300-450 ° C.) and the like have been confirmed.
  • DOP diisononyl phthalate
  • DINP diisononyl phthalate
  • DOA dioctyl adipate
  • Boiling point 335 ° C. Dibutyl phthalate
  • DBP dibutyl phthalate
  • EPDM ethylene propylene rubber
  • the content of organic impurities having a boiling point of 300 ° C. or higher in the treatment liquid is measured by DI-MS (Direct Injection Mass Chromatography).
  • DI-MS Direct Injection Mass Chromatography
  • Examples of the method for keeping the content of organic impurities 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 treatment liquid of the present invention preferably has a low content of metal impurities contained in the treatment liquid. Further, it is preferable that the content of each metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb in the treatment liquid is 0.001 to 100 mass ppt with respect to the total mass of the treatment liquid. ..
  • the metal component is present to a certain extent in the organic solvent, and may be mixed in the treatment liquid solution through these. Recently, it has been found that a metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb contained in the treatment liquid has a particularly large effect on defect performance.
  • the defect suppressing ability is excellent and 1 mass ppt or less. Has a more remarkable effect of suppressing defects. If the content of the metal component containing an element selected from the group consisting of Fe, Cr, Ni and Pb exceeds 100 mass ppt with respect to the total mass of the treatment liquid, metal particles (deterioration of defects) are invited and 0. When it exceeds .001 mass ppt, the production control can be performed stably, so that the quality of each production lot is stable.
  • the total amount satisfies the above range.
  • the content of metal impurities in the treatment liquid is measured by ICP-MS (inductively coupled plasma mass spectrometer). If the measurement is less than 1 mass ppt, it is difficult to measure with the undiluted solution. Therefore, it can be measured by concentrating the treatment solution as necessary. Examples of the method for keeping the content of metal impurities in the treatment liquid within the above range include the methods described in the purification step described later (for example, filter treatment using an ion exchange resin or a metal adsorption member).
  • the “base” as used in the present invention includes, for example, a semiconductor substrate made of a single layer and a semiconductor substrate made 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.
  • the configuration is not particularly limited, and for example, exposed integration of interconnect features such as metal wires and dielectric materials on the above-mentioned semiconductor substrate such as silicon. It may have a circuit structure.
  • Metals and alloys used in the interconnect structure include, but are limited to, aluminum and copper and alloyed aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It is not something that is done. Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide and carbon-doped silicon oxide may be provided on the semiconductor substrate.
  • the treatment liquid of the present invention preferably carries out the following purification steps in order to keep the contents of metal components, organic impurities having a boiling point of 300 ° C. or higher, and water 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 materials used in the production of the organic solvent before the production of the organic solvent constituting the treatment liquid. Further, the purification treatment II is a treatment for purifying the organic solvent constituting the treatment liquid at the time of production and / or after production. Further, the purification treatment III is a treatment for purifying each component 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 is preferable to obtain the desired treatment liquid. Purification may be carried out after purifying each organic solvent and then mixing, or after mixing each organic solvent, purification may be performed. In particular, a method of blending a purified organic solvent is preferable because 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 low 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".
  • a first ion exchange treatment for performing an ion exchange treatment of the liquid to be purified a dehydration treatment for dehydrating the liquid to be purified after the first ion exchange treatment, and a distillation for distilling the liquid to be purified after the dehydration treatment.
  • An embodiment in which the second ion exchange treatment for performing the ion exchange treatment of the liquid to be purified after the treatment and the distillation treatment and the organic impurity removal treatment for removing the organic impurities of the liquid to be purified after the second ion exchange treatment are carried out in this order.
  • 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 ion.
  • the organic impurity removing treatment for removing the organic impurities in the liquid to be purified after the exchange treatment may be carried out in this order.
  • ionic components for example, metal components
  • a first ion exchange means such as an 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 bed 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 membrane made of a polymer-based material such as polyimide-based, cellulosic-based and 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, it can be removed, and eluates from pipes such as stainless steel (SUS) used as a liquid feeding line can be removed.
