WO2021065549A1 - 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び、電子デバイスの製造方法 - Google Patents

感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び、電子デバイスの製造方法 Download PDF

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WO2021065549A1
WO2021065549A1 PCT/JP2020/035312 JP2020035312W WO2021065549A1 WO 2021065549 A1 WO2021065549 A1 WO 2021065549A1 JP 2020035312 W JP2020035312 W JP 2020035312W WO 2021065549 A1 WO2021065549 A1 WO 2021065549A1
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group
sensitive
general formula
radiation
carbon atoms
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PCT/JP2020/035312
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English (en)
French (fr)
Japanese (ja)
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金子　明弘
啓太 加藤
研由 後藤
雅史 小島
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富士フイルム株式会社
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Priority to JP2021550612A priority Critical patent/JPWO2021065549A1/ja
Publication of WO2021065549A1 publication Critical patent/WO2021065549A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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

Definitions

  • the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition, a sensitive light-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device.
  • Patent Document 1 is a resist composition containing a base material component (A) whose solubility in a developing solution is changed by the action of an acid and an acid generator component (B) that generates an acid by exposure.
  • a resist composition in which the component (A) has a specific structure and the acid generator component (B) has a specific structure is disclosed.
  • the line width of the line portion may be made as small as possible, or the adjacent line portion may be formed. In some cases, it may be required to increase the line width of the line and make the space between the lines as small as possible. In order to meet such a demand, it is generally considered to adjust the composition of the resist composition for forming the pattern, but the line width is increased while ensuring the roughness performance of the obtained pattern. It has been very difficult to resolve a pattern in which the distance between adjacent lines is extremely small or a pattern in which the distance between adjacent lines is extremely small. Although the positive photosensitive composition described in Patent Document 2 is known, the pattern formed by using EB and EUV light has not been miniaturized.
  • the present invention provides a sensitive light-sensitive or radiation-sensitive resin composition capable of reducing the collapse front width, increasing the bridge front width, excellent resolution margin, and forming a pattern excellent in roughness performance. That is the issue.
  • Another object of the present invention is to provide a sensitive light-sensitive or radiation-sensitive resin film, a pattern forming method, and a method for manufacturing an electronic device with respect to the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. ..
  • B Compounds that generate acid by irradiation with active light or radiation, A sensitive light-sensitive or radiation-sensitive resin composition containing A light-sensitive or radiation-sensitive resin composition in which the resin (A) does not have a repeating unit having an epoxy group and / or an oxetanyl group.
  • R 1 and R 2 independently represent a hydrogen atom or an organic group. R 1 and R 2 may be combined with each other to form a ring. * Represents the bond position.
  • R 3 independently represents a hydrogen atom or an organic group.
  • R 4 independently represents a hydrogen atom or an organic group. * Represents the bond position.
  • X 1 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group.
  • Y 1 represents a single bond or a divalent linking group.
  • Z 1 represents a single bond or (n 1 + 1) valent linking group.
  • R 21 and R 22 independently represent a hydrogen atom or an organic group. R 21 and R 22 may be combined with each other to form a ring.
  • n 1 represents an integer of 1 or more.
  • the plurality of R 21s may be the same or different, and the plurality of R 22s may be the same or different.
  • At least one of X 1 , Y 1 , Z 1 , R 21 and R 22 contains an aromatic group.
  • X 2 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group.
  • Y 2 represents a single bond or a divalent linking group.
  • Z 2 represents a single bond or (n 2 + 1) valent linking group.
  • R 23 represents a hydrogen atom or an organic group.
  • R 24 represents a hydrogen atom or an organic group.
  • n 2 represents an integer of 1 or more. When n 2 represents an integer of 2 or more, the plurality of R 23s may be the same or different, and the plurality of R 24s may be the same or different. At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 contains an aromatic group.
  • X 3 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
  • Y 3 represents a single bond or a divalent linking group.
  • Ar represents an aromatic group.
  • Z 3 represents a single bond or (n + 1) valent linking group.
  • R 31 and R 32 each independently represent a hydrogen atom or an organic group. R 31 and R 32 may be combined with each other to form a ring.
  • n represents an integer of 1 or more. When n represents an integer of 2 or more, the plurality of R 31s may be the same or different, and the plurality of R 32s may be the same or different.
  • Y 3 in the general formula (3) is a single bond, -COO-, or -CONR 6 - represents, R 6 represents a hydrogen atom or an alkyl group, [3] to any one of [5]
  • the sensitive light-sensitive or radiation-sensitive resin composition according to.
  • R 31 and R 32 in the above general formula (3) independently form a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
  • the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [3] to [6].
  • X 4 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
  • Y 4 represents a single bond or a divalent linking group.
  • R 41 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
  • the process of exposing the resist film and A pattern forming method comprising a step of developing the exposed resist film using a developing solution to form a pattern.
  • a sensitive light-sensitive or radiation-sensitive resin composition capable of reducing the collapse front width, increasing the bridge front width, excellent resolution margin, and forming a pattern excellent in roughness performance. can do. Further, according to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin film, a pattern forming method, and a method for manufacturing an electronic device with respect to the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. ..
  • the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified.
  • Y when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
  • (meth) acrylic is a general term including acrylic and methacrylic, and means “at least one of acrylic and methacrylic”.
  • (meth) acrylic acid means “at least one of acrylic acid and methacrylic acid”.
  • active ray 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:). It means Electron Beam) and the like.
  • light means active light or radiation.
  • exposure refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified 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.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Toso).
  • 1 ⁇ is 1 x 10-10 m.
  • the acid dissociation constant (pKa) represents pKa in an aqueous solution, and specifically, using the following software package 1, a value based on a database of Hammett's substituent constants and known literature values is used. , It is a value obtained by calculation. All pKa values described herein indicate values calculated using this software package.
  • pKa can also be obtained by the molecular orbital calculation method.
  • a specific method for this there is a method of calculating H + dissociation free energy in a solvent based on a thermodynamic cycle.
  • water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when pKa cannot be obtained with water.
  • the calculation method of H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature and are not limited thereto.
  • DFT density functional theory
  • There are a plurality of software that can perform DFT and examples thereof include Gaussian16.
  • pKa in the present specification refers to a value obtained by calculation based on a database of Hammett's substituent constants and known literature values using software package 1. If it cannot be calculated, the value obtained by Gaussian 16 based on DFT (Density Functional Theory) shall be adopted.
  • the notation that does not describe substitution or non-substituent 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.
  • the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent” are not particularly limited.
  • the number of substituents may be, for example, one, two, three, or more.
  • the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, the following substituent T can be selected.
  • the substituent T includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkoxy group such
  • Acrylic groups alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfonyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group ; And combinations of these.
  • the actinic or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “resist composition”) will be described.
  • the resist composition of the present invention may be a positive type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
  • the composition of the present invention is typically a chemically amplified resist composition.
  • the sensitive light-sensitive or radiation-sensitive resin composition of the present invention includes (A) at least one of a partial structure represented by the general formula (1a) described later and a partial structure represented by the general formula (1b) described later. It contains a resin containing a repeating unit (a1) having an aromatic group, and (B) a compound that generates an acid by irradiation with active light or radiation.
  • the collapse front width can be reduced, the bridge front width can be increased, the margin of resolution is excellent, and a pattern having excellent roughness performance can be formed.