  • the second ion exchange means include those in which an ion exchange resin is filled in a tower-shaped container and an ion adsorption film, and an ion adsorption film is preferable because it can be processed at a high flow velocity.
  • the ion adsorption membrane include Neocepta (trade name, manufactured by Astom).
  • each of the above-mentioned treatments is preferably carried out in a hermetically sealed state and under an inert gas atmosphere in which water is unlikely to be mixed into the liquid to be purified. Further, each treatment is preferably performed in an inert gas atmosphere having a dew point temperature of ⁇ 70 ° C. or lower in order to suppress the mixing of water as much as possible. This is because, in an inert gas atmosphere of ⁇ 70 ° C. or lower, the water concentration in the gas phase is 2 mass ppm or less, so that the possibility of water being mixed in the liquid to be purified is reduced.
  • the purification step includes an adsorption purification treatment of a metal component using silicon carbide, which is described in International Publication No. WO2012 / 043496.
  • organic impurity removing treatment high boiling point organic impurities and the like (including organic impurities 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. It should be noted that having an organic 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 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.
  • n-long-chain alkyl alcohol structural isomer when 1-long-chain alkyl alcohol is used as the solvent
  • an alkyl group can be mentioned as the organic skeleton.
  • the base material (material) constituting the organic impurity adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin supporting activated carbon.
  • 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 thus 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 “filtration member” described later, and a filter having a pore diameter of less than 3 nm is used as an “organic impurity removing filter”.
  • 1 ⁇ angstrom
  • the purification step of the present invention may further include, for example, purification treatment V and purification treatment 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 step 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 carboxy 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 the filtration means is carried out using a filtration member provided with a filter having a particle removal diameter of 20 nm or less.
  • 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 when the liquid to be purified is purified. Examples include dust, dust, particles of organic solids and inorganic solids brought in as contaminants, and those that finally exist as particles without being dissolved in the liquid to be purified are applicable.
  • the "particulate impurities” also include colloidal impurities containing metal atoms.
  • the metal atom is not particularly limited, but is derived from Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, and Pb (preferably Fe, Cr, Ni, and Pb).
  • impurities containing these metal atoms Is easy to colloid. With the metal ion adsorption member, it tends to be difficult to remove colloidal impurities.
  • a filter having a particle removal diameter of 20 nm or less for example, a microfiltration membrane having a pore diameter 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 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 removal diameter of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm.
  • the filtration member may further include a filter having a particle removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles having a pore diameter of 50 nm or more).
  • a filter having a particle removal diameter of 20 nm or less for example, pore size.
  • the liquid to be purified is filtered using a filter with a particle removal diameter of 50 nm or more (for example, a precision filtration film for removing fine particles having a pore size of 50 nm or more).
  • the liquid to be purified obtained by obtaining each of these treatments can be used in the composition of the treatment liquid of the present invention or as the treatment liquid of the present invention itself.
  • 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. .. In addition, 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 It is also possible to store the treatment 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 Corporation 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, tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexfluoride.
  • FEP tetrafluoroethylene-ethylene copolymer resin
  • ETFE tetrafluoroethylene-ethylene copolymer resin
  • ECTFE ethylene trifluorochloride-ethylene copolymer resin
  • PVDF vinylidene fluoride resin
  • a container having an inner wall made of a fluororesin when a container having an inner wall made of a fluororesin is used, it is said that ethylene or a propylene oligomer is eluted as compared with a case where a container having an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin is used.
  • the occurrence of defects can be suppressed.
  • Specific examples of such a container in which the inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris.
  • Containers can also be used.
  • the inner wall of the non-metal material it is preferable that the elution of the organic component in the non-metal material into the treatment liquid is suppresse
  • 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 electropolishing 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>- ⁇ 0014> of JP2015-227501 and paragraphs ⁇ 0036>- ⁇ 0042> of JP2008-264929 can be used.
  • the metal material is electropolished so that the chromium content in the passivation layer on the surface is higher than the chromium content in the parent phase. Therefore, it is presumed that a solution having a reduced metal component (metal impurities) can be obtained because the metal component does not easily flow out into the solution from the inner wall coated with the electropolished metal material.