  • the "falling front width” means a line width that can be formed (resolved) without the line portion falling.
  • the "bridge front width” means a line width that can be formed (resolved) without contacting adjacent line portions.
  • the “resolution margin” means the value obtained by subtracting the collapse front width from the bridge front width. The larger this value is, the larger the tolerance of resolution (the range of the line width that can be formed in the line portion) is, which means that the value is excellent.
  • the resin (A) has a partial structure represented by the general formula (1a) described later and a partial structure represented by the general formula (1b) described later. Includes a repeating unit (a1) having at least one of and an aromatic group.
  • at least one of the partial structure represented by the general formula (1a) and the partial structure represented by the general formula (1b) described later has a sulfonamide group having a very high polarity. Therefore, the difference in surface energy between the sensitive light-sensitive or radiation-sensitive film formed from the above composition and the substrate is small, so that the adhesion between the sensitive light-sensitive or radiation-sensitive film and the substrate is improved.
  • the sulfonamide group as a highly polar group improves the adhesion between the sensitive light-sensitive or radiation-sensitive film and the substrate as described above, but on the other hand, the exposed portion and the unexposed portion It is considered that the dissolution contrast with respect to the developing solution during the period tends to decrease.
  • the unexposed portion is also highly polarized by the sulfonamide group (the unexposed portion is easily dissolved by the alkaline developer).
  • the dissolution contrast is lowered, and it becomes difficult to form a pattern in which the line width of the line portion is extremely small.
  • it becomes difficult to form a pattern in which the spacing between adjacent line portions is extremely small even if the line width of the adjacent line portions is increased to make the spacing between the line portions as small as possible, the above dissolution Due to the decrease in contrast, it is difficult to dissolve the line portion and the line portion with an alkaline developer, and the line portion and the line portion are easily connected (bridged)).
  • the unexposed portion is also highly polarized by the sulfonamide group (the unexposed portion becomes difficult to be dissolved by the organic developer).
  • the dissolution contrast is lowered, and it becomes difficult to form a pattern in which the line width of the line portion is extremely small.
  • it becomes difficult to form a pattern in which the spacing between adjacent line portions is extremely small even if the line width of the adjacent line portions is increased to make the spacing between the line portions as small as possible, the above dissolution Due to the decrease in contrast, it is difficult to dissolve the unexposed part with an organic developer, and the line part and the line part are connected (bridged) (because).
  • the line portion is less likely to fall due to the high adhesion to the substrate, and the dissolution contrast between the exposed portion and the unexposed portion with respect to the developing solution is not impaired. It is considered that the fall front width can be reduced.
  • the bridge front width can be increased according to the present invention because the dissolution contrast of the exposed portion and the unexposed portion with respect to the developing solution is not impaired.
  • the fall front width can be reduced and the bridge front width can be increased.
  • the exposure margin corresponding to the difference between the bridge front width and the collapse front width is also excellent.
  • the photoacid generator may have a polar group, or may be an ionic compound. Therefore, the photoacid generators tend to agglomerate with each other.
  • the sulfonamide group as a highly polar group contained in the resin (A) can suppress the aggregation of the photoacid generator described above by interacting with the photoacid generator. Therefore, the photoacid generator is more uniformly contained in the actinic light-sensitive or radiation-sensitive film, and as a result, the reaction between the acid generated from the photoacid generator and the resin in the exposed portion becomes more uniform. Since it is performed uniformly, it is considered that the roughness performance is further excellent.
  • the resist composition is a repeating unit (a1) having (A) at least one of a partial structure represented by the general formula (1a) described later and a partial structure represented by the general formula (1b) described later, and an aromatic group.
  • the resist composition is a repeating unit (a1) having (A) at least one of a partial structure represented by the general formula (1a) described later and a partial structure represented by the general formula (1b) described later, and an aromatic group.
  • the resin (A) does not have a repeating unit having an epoxy group and / or an oxetanyl group.
  • the resin (A) contains a repeating unit (a1) having at least one of the partial structure represented by the following general formula (1a) and the partial structure represented by the following general formula (1b) and an aromatic group.
  • R 1 and R 2 independently represent a hydrogen atom or an organic group. R 1 and R 2 may be combined with each other to form a ring. * Represents the bond position.
  • R 3 independently represents a hydrogen atom or an organic group.
  • R 4 independently represents a hydrogen atom or an organic group. * Represents the bond position.
  • the organic group as R 1 and R 2 is not particularly limited, but specifically, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
  • the group is mentioned.
  • the alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the heteroaryl group preferably has 4 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms.
  • the alkylcarbonyl group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms.
  • the arylcarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 15 carbon atoms.
  • the alkylsulfonyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
  • the arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the organic group may have an acid-decomposable group.
  • the acid-decomposable group include those described as the acid-decomposable group in the repeating unit having the acid-decomposable group described later.
  • the organic group may further have a substituent.
  • the further substituent is not particularly limited, but the above-mentioned Substituent T is preferable, and a hydroxyl group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, and a combination thereof are further preferable.
  • At least one of R 1 and R 2 is preferably a hydrogen atom, and more preferably one of them is a hydrogen atom.
  • the organic group as R 3 is not particularly limited, and specific examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the heteroaryl group preferably has 4 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms.
  • the organic group may further have a substituent.
  • the further substituent is not particularly limited, but the above-mentioned Substituent T is preferable.
  • the organic group as R 4 is not particularly limited, and specific examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the heteroaryl group preferably has 4 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms.
  • the organic group may further have a substituent.
  • the further substituent is not particularly limited, but the above-mentioned Substituent T is preferable.
  • the repeating unit (a1) has an aromatic group.
  • the aromatic ring constituting the aromatic group is not particularly limited, and examples thereof include an aromatic ring having 1 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. it can. It is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
  • the aromatic group may further have a substituent.
  • the further substituent is not particularly limited, but the above-mentioned Substituent T is preferable.
  • the repeating unit (a1) preferably has at least one of the partial structure represented by the general formula (1a) and the partial structure represented by the general formula (1b) on the side chain.
  • the repeating unit (a1) is preferably represented by the following general formula (2a) or general formula (2b).
  • X 1 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group.
  • Y 1 represents a single bond or a divalent linking group.
  • Z 1 represents a single bond or (n 1 + 1) valent linking group.
  • R 21 and R 22 independently represent a hydrogen atom or an organic group. R 21 and R 22 may be combined with each other to form a ring.
  • n 1 represents an integer of 1 or more.
  • the plurality of R 21s may be the same or different, and the plurality of R 22s may be the same or different.
  • At least one of X 1 , Y 1 , Z 1 , R 21 and R 22 contains an aromatic group.
  • X 2 represents a hydrogen atom, a halogen atom, a cyano group, or an organic group.
  • Y 2 represents a single bond or a divalent linking group.
  • Z 2 represents a single bond or (n 2 + 1) valent linking group.
  • R 23 represents a hydrogen atom or an organic group.
  • R 24 represents a hydrogen atom or an organic group.
  • n 2 represents an integer of 1 or more. When n 2 represents an integer of 2 or more, the plurality of R 23s may be the same or different, and the plurality of R 24s may be the same or different. At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 contains an aromatic group.
  • the organic group as X 1 is not particularly limited, and specific examples thereof include an alkyl group, a cycloalkyl group, and an aryl group.
  • the alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the organic group may further have a substituent.
  • the further substituent is not particularly limited, but the above-mentioned Substituent T is preferable.
  • the divalent linking group as Y 1 is not particularly limited, but is limited to an alkylene group, a cycloalkylene group, an aromatic group, -CO-, -COO-, -SO-, -SO 2- , -CONR 5- , and. these represent two or more combination comprising group, R 5 represents a hydrogen atom or an alkyl group.
  • the alkylene group may be linear or branched, preferably having 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • the cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.
  • an aromatic group having 6 to 20 carbon atoms is preferable, and an aromatic group having 6 to 15 carbon atoms is more preferable.
  • the alkyl group as R 5 may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • Z 1 represents a single bond or (n 1 + 1) valent linking group.
  • R 21 and R 22 independently represent a hydrogen atom or an organic group.
  • the organic groups as R 21 and R 22 are the same as the organic groups described as R 1 and R 2.
  • n 1 represents an integer of 1 or more.
  • the upper limit of n 1 is not particularly limited, but is preferably 5 or less.
  • n 1 is more preferably an integer of 1 to 2.
  • At least one of X 1 , Y 1 , Z 1 , R 21 and R 22 contains an aromatic group.
  • the organic group as X 2 is the same as the organic group described as X 1.
  • the divalent linking group as Y 2 is the same as the divalent linking group described as Y 1.
  • Z 2 represents a single bond or (n 2 + 1) valent linking group.
  • Z The 2 (n 2 +1) -valent linking group for example, from the divalent linking group as described above for Y 2, be a group formed by removing (n 2 -1) hydrogen atoms it can.
  • the organic group as R 23 is the same as the organic group described as R 3.
  • the organic group as R 24 is the same as the organic group described as R 4.
  • n 2 represents an integer of 1 or more.
  • the upper limit of n 2 is not particularly limited, but is preferably 5 or less.
  • n 2 is more preferably an integer of 1 to 2.
  • At least one of X 2 , Y 2 , Z 2 , R 23 and R 24 contains an aromatic group.
  • the repeating unit represented by the general formula (2a) or the general formula (2b) is preferably the repeating unit represented by the following general formula (3).
  • X 3 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
  • Y 3 represents a single bond or a divalent linking group.
  • Ar represents an aromatic group.
  • Z 3 represents a single bond or (n + 1) valent linking group.
  • R 31 and R 32 each independently represent a hydrogen atom or an organic group. R 31 and R 32 may be combined with each other to form a ring.
  • n represents an integer of 1 or more. When n represents an integer of 2 or more, the plurality of R 31s may be the same or different, and the plurality of R 32s may be the same or different.
  • the alkyl group as X 3 is similar to the alkyl group described as the organic group of X 1.
  • the cycloalkyl group as X 3 is similar to the cycloalkyl group described as the organic group of X 1.
  • the alkyl group and cycloalkyl group as X 3 may further have a substituent.
  • Y 3 represents a single bond or a divalent linking group.
  • the divalent linking group as Y 3 is the same as the divalent linking group described as Y 1.
  • Ar represents an aromatic group.
  • the aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
  • Z 3 represents a single bond and n represents an integer of 2 or more
  • Ar represents a (n + 1) -valent aromatic group, and specifically, from the above divalent aromatic group (n). -1) It is a group formed by removing 1 hydrogen atom.
  • Z 3 represents a single bond or (n + 1) valent linking group.
  • R 31 and R 32 each independently represent a hydrogen atom or an organic group.
  • the organic groups as R 31 and R 32 are the same as the organic groups described as R 1 and R 2.
  • n represents an integer of 1 or more.
  • the upper limit of n is not particularly limited, but is preferably 5 or less.
  • n is more preferably an integer of 1 to 2.
  • Y 3 in the general formula (3) represents a single bond, -COO-, or -CONR 6-
  • R 6 represents a hydrogen atom or an alkyl group.
  • Z 3 in the general formula (3) represents a single bond.
  • R 31 and R 32 in the above general formula (3) independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, respectively.
  • Alkyl groups, cycloalkyl groups, aryl groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, or arylsulfonyl groups as R 31 and R 32 are described as organic groups of R 1 and R 2, respectively. Similar to alkyl, cycloalkyl, aryl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, or arylsulfonyl groups.
  • the alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group as R 31 and R 32 may further have a substituent.
  • X 4 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
  • Y 4 represents a single bond or a divalent linking group.
  • R 41 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.
  • the alkyl group as X 4 is similar to the alkyl group described as the organic group of X 1.
  • the cycloalkyl group as X 4 is similar to the cycloalkyl group described as the organic group of X 1.
  • the alkyl group and cycloalkyl group as X 4 may further have a substituent.
  • the divalent linking group as Y 4 is the same as the divalent linking group described as Y 1.
  • the alkyl group, cycloalkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group as R 41 are described as the organic groups of R 1 and R 2, respectively. Similar to cycloalkyl groups, aryl groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, or arylsulfonyl groups.
  • R 41 in the above general formula (4) represents an alkylcarbonyl group or an arylcarbonyl group.
  • the content of the repeating unit (a1) in the resin (A) is preferably 7 to 60 mol%, more preferably 10 to 50 mol%, based on all the repeating units of the resin (A). , 15 to 50 mol% is particularly preferable. As a preferred embodiment, the content of the repeating unit (a1) in the resin (A) is preferably 10 mol% or more with respect to all the repeating units of the resin (A).
  • the repeating unit (a1) may be used alone or in combination of two or more.
  • At least one of the repeating unit (a1) and the repeating unit other than the repeating unit (a1) has an acid-degradable group.
  • Examples of the acid-degradable group when the repeating unit (a1) has an acid-degradable group include those described as the acid-degradable group in the repeating unit having an acid-degradable group described later. it can.
  • repeating unit corresponding to the repeating unit (a1) will be illustrated, but the present invention is not limited thereto.
  • the resin (A) may contain a repeating unit other than the repeating unit (a1).
  • the resin (A) contains the repeating unit (a1) and is preferably an acid-degradable resin.
  • the resin (A) is typically a resin in which the polarity is increased by the action of an acid, the solubility in an alkaline developer is increased, and the solubility in an organic solvent is decreased.
  • the resin (A) has a group that decomposes by the action of an acid to generate a polar group (in other words, a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid). Such a group (structure) is also called an acid-degradable group.
  • a resin having an acid-degradable group (that is, a resin having a repeating unit having an acid-degradable group) has an increased polarity due to the action of an acid, an increase in solubility in an alkaline developer, and a decrease in solubility in an organic solvent.
  • the resin (A) may further contain a repeating unit having an acid-degradable group (also referred to as “repeating unit (a2)”).
  • the acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) that is eliminated by the action of an acid.
  • the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkylcarbonyl).
  • Imid group bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl)
  • acidic groups such as methylene groups (typically, groups dissociating in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups and the like.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the ⁇ -position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.).
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
  • a carboxyl group a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
  • Examples of the group desorbed by the action of an acid include groups represented by the formulas (Y1) to (Y4).