  • the metal material is preferably buffed.
  • the method of buffing is not particularly limited, and a known method can be used.
  • the size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
  • the buffing is preferably performed before the electrolytic polishing.
  • the metal material may be processed by combining one 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 abrasive grains. ..
  • a container having the above-mentioned container and the above-mentioned treatment liquid contained in the container may be 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 production of the treatment liquid of the present invention, the opening and / or cleaning of the storage container, the handling including the filling of the treatment liquid, the treatment analysis, and the measurement are all preferably performed in a clean room.
  • the clean room preferably meets the 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
  • ISO class 2 ISO class 3
  • ISO class 4 more preferably ISO class 1 or ISO class 2
  • the treatment liquid of the present invention or the organic solvent contained in the treatment liquid can keep the contents of organic impurities, metal components, and water having a boiling point of 300 ° C. or higher within a desired range, and remove foreign substances and coarse particles. In order to do so, it is preferably filtered.
  • the filter used for filtering can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. Examples of the material constituting the filter include a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, polyethylene, and a polyolefin resin such as polypropylene (PP) (high density and ultrahigh molecular weight). ) Etc. can be mentioned.
  • polyamide resins, PTFE, and polypropylene are preferable, and by using a filter formed of these materials, highly polar foreign substances that easily cause particle defects can be removed. In addition to being able to be effectively removed, the amount of metal components (metal impurities) can be reduced more efficiently.
  • the critical surface tension of the filter is preferably 70 mN / m or more as the lower limit.
  • the upper limit is preferably 95 mN / m or less.
  • the critical surface tension of the filter is more preferably 75 mN / m or more and 85 mN / m or less.
  • the value of the critical surface tension is a nominal value of the manufacturer.
  • the filter used for filtering is not particularly limited as long as it has been conventionally used for filtering purposes.
  • the material constituting the filter include a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, polyethylene, and a polyolefin resin such as polypropylene (PP) (high density and ultrahigh molecular weight). ) Etc. can be mentioned.
  • a fluororesin such as PTFE (polytetrafluoroethylene)
  • a polyamide resin such as nylon
  • polyethylene polyethylene
  • PP polyolefin resin
  • Etc. polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably about 0.001 to 1.0 ⁇ m, more preferably about 0.01 to 0.5 ⁇ m, and even more preferably about 0.01 to 0.1 ⁇ m.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When different filters are combined and filtering is performed twice or more, the filters may be of the same type or different types of each other, but they are different types of each other. Is preferable. Typically, it is preferable that the first filter and the second filter differ in at least one of the pore diameter and the constituent material. It is preferable that the pore diameters of the second and subsequent filters are the same or smaller than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., and the like.
  • P-nylon filter (pore diameter 0.02 ⁇ m, critical surface tension 77 mN / m) made of polyamide; (manufactured by Nippon Pole Co., Ltd.), "PE clean filter (pore diameter 0.02 ⁇ m)” made of high-density polyethylene; (Manufactured by Nippon Pole Co., Ltd.) and "PE / Clean Filter (pore diameter 0.01 ⁇ m)” made of high-density polyethylene; (manufactured by Nippon Pole Co., Ltd.) can also be used.
  • the purified liquid and the filter used for filtering are used.
  • the relationship with the material is the interaction radius (R0) in the Hansen solubility parameter (HSP) space that can be derived from the material of the filter used for filtering, and the Hansen space that can be derived from the treatment liquid or the liquid contained in the organic solvent contained in the treatment liquid.
  • It is preferably an organic solvent contained.
  • (Ra / R0) ⁇ 0.98 is preferable, and (Ra / R0) ⁇ 0.95 is more preferable.
  • the lower limit is preferably 0.5 or more, more preferably 0.6 or more, and further preferably 0.7. Although the mechanism is not clear, if it is within this range, the formation of the particle metal or the growth of the particle metal during long-term storage is suppressed.