  • Equation (Y1): -C (Rx 1 ) (Rx 2 ) (Rx 3 ) Equation (Y2): -C ( O) OC (Rx 1 ) (Rx 2 ) (Rx 3 ) Equation (Y3): -C (R 36 ) (R 37 ) (OR 38 )
  • Rx 1 to Rx 3 are independently alkyl groups (linear or branched chain), cycloalkyl groups (monocyclic or polycyclic), or aryl groups (monocyclic or polycyclic), respectively. Represents monocyclic or polycyclic). Among them, Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. Is more preferable. Two of Rx 1 to Rx 3 may be combined to form a monocyclic or polycyclic ring.
  • the alkyl group of Rx 1 to Rx 3 is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Further, an alkyl group having 1 to 4 carbon atoms such as a t-butyl group is preferable.
  • the cycloalkyl group of Rx 1 to Rx 3 is not particularly limited, and examples thereof include a cycloalkyl group having 3 to 20 carbon atoms, a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group. , Tetracyclodecanyl group, tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
  • the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • the alkyl group, cycloalkyl group, and aryl group may have a substituent.
  • Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
  • a polycyclic cycloalkyl group such as an nyl group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
  • the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 may have a substituent.
  • 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.
  • L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined).
  • .. M represents a single bond or a divalent linking group.
  • Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, and an aldehyde.
  • the alkyl group and the cycloalkyl group for example, one of the methylene groups may be replaced with a 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.
  • Tg glass transition temperature
  • activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group or an aryl group.
  • Rn and Ar may be combined with each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • the resin (A) preferably has an acetal structure.
  • the acid-degradable group preferably has an acetal structure.
  • the acetal structure is a structure in which polar groups such as a carboxyl group, a phenolic hydroxyl group, and a fluorinated alcohol group are protected by a group represented by the above formula (Y3).
  • the repeating unit represented by the formula (A) is preferable.
  • L 1 represents a divalent linking group
  • R 1 to R 3 independently represent a hydrogen atom or a monovalent substituent
  • R 4 represents a group that is decomposed and eliminated by the action of an acid.
  • L 1 represents a divalent linking group.
  • the divalent linking group include -CO- , -O-, -S-, -SO-, -SO 2- , 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 are linked is mentioned.
  • the L 1, -CO- an 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.
  • R 1 to R 3 independently represent a hydrogen atom or a monovalent substituent.
  • the monovalent substituent include an alkyl group, a cycloalkyl group, and a halogen atom.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the number of carbon atoms of this cycloalkyl group is preferably 3 to 8.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 4 represents a group (leaving group) that is eliminated by the action of an acid.
  • examples of the leaving group include groups represented by the above formulas (Y1) to (Y4), and groups represented by the above formula (Y3) are preferable.
  • the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • 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.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). 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 cycloalkyl group (monocyclic or polycyclic).
  • the alkyl group for example, include groups represented by methyl group or -CH 2 -R 11.
  • R 11 represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms and having 3 or less carbon atoms.
  • Alkyl groups are preferred, and methyl groups are more preferred.
  • Xa 1 a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
  • Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -O-Rt- group and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a -COO-Rt- group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH 2- group,- (CH 2 ) 2- group, or- (CH 2 ) 3- Groups are more preferred.
  • Examples of the alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the polycyclic cycloalkyl group of is preferred.
  • a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used.
  • Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
  • the repeating unit represented by the general formula (AI) for example, it is preferable that Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
  • the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • the repeating unit represented by the general formula (AI) is preferably an acid-degradable (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 resin (A) may contain a repeating unit having an acid-degradable group alone or in combination of two or more.
  • the repeating unit (a1) When the repeating unit (a1) has an acid-degradable group, the repeating unit (a1) also corresponds to the repeating unit (a2).
  • the content of the repeating unit having an acid-degradable group contained in the resin (A) (the total of a plurality of repeating units having an acid-degradable group) is determined with respect to all the repeating units of the resin (A). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 25 to 75 mol%.
  • the resin (A) may further have a repeating unit having a lactone group or a sultone group (also referred to as "repeating unit (a3)").
  • a repeating unit having a lactone group or a sultone group also referred to as "repeating unit (a3)"
  • the lactone group or sultone group any group having a lactone structure or a sultone structure can be used, but a group having a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
  • the 5- to 7-membered ring lactone structure has a bicyclo structure or a spiro structure in which another ring structure is fused, or the 5- to 7-membered ring sultone structure has a bicyclo structure or a spiro structure. It is more preferable that the other ring structure is condensed in the form of forming.
  • a group having a lactone structure or a sultone structure may be directly bonded to the main chain.
  • a lactone structure represented by the general formula (LC1-22) or a sultone structure represented by the general formula (SL1-1) is preferable.
  • the lactone structure portion or the 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.
  • repeating unit having a group having a lactone structure or a sultone structure examples include a repeating unit represented by the following general formula (AI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab is a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
  • Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornene group is preferable.
  • V represents a group having a lactone structure or a sultone structure.
  • Examples of the group having a lactone structure or sultone structure of V include the structures represented by the above-mentioned general formulas (LC1-1) to (LC1-22) and the general formulas (SL1-1) to (SL1-3).
  • the group is formed by removing one hydrogen atom from one carbon atom constituting the lactone structure or the sultone structure. It is preferable that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting a substituent (Rb 2).
  • the repeating unit having a group having a lactone structure or a sultone structure usually has an optical isomer, but 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.
  • Rx represents H, CH 3 , CH 2 OH, or CF 3 .
  • the content thereof is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and 10 to 10 to all the repeating units in the resin (A). 40 mol% is more preferable.
  • the resin (A) may further have a repeating unit having a carbonate group (also referred to as “repeating unit (a4)").
  • the carbonate group in the repeating unit having a carbonate group is preferably contained in the cyclic carbonate group.
  • the repeating unit having a carbonate group is preferably a repeating unit represented by the general formula (A4).
  • RA 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
  • n represents an integer of 0 or more (preferably 0 to 3).
  • RA 2 represents a substituent. when n is 2 or more, R A 2 existing in plural, may each be the same or different.
  • A represents a single bond or a divalent linking group.
  • the divalent linking group is an alkylene group (preferably having 1 to 4 carbon atoms), a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, and a carboxylic acid. A group or a divalent group in which these are combined is preferable.
  • Z represents an atomic group forming a monocyclic or polycyclic ring together with a group represented by —O—CO—O— in the formula.
  • the monocyclic or polycyclic ring formed by Z together with the group represented by —O—CO—O— in the formula is preferably a 5-membered cyclic carbonate group, and is represented by the following general formula (CC1-1).
  • a cyclic carbonate structure is more preferred. That is, it is preferable that A in the general formula (A4) is bonded to a group formed by extracting one hydrogen atom from the ring member atom of the cyclic carbonic acid ester structure represented by the following general formula (CC1-1). ..
  • the cyclic carbonate structure portion in the general formula (CC1-1) may have a substituent (Rb2).
  • Preferred substituents (Rb2) include, for example, 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 carboxylic group. Examples thereof include an acid group, a halogen atom (preferably a fluorine atom), a hydroxyl group, and a cyano group.
  • n3 represents an integer of 0 or 1.
  • the content thereof is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and 7 to 7 to all the repeating units of the resin (A). 45 mol% is more preferred.
  • the repeating unit (a4) may be used alone or in combination of two or more.
  • the resin (A) further contains a repeating unit (a1), a repeating unit (a3), and a repeating unit having a polar group different from that of the repeating unit (a4) (also referred to as “repeating unit (a5)”). May be good.
  • the polar group of the repeating unit (a5) includes a sulfonate group, a carboxylic acid group, a sulfonic acid group, a carbamate group, an alcoholic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfoxide group, a sulfonyl group and a ketone. It is preferably at least one group selected from the group consisting of a group, an imide group, an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group.
  • the repeating unit (a5) is preferably a repeating unit represented by the general formula (A5).
  • X Q5 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • RQ5 represents an alkylene group (linear or branched chain, preferably 1 to 5 carbon atoms) or a non-aromatic ring group.
  • Examples of the non-aromatic ring group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group.
  • Examples of the monocyclic hydrocarbon ring group include a cycloalkane ring group having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and a cycloalkene ring group having 3 to 12 carbon atoms.
  • Examples of the polycyclic hydrocarbon ring group include a ring-assembled hydrocarbon ring group and a crosslinked ring-type hydrocarbon ring group.
  • Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring and the like.
  • the crosslinked cyclic hydrocarbon ring may be a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
  • the crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclo [5, 2, 1, 02, 6] decane ring group.
  • alkyl group and the non-aromatic ring group do not have a substituent other than ⁇ (OH) q5.
  • the repeating unit (a5) is preferably a repeating unit represented by the general formula (A6).
  • X Q6 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • RQ6 represents an alkylene group (linear or branched chain, preferably 1 to 5 carbon atoms), a non-aromatic ring group, an aromatic ring group, or a group composed of a combination of two or more of these. ..
  • Examples of the non-aromatic ring group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group.
  • Examples of the monocyclic hydrocarbon ring group include a cycloalkane ring group having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and a cycloalkene ring group having 3 to 12 carbon atoms.
  • Examples of the polycyclic hydrocarbon ring group include a ring-assembled hydrocarbon ring group and a crosslinked ring-type hydrocarbon ring group.
  • Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring and the like.
  • the crosslinked cyclic hydrocarbon ring may be a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
  • the crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclo [5, 2, 1, 02, 6] decane ring group.
  • the aromatic ring group preferably has an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, an anthracene ring group, or a biphenylene ring group.
  • alkylene group, the non-aromatic ring group, and the aromatic ring group do not have a substituent other than ⁇ ( ⁇ C (CF 3 ) 2 OH) q6.
  • q6 represents an integer from 1 to 5.
  • the content thereof is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and 7 to 7 to all the repeating units of the resin (A). 45 mol% is more preferred.
  • the repeating unit (a5) may be used alone or in combination of two or more.
  • the resin (A) may further contain a repeating unit having a phenolic hydroxyl group represented by the following general formula (B2) (also referred to as “repeating unit (a6)”).
  • X represents a hydrogen atom, an alkyl group, or a halogen atom.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • the substituent of the alkyl group is preferably a hydroxyl group or a halogen atom.
  • the alkyl group has a substituent, it is preferable that the alkyl group has only a hydroxyl group and / or a halogen atom as the substituent.
  • the alkyl group is preferably -CH 3.
  • X 4 represents a single bond, -COO-, or -CONR 64-
  • R 64 is a hydrogen atom or an alkyl group (which may be linear or branched, preferably having a number of carbon atoms). Represents 1 to 5).
  • the carbonyl carbon in -COO- is preferably directly attached to the main chain of the repeating unit.
  • L 4 represents a single bond or an alkylene group (which may be linear or branched, preferably having 1 to 20 carbon atoms).
  • Ar 4 represents an (n + 1) -valent aromatic ring group.
  • the aromatic ring group is an arylene group having 6 to 18 carbon atoms such as a benzene ring group, a naphthalene ring group, and an anthracene ring group, or a thiophene ring group, a furan ring group, a pyrrole ring group, a benzothiophene ring group, and a benzofuran.
  • Aromatic ring groups containing heterocycles such as a ring group, a benzopyrol ring group, a triazine ring group, an imidazole ring group, a benzoimidazole ring group, a triazole ring group, a thiadiazol ring group, and a thiazole ring group are preferable, and a benzene ring group is preferable. More preferred.
  • n represents an integer from 1 to 5.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituent that the above-mentioned alkyl group of R 64 , alkylene group of L 4 and Ar 4 (n + 1) -valent aromatic ring group can have include a halogen atom (preferably a fluorine atom) and a methoxy group. Examples thereof include an alkoxy group such as an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like. Further , examples of the substituent that the (n + 1) -valent aromatic ring group of Ar 4 can have include an alkyl group (which may be linear or branched, preferably having 1 to 20 carbon atoms).
  • a represents 1 or 2.
  • R represents a hydrogen atom or a methyl group
  • a represents an integer of 1 to 3.
  • the content thereof is preferably 1 to 75 mol%, more preferably 5 to 70 mol%, and 10 to 10 to all the repeating units of the resin (A). 70 mol% is more preferable.
  • the repeating unit (a6) may be used alone or in combination of two or more.
  • the resin (A) may further contain a repeating unit represented by the following formula (D) (also referred to as “repeating unit (a7)”).
  • cylic represents a group forming a main chain with a cyclic structure.
  • the number of constituent atoms of the ring is not particularly limited.
  • Examples of the repeating unit represented by the formula (D) include the following repeating units.
  • R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and the like.
  • An ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxylic acid 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
  • 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 greater than or equal to 0. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
  • the content thereof is preferably 1 to 50 mol% with respect to all the repeating units of the resin (A). 3 to 40 mol% is more preferable, and 5 to 30 mol% is further preferable.
  • the repeating unit (a7) may be used alone or in combination of two or more.
  • the resin (A) may further contain a repeating unit represented by the following formula (E) (also referred to as “repeating unit (a8)").
  • 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.
  • Examples of the repeating unit represented by the formula (E) include the following repeating units.
  • R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen. It represents an atom, an ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxylic acid 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.
  • 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 greater than or equal to 0. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
  • the formula (E-2), the formula (E-4), the formula (E-6), the formula (E-8), and the formula (E-13) the two Rs are bonded to each other to form a ring. You may be doing it.
  • the content thereof is preferably 1 to 50 mol% with respect to all the repeating units of the resin (A), and 3 to 40. More preferably mol%, more preferably 5 to 35 mol%.
  • the repeating unit (a8) may be used alone or in combination of two or more.
  • the resin (A) may contain a repeating unit other than the above as the other repeating unit as long as the effect of the present invention is not impaired.
  • the resin (A) may have a repeating unit having a photoacid generating group. Good.
  • the repeating unit having the photoacid generator is not particularly limited, but is preferably a repeating unit represented by the general formula (A7) (also referred to as “repeating unit (a9)”).
  • the two Xfs independently represent an alkyl group (preferably CF 3 ) substituted with a hydrogen atom, a fluorine atom, or at least one fluorine atom. Of the two Xfs, at least one is preferably a non-hydrogen atom.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • the alkyl group preferably has only a fluorine atom as a substituent.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of them, R 1 and R 2 may be the same or different.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • the substituent of the alkyl group is preferably a fluorine atom. When the alkyl group has a substituent, it is preferable that the alkyl group has only a fluorine atom as the substituent.
  • L represents a divalent linking group, and when a plurality of L are present, L may be the same or different.