  • the combination of these filters and the treatment liquid or the organic solvent contained in the treatment liquid is not particularly limited, and examples thereof include those of US Pat. No. 6,2016,089622.
  • the second filter a filter made of the same material as the first filter described above can be used.
  • a filter having the same pore size as the first filter described above can be used.
  • the ratio of the pore diameter of the second filter to the pore diameter of the first filter (the pore diameter of the second filter / the pore diameter of the first filter). ) Is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.9.
  • the present invention is composed of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Pd, and Zn with respect to the treatment liquid or the organic solvent contained in the treatment liquid.
  • the content of one or more metal elements selected from the group is particularly low (for example, the content of the above-mentioned metal elements is 1000 mass by mass with respect to the treatment liquid or the organic solvent contained in the treatment liquid.
  • Impurities containing these metal elements tend to colloid (in the case of ppt or less). Therefore, it tends to be difficult to remove colloidal impurities with the ion adsorption membrane. Therefore, the present inventors have found that colloidal impurity components can be removed by purification using a microfiltration membrane having a pore size of 20 nm or less.
  • the treatment liquid of the present invention or the organic solvent contained in the treatment liquid is preferably purified by using an ion adsorption means in addition to the above-mentioned filter.
  • an ion adsorption means the surface of cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluororesin or the like is modified with an anionic group such as a sulfo group or a carboxy group, a cationic group, or both. It is preferably an ion adsorption means.
  • the ion adsorbing means modified with an anionic group can remove cations such as Na ion and Ca ion, and the ion adsorbing means modified with a cationic group can remove anions such as Cl ions and acid components. Can be removed.
  • the ion adsorption means may use an anionic group, a cationic group, or a combination thereof, depending on the intended purpose.
  • the ion adsorption means may be a filter.
  • the above filtration step may be repeated a plurality of times depending on the purpose.
  • the filter used is preferably treated before filtering the treatment liquid or the organic solvent contained in the treatment liquid.
  • the liquid used for this treatment is not particularly limited, but if it is an organic solvent contained in the treatment liquid of the present invention, the desired effect of the present invention can be remarkably obtained.
  • the upper limit of the temperature at the time of filtering is preferably room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower.
  • the lower limit of the temperature at the time of filtering is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher. Filtering can remove particulate foreign matter or impurities, but when performed at the above temperature, the amount of particulate foreign matter or impurities dissolved in the treatment liquid or the organic solvent contained in the treatment liquid is reduced. , Filtering is done more efficiently.
  • metal components metal impurities
  • filtering at the above temperature some of the metal components (metal impurities) floating in a colloid are aggregated, and these agglomerated substances are efficiently removed by filtering, so that the metal components (metals) It is considered that the content of (impurities) can be easily adjusted to a predetermined amount.
  • the pressure pulsation during filtration is as small as possible.
  • the filtration rate is not particularly limited, but from the viewpoint of being more excellent in the effect of the present invention, 0.6 L / min / m 2 or more is preferable, and 0 .75L / min / m 2 or more preferably, 1.0 L / min / m 2 or more is more preferable.
  • the filter is set with a differential pressure resistance that guarantees filter performance (the filter does not break), and when this value is large, the filtration rate can be increased by increasing the filtration pressure. That is, the upper limit of the filtration rate usually depends on the differential pressure resistance of the filter, but is usually preferably 10.0 L / min / m 2 or less.
  • the filtration pressure is preferably 0.001 MPa or more and 1.0 MPa or less, and 0.003 MPa or more and 0. It is more preferably 5 MPa or less, and particularly preferably 0.005 MPa or more and 0.3 MPa or less.
  • the filtration pressure is 0.005 MPa or more and 0.3 MPa or less.
  • the filtration speed decreases. For example, by connecting a plurality of filters equipped with the same type of filtration filter membrane in parallel, the filtration area is expanded and the filtration pressure is increased. As it is lowered, this makes it possible to compensate for the decrease in filtration rate.
  • a 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 pipeline and passing the purified liquid or the like through the grounded mesh.