  • the divalent linking group of L is -COO-, -CO- , -O-, -S-, -SO-, -SO 2- , alkylene group, cycloalkylene group, alkenylene group, and a plurality of these. Examples thereof include linked linking groups, and linking groups having a total carbon number of 12 or less are preferable.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • X 7 represents a hydrogen atom, an alkyl group, or a halogen atom.
  • examples of the alkyl group include a linear or branched alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, or a propyl group, and a methyl group or a branched chain group. Ethyl groups are more preferred, and methyl groups are even more preferred.
  • substituent when the alkyl group has a substituent include the substituent described in the Substituent T.
  • halogen atom when X 7 represents a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • M + represents a cation.
  • M + for example, the same cation as M + in the general formula (PA-1) described later can be used.
  • the content thereof is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, and 5 to 5 to all the repeating units of the resin (A). 20 mol% is more preferred.
  • the repeating unit (a9) may be used alone or in combination of two or more.
  • 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 4,500 to 15,000.
  • the weight average molecular weight of the resin (A) is set to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and further, deterioration of developability and high viscosity can be prevented. It is possible to prevent the film property from deteriorating.
  • 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 repeating unit having an aromatic group in the resin (A) is preferably 10 to 100 mol%, preferably 15 to 100 mol%, based on all the repeating units of the resin (A). More preferred.
  • the content of the repeating unit having an aromatic group can be measured by 1 1 H-NMR or 13 C-NMR.
  • 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. Further, the resin (A) may be used alone or in combination of two or more.
  • the resist composition may contain a compound that generates an acid by irradiation with active light or radiation (also referred to as a photoacid generator or a photoacid generator (B)).
  • the photoacid generator is a compound that generates an acid by exposure (preferably exposure to electron beam (EB) or EUV light).
  • 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, still more preferably 1000 or less.
  • 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, and among them, a compound that generates an organic acid by irradiation with electron beam (EB) or EUV light is preferable, and a photoacid generator having a fluorine atom or an iodine atom in the molecule is more preferable. ..
  • the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonyl. Examples thereof include sulfonylimide acid, bis (alkylsulfonyl) imide acid, and tris (alkylsulfonyl) methidoic acid.
  • the volume of the acid generated from the photoacid generator is not particularly limited, and suppress the diffusion of the non-exposed portion of the acid generated by exposure, from the viewpoint of improving the resolution, 240 ⁇ 3 or more are preferred, 305 ⁇ 3 The above is more preferable, 350 ⁇ 3 or more is further preferable, and 400 ⁇ 3 or more is particularly preferable.
  • the volume of the acid generated by the photoacid generator is preferably 1500 ⁇ 3 or less, 1000 ⁇ 3, more preferably less, 700 ⁇ 3 or less is more preferable.
  • the above volume value is obtained using "WinMOPAC" manufactured by Fujitsu Limited.
  • volume value In calculating the volume value, first, the chemical structure of the acid according to each example is input, and then each acid is calculated by molecular mechanics using the MM (Molecular Mechanics) 3 method with this structure as the initial structure. The most stable conformation of each acid can be determined, and then the molecular orbital calculation of these most stable conformations using the PM (Parameterized Model number) 3 method can be performed to calculate the "accessible volume" of each acid.
  • MM Molecular Mechanics
  • the structure of the acid generated by the photoacid generator is not particularly limited, but it is between the acid generated by the photoacid generator and the resin (A) in terms of suppressing the diffusion of the acid and improving the resolution. It is preferable that the interaction is strong. From this point, when the acid generated by the photoacid generator is an organic acid, for example, a sulfonic acid group, a carboxylic acid group, a carbonylsulfonylimide acid group, a bissulfonylimide acid group, a trissulfonylmethidoic acid group, etc. It is preferable to have a polar group in addition to the organic acid group of.
  • Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group, and a mercapto.
  • the group is mentioned.
  • the number of polar groups contained in the generated acid is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than 6, and more preferably less than 4.
  • the photoacid generator is preferably a photoacid generator that generates the acids exemplified below.
  • the calculated value of the volume is added to a part of the example (unit: ⁇ 3 ).
  • the photoacid generator is preferably a photoacid generator having anions and cations because the effect of the present invention is more excellent.
  • the photoacid generator preferably contains a compound represented by the general formula (PA-1).
  • a 1 and A 2 are each independently, -SO 2 -R P, or represents -CO-R P.
  • R P represents an organic group.
  • R P present two in the general formula (PA-1) may be the same or different.
  • R P is a group represented by the general formula (RF) is preferred.
  • LRF represents a single bond or a divalent linking group.
  • the divalent linking group include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2- , and an alkylene group (linear or branched chain). It may be preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (may be linear or branched chain, preferably 2 to 6 carbon atoms), and these.
  • a divalent linking group obtained by combining a plurality of the above can be mentioned.
  • the substituent that can be possessed when these divalent linking groups are possible, a halogen atom is preferable, and a fluorine atom is more preferable.
  • the above-mentioned alkylene group (including an alkylene group that can be contained in a divalent linking group in which a plurality of them are combined) is a perfluoroalkylene group.
  • the divalent linking group is preferably -alkylene group-COO- or -alkylene group-SO 2- .
  • the alkylene group is preferably present on the N- side.
  • R RF represents a cycloalkyl group or an alkyl group.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the cycloalkyl group preferably has 3 to 15 carbon atoms, and more preferably 5 to 10 carbon atoms. Examples of the cycloalkyl group include a norbornyl group, a decalynyl group, and an adamantyl group.
  • the substituent that the cycloalkyl group may have is preferably an alkyl group (linear or branched chain, preferably 1 to 5 carbon atoms). It is also preferable that the cycloalkyl group has no other substituent.
  • One or more of the carbon atoms which are ring member atoms of the cycloalkyl group may be replaced with carbonyl carbon atoms and / or heteroatoms.
  • the carbon atom (-CH ⁇ ) bonded to LRF in the cycloalkyl group may be replaced by the nitrogen atom (-N ⁇ ).
  • R RF is an alkyl group
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • the substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group.
  • the above alkyl group has no substituent other than these.
  • the cycloalkyl group as the substituent include, for example, the cycloalkyl group described in the case where R RF is a cycloalkyl group.
  • the alkyl group may or may not be a perfluoroalkyl group.
  • the alkyl group has a fluorine atom as the substituent, it is also preferable that a part or all of the alkyl group is a perfluoromethyl group.
  • M + represents a cation.
  • the M + cation is preferably an organic cation.
  • the organic cations are preferably cations represented by the general formula (ZaI) (cations (ZaI)) or cations represented by the general formula (ZaII) (cations (ZaII)) independently of each other.
  • 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 usually 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 group, an amide group, or a carbonyl group.
  • the two of the group formed by bonding of the R 201 ⁇ R 203 for example, an alkylene group (e.g., butylene, pentylene), and, -CH 2 -CH 2 -O-CH 2 -CH 2 - Can be mentioned.
  • Examples of the cation in the general formula (ZaI) include a cation (ZaI-1), a cation (ZaI-2), and a cation represented by the general formula (ZaI-3b) (cation (ZaI-3b)), which will be described later.
  • a cation represented by the general formula (ZaI-4b) (cation (ZaI-4b)) can be mentioned.