  • the static elimination step may be performed at any time from the supply of the raw material to the filling of the purified product, and is selected from the group consisting of, for example, the raw material supply step, the reaction step, the liquid preparation step, the purification step, the filtration step, and the filling step. It is preferably contained before at least one step to be carried out. In particular, it is preferable to perform the 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.
  • photoacid generator As the photoacid generator, the photoacid generator (B-1) shown below was used.
  • the acid diffusion control agent As the acid diffusion control agent, the acid diffusion control agent (E-1) shown below was used.
  • ⁇ Exposure> The prepared wafer with a resist film was subjected to EUV exposure with NA (numerical aperture of lenses, Natural Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, (1) a line-and-space pattern having a pitch of 40 nm and a width of 20 nm (corresponding to a mask for forming a “dense pattern” in Table 2), or (2) a line having a pitch of 108 nm and a width of 20 nm. EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming an and-space pattern (corresponding to the “sparse pattern” forming mask in Table 2). After irradiation, it was taken out from the EUV exposure apparatus and immediately baked (PEB) at 90 ° C. for 60 seconds.
  • PEB immediately baked
  • ⁇ Rinse> (Preparation of treatment solution) As shown in Table 1 described later, by mixing the first organic solvent and the second organic solvent in a predetermined ratio, or by mixing the first organic solvent, the second organic solvent, and the third organic solvent. Each treatment liquid was prepared by mixing at a predetermined ratio. As the first organic solvent, the second organic solvent, and the third organic solvent used in each treatment liquid, semiconductor grade solvents were used. Each of the obtained treatment liquids was used as a rinse liquid in the rinse treatment described later.
  • the drying time of the treatment liquid was evaluated by the following procedure. Generally, it is considered that the longer the drying time of the treatment liquid, the greater the influence of the capillary force and the faster the collapse. Therefore, the shorter the drying time of the treatment liquid, the more the pattern collapse is suppressed, which is preferable.
  • each treatment solution (23 ° C.) shown in Table 1 was spray-discharged at a flow rate of 200 mL / min for 5 seconds, and 2000 rpm (rpm). The time taken for the solvent to dry was visually observed when it was dried in. The evaluation results are shown in "Drying time (seconds)" in Table 1.
  • ⁇ Resolution (pattern collapse performance)> The resolution of line-and-space patterns exposed at different exposure amounts was observed at a magnification of 200 k using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), and the pattern collapsed within the observed field of view. The minimum line width in which is not occurring was calculated and used as an index of pattern collapse. The smaller this value is, the better the pattern collapse performance is. The minimum line width obtained was evaluated according to the following evaluation criteria. The pattern collapse performance was evaluated for both the pattern formed by using the dense pattern forming mask and the pattern formed by using the sparse pattern forming mask.
  • A Minimum line width is 16 nm or less
  • B Minimum line width is more than 16 nm and 18 nm or less
  • C Minimum line width is more than 18 nm and 20 nm or less
  • D Minimum line width is more than 20 nm and 22 nm or less
  • E The minimum line width is over 22 nm
  • a dot pattern for evaluating bridge defect suppression was produced by the following procedure.
  • resist film formation Each of the resist compositions of Examples and Comparative Examples was applied onto a 12-inch silicon wafer and baked (PB) at 120 ° C. for 60 seconds to form a resist film having a film thickness of 40 nm.
  • EUV exposure The prepared wafer with a resist film was subjected to EUV exposure with NA (numerical aperture of lenses, Natural Aperture) 0.25 and Quasar illumination (Quasar 45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a dot pattern having a pitch of 60 nm and dots of 30 nm on the wafer. After irradiation, it was taken out from the EUV exposure apparatus and immediately baked (PEB) at 90 ° C. for 60 seconds.
  • PEB immediately baked
  • Tables 1 and 2 are shown below. In the following, the composition of each treatment liquid is shown in Table 1. Further, Table 2 corresponds to the evaluation result of the pattern formed by using each treatment liquid shown in Table 1.