  • the cation (ZaI-1) is an aryl sulfonium cation in which at least one of R 201 to R 203 of the above general formula (ZaI) is an aryl group.
  • the aryl sulfonium cation all of R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
  • R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, and the like may be formed in the ring. It may contain an ester group, an amide group, or a carbonyl group.
  • a group formed by bonding two of R 201 to R 203 for example, one or more methylene groups are substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group.
  • alkylene group e.g., butylene group, pentylene group, or -CH 2 -CH 2 -O-CH 2 -CH 2 -
  • aryl sulfonium cation examples include a triaryl sulfonium cation, a diallyl alkyl sulfonium cation, an aryl dialkyl sulfonium cation, a diallyl cycloalkyl sulfonium cation, and an aryl dicycloalkyl sulfonium cation.
  • the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like.
  • the aryl sulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group that the arylsulfonium cation has as needed is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms.
  • a cycloalkyl group of 15 is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
  • the aryl group, alkyl group, and substituent that the cycloalkyl group of R 201 to R 203 may have are independently an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon number of carbon atoms). 3 to 15), aryl group (for example, 6 to 14 carbon atoms), alkoxy group (for example, 1 to 15 carbon atoms), cycloalkylalkyl group (for example, 1 to 15 carbon atoms), halogen atom, hydroxyl group, or phenylthio group. preferable.
  • the above-mentioned substituent may further have a substituent when possible. For example, even if the above-mentioned alkyl group has a halogen atom as a substituent and is an alkyl halide group such as a trifluoromethyl group. Good.
  • the cation (ZaI-2) is a cation in which R 201 to R 203 in the formula (ZaI) independently represent an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a hetero atom.
  • the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and are linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or Alkoxycarbonylmethyl groups are more preferred, and linear or branched 2-oxoalkyl groups are even more preferred.
  • Examples of the alkyl group and cycloalkyl group of R 201 to R 203 include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, and a propyl group). Groups, butyl groups, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl groups, cyclohexyl groups, and norbornyl groups) can be mentioned.
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • the cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).
  • R 1c to R 5c independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, and a hydroxyl group.
  • R 6c and R 7c independently represent a hydrogen atom, an alkyl group (t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
  • R x and R y independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group, respectively.
  • R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be combined to form a ring, respectively.
  • This ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
  • the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
  • Examples of the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include an alkylene group such as a butylene group and a pentylene group. ..
  • the methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.
  • the group formed by bonding R 5c and R 6c , and R 5c and R x is preferably a single bond or an alkylene group.
  • Examples of the alkylene group include a methylene group and an ethylene group.
  • the cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).
  • l represents an integer of 0 to 2.
  • r represents an integer from 0 to 8.
  • R 13 is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be used, and a group containing a cycloalkyl group as a part). May be). These groups may have substituents.
  • R 14 is a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be a cycloalkyl group). It may be a group containing a group as a part). These groups may have substituents. When a plurality of R 14 are present, each independently represents the above group such as a hydroxyl group.
  • R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents.
  • R 15 Bonded to two R 15 each other may form a ring.
  • an oxygen atom or may contain a hetero atom such as nitrogen atom.
  • two R 15 is an alkylene group, preferably bonded together to form a ring structure.
  • the alkyl groups of R 13 , R 14 and R 15 are linear or branched chain.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like.
  • R 204 and R 205 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group of R 204 and R 205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom or the like.
  • Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 and R 205 are a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group).
  • a group or a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms is preferable.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). ⁇ 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.
  • the photoacid generator preferably contains a compound represented by the general formula (PB).
  • PB general formula (PB)
  • a resist film can be constant each occurrence ratio of the structure. Therefore, the present inventors presume that even when the resist film is exposed, the amount and diffusion of the acid generated in the resist film tends to be uniform, and the width of the pattern obtained after development is stable.
  • M 1 + and M 2 + each independently represents an organic cation.
  • M 1 + and M 2 + organic cation each independently, an organic cation listed in the description of the M + of the general formula (PA-1) can be used as well.
  • L represents a divalent organic group.
  • the divalent organic group include -COO-, -CONH-, -CO-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), and a cycloalkylene group (preferably. 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these groups can be mentioned.
  • One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
  • These divalent linking groups also preferably have a group selected from the group consisting of -O-, -S-, -SO-, and -SO 2-.
  • L is preferably a group represented by the following general formula (L). * A-LA-LB-LC-LD-LE- * B (L)
  • * A represents the connection position with A ⁇ in the general formula (PB).
  • * B represents the connection position with B ⁇ in the general formula (PB).
  • LA represents ⁇ (C (R LA1 ) (R LA2 )) XA ⁇ .
  • the XA represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
  • R LA1 and R LA2 each independently represent a hydrogen atom or a substituent.
  • the substituents of R LA1 and R LA2 are independently preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and further preferably a fluorine atom or a perfluoromethyl group.
  • the R LA1s in which XA are present may be the same or different.
  • the R LA2 having XA may be the same or different.
  • -(C (R LA1 ) (R LA2 ))- is preferably -CH 2- , -CHF-, -CH (CF 3 )-, or -CF 2- .
  • the general formula (PB) in A - and a direct bond to - (C (R LA1) ( R LA2)) - is, -CH 2 -, - CHF - , - CH (CF 3) -, or - CF 2 -is preferable.
  • Formula (PB) in A - and a direct bond to - (C (R LA1) ( R LA2)) - other than the - (C (R LA1) ( R LA2)) - are each independently, -CH 2 -, -CHF-, or -CF 2 --is preferable.
  • LB represents a single bond, an ester group (-COO-), or a sulfonyl group (-SO 2- ).
  • LC represents a single bond, an alkylene group, a cycloalkylene group, or a group composed of a combination thereof (such as "-alkylene group-cycloalkylene group-").
  • the alkylene group may be linear or branched.
  • the carbon number of the alkylene group is preferably 1 to 5, more preferably 1 to 2, further preferably 1, and the number of carbon atoms of the cycloalkylene group is preferably 3 to 15, more preferably 5 to 10.
  • the cycloalkylene group may be monocyclic or polycyclic. Examples of the cycloalkylene group include a norbornanediyl group and an adamantandiyl group.
  • the substituent that the cycloalkylene group may have is preferably an alkyl group (linear or branched chain, preferably 1 to 5 carbon atoms).
  • One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
  • the alkylene group portion is preferably present on the LB side.
  • the LC is preferably a single bond or a cycloalkylene group.
  • LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).
  • LE is a single bond or - (C (R LE1) ( R LE2))
  • XE - represents a.
  • XE- represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
  • R LE1 and R LE2 independently represent a hydrogen atom or a substituent. When the number of XEs is 2 or more, the R LE1s having XEs may be the same or different from each other. When the number of XEs is 2 or more, the R LE2s having XEs may be the same or different from each other.
  • -(C (R LE1 ) (R LE2 ))- is preferably -CH 2-.
  • L when LB, LC, and LD are single bonds, it is preferable that LE is also a single bond.
  • a ⁇ represents an acid anion group.
  • An acid anion group is a group having an anion atom.
  • a ⁇ is preferably a group represented by any of the general formulas (A-1) to (A-2).
  • RA represents an organic group.
  • RA is preferably an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • the substituent that the alkyl group may have is preferably a fluorine atom.