  • the "SP value” in each table is a numerical value calculated based on the Fedors method, and the unit is MPa 1/2 .
  • the calculation method of the "SP value” is as described above.
  • “ ⁇ D”, “ ⁇ P” and “ ⁇ H” in each table are obtained by the following formulas (1) to (3), respectively.
  • the treatment liquid further contains an alcohol solvent having an SP value of 19.0 to 21.0 MPa 1/2 , which is a third organic solvent, the effect of suppressing pattern collapse, which is improved by the contribution of the first organic solvent, is improved. It is clear that the occurrence of bridge defects is more suppressed without excessively reducing.
  • the content of the second organic solvent in the treatment liquid is 80% by mass or more with respect to the total content of the first organic solvent and the second organic solvent, the amount of change in LWR of the formed pattern was confirmed to be smaller.
  • the resistivity of the treatment liquid is smaller. It was confirmed that.

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Abstract

Le problème abordé par la présente invention est de fournir une solution de traitement pour la formation de motifs sur film de réserve, cette solution de traitement permettant de limiter l'affaissement de motif pendant la formation de motif et d'obtenir une faible résistivité. Un autre problème abordé par la présente invention est de fournir un procédé de formation de motif utilisant la solution de traitement susmentionnée pour la formation de motifs sur film de réserve.　Cette solution de traitement est utilisée pour réaliser un développement et/ou un nettoyage par rapport à un film de réserve obtenu à partir d'une composition sensible aux rayons actiniques ou au rayonnement, et elle est destinée à former des motifs sur un film de réserve contenant un solvant organique. La solution de traitement contient un premier solvant organique qui satisfait des conditions prédéterminées et une seconde solution organique qui satisfait des conditions prédéterminées. La teneur du second solvant organique est d'au moins 10 % en masse par rapport à la teneur totale du premier solvant organique et du second solvant organique, et la teneur du second solvant organique est d'au moins 10 % en masse par rapport à la masse totale de la solution de traitement.
PCT/JP2020/013751 2019-03-29 2020-03-26 Solution de traitement et procédé de formation de motif WO2020203670A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016017232A1 (fr) * 2014-07-31 2016-02-04 富士フイルム株式会社 Procédé de formation de motif, motif de photorésine, procédé de fabrication d'un dispositif électronique et dispositif électronique
WO2016136476A1 (fr) * 2015-02-27 2016-09-01 富士フイルム株式会社 Procédé de formation de motifs, composition de résine sensible à une lumière active ou sensible à un rayonnement, film sensible à une lumière active ou sensible à un rayonnement, procédé de fabrication de dispositif électronique et dispositif électronique
WO2016208300A1 (fr) * 2015-06-24 2016-12-29 富士フイルム株式会社 Procédé de formation de motif, stratifié et composition de réserve pour un développement de solvant organique
WO2017056832A1 (fr) * 2015-09-30 2017-04-06 富士フイルム株式会社 Composition sensible à une lumière active ou sensible à un rayonnement, film de résist l'utilisant, procédé de formation de motif et procédé de fabrication d'un dispositif électronique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016017232A1 (fr) * 2014-07-31 2016-02-04 富士フイルム株式会社 Procédé de formation de motif, motif de photorésine, procédé de fabrication d'un dispositif électronique et dispositif électronique
WO2016136476A1 (fr) * 2015-02-27 2016-09-01 富士フイルム株式会社 Procédé de formation de motifs, composition de résine sensible à une lumière active ou sensible à un rayonnement, film sensible à une lumière active ou sensible à un rayonnement, procédé de fabrication de dispositif électronique et dispositif électronique
WO2016208300A1 (fr) * 2015-06-24 2016-12-29 富士フイルム株式会社 Procédé de formation de motif, stratifié et composition de réserve pour un développement de solvant organique
WO2017056832A1 (fr) * 2015-09-30 2017-04-06 富士フイルム株式会社 Composition sensible à une lumière active ou sensible à un rayonnement, film de résist l'utilisant, procédé de formation de motif et procédé de fabrication d'un dispositif électronique

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