  • the alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.
  • B ⁇ represents a group represented by any of the general formulas (B-1) to (B-4).
  • B ⁇ is preferably a group represented by any of the general formulas (B-1) to (B-3), and a group represented by any of the general formulas (B-1) to (B-2) is preferable. More preferred.
  • R B represents an organic group.
  • R B is a cycloalkyl group or an alkyl group. If R B is a cycloalkyl group, the carbon number of the cycloalkyl group is preferably 3 to 15, and more preferably 5-10.
  • the cycloalkyl group may be monocyclic or polycyclic. Examples of the cycloalkyl group include a norbornyl group and an adamantyl group.
  • the substituent that the cycloalkyl group may have is preferably an alkyl group (linear or branched chain, preferably 1 to 5 carbon atoms).
  • R B is an alkyl group
  • the alkyl group may be either linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • the substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. Examples of the cycloalkyl group as the substituent, R B is a cycloalkyl group as described in the case a cycloalkyl group as well.
  • the alkyl group may or may not be a perfluoroalkyl group.
  • the alkyl group has a fluorine atom as the substituent, it is also preferable that a part or all of the alkyl group is a perfluoromethyl group.
  • the pKa of the group represented by HA is BH. It is lower than the pKa of the represented group. More specifically, HA-L-BH when obtained an acid dissociation constant for the compound represented by the "HA-L-BH” is - a pKa at which the "A -L-BH""HA and in the pKa of a group represented by "further” a - a pKa of the group represented by "BH a pKa at which the '" - -L-BH "is” a - -L-B.
  • PKa of the group represented by HA and “pKa of the group represented by BH” are obtained by using “Software Package 1" or "Gaussian 16", respectively.
  • the pKa of the group represented by HA is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and even more preferably -5.00 to 0.00.
  • the pKa of the group represented by HB is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and even more preferably -1.00 to 5.00.
  • the difference between the pKa of the group represented by HB and the pKa of the group represented by HA (“pKa of the group represented by HB”-“pKa of the group represented by HA”) is 0.10 to 20. It is preferably .00, more preferably 0.50 to 17.00, and even more preferably 2.00 to 15.00.
  • photoacid generators As the resist composition, other photoacid generators other than those described above may be used.
  • Other photoacid generators for example, "M + Z - (M + represents a cation and Z - represents an anion)” include compounds represented by (onium salt).
  • M + Z - in a compound represented by, M + represents a cation, include the same cations as the cation in formula (PA-1).
  • Z - "M + Z" - represents an anion
  • the ability of causing a nucleophilic reaction is extremely low anion preferred.
  • the anion include sulfonic acid anions (aliphatic sulfonic acid anions such as fluoroalkyl sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.) and carboxylic acid anions (aliphatic carboxylic acid anions, aromatics).
  • 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 may be a linear or branched alkyl group having 1 to 30 carbon atoms. , A cycloalkyl group having 3 to 30 carbon atoms is preferable.
  • the aromatic ring group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • Examples of the substituents that the alkyl group, cycloalkyl group, and aryl group mentioned above can have include a halogen atom such as a nitro group and a fluorine atom, a carboxylic acid group, a hydroxyl group, an amino group, a cyano group, and an alkoxy group.
  • cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (Preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkyl Iminosulfonyl group (preferably 1 to 15 carbon atoms), aryloxysulfonyl group (preferably 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms) 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms), and a cyclo
  • the aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
  • the alkyl group in the tris (alkylsulfonyl) methideanion 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, and a cycloalkylaryloxysulfonyl group.
  • an alkyl group substituted with a fluorine atom or a fluorine atom is preferable.
  • non-nucleophilic anions e.g., fluorinated phosphorus (e.g., PF 6 -), fluorinated boron (e.g., BF 4 -), and fluorinated antimony (e.g., SbF 6 -) and the like.
  • fluorinated phosphorus e.g., PF 6 -
  • fluorinated boron e.g., BF 4 -
  • fluorinated antimony e.g., SbF 6 -
  • the non-nucleophilic anion is 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, or an alkyl group in which fluorine is used.
  • Atomically substituted tris (alkylsulfonyl) methideanions are preferred.
  • perfluoroaliphatic sulfonic acid anion preferably 4 to 8 carbon atoms
  • benzenesulfonic acid anion having a fluorine atom is more preferable
  • nonafluorobutanesulfonic acid anion, perfluorooctanesulfonic acid anion, pentafluorobenzenesulfone acid anions or 3,5-bis (trifluoromethyl) benzenesulfonic acid anions are more preferred.
  • 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 preferable.
  • Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R 1 and R 2 may be the same or different, respectively.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the general formula (AN1) will be described in more detail.
  • the number of carbon atoms of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4.
  • the alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf is, for example, fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C.
  • fluorine atom or CF. 3 is preferable.
  • both Xfs are fluorine atoms.
  • the alkyl groups of R 1 and R 2 may have a substituent (preferably a fluorine atom), and the number of carbon atoms in the substituent is preferably 1 to 4.
  • the substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Alkyl groups having substituents for R 1 and R 2 include, for example, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , C 7 F 15 , C.
  • R 1 and R 2 are preferably a fluorine atom or CF 3.
  • x is preferably an integer of 1 to 10, and more preferably 1 to 5.
  • y is preferably an integer of 0 to 4, more preferably 0.
  • z is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.
  • the divalent linking group of L include -COO-, -CO- , -O-, -S-, -SO-, -SO 2- , alkylene group, cycloalkylene group, alkenylene group, and these.
  • Examples thereof include a linking group in which a plurality of the above groups are linked, and a linking group having a total carbon number of 12 or less is preferable. Among them, -COO-, -CO-, or -O- is preferable, and -COO- is more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and has an alicyclic group, an aromatic ring group, and a heterocyclic group (not only those having aromaticity but also aromaticity). (Including those that do not), etc.
  • the alicyclic group may be monocyclic or polycyclic, and a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group is preferable, and in addition, a norbornyl group, a tricyclodecanyl group, and a tetracyclo Polycyclic cycloalkyl groups such as a decanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.
  • a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group is preferable, and in addition, a norbornyl group, a tricyclodecanyl group, and a tetracyclo Polycyclic cycloalkyl groups such as a decanyl group,
  • alicyclic groups having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are used in the post-exposure heating step. It is preferable from the viewpoint of suppressing the diffusibility in the membrane and improving the MEEF (Mask Error Enhancement Factor).
  • the aromatic ring group include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring and the like.
  • heterocyclic group examples include groups derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring and the like. Of these, a group derived from a furan ring, a thiophene ring, or a pyridine ring is preferable.
  • examples of the cyclic organic group include a lactone structure, and specific examples thereof include lactone structures represented by the above-mentioned general formulas (LC1-1) to (LC1-22).
  • the cyclic organic group may have a substituent.
  • the substituent may be an alkyl group (linear or branched chain, and may contain a cyclic structure, preferably having 1 to 12 carbon atoms) or a cycloalkyl group (monocyclic or polycyclic). It may be a spiro ring in the case of a polycycle, preferably having a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, and an amide.
  • Examples thereof include a group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.
  • the carbon constituting the cyclic organic group may be a carbonyl carbon.
  • the photoacid generator may be a betaine compound having a cation portion and an anion portion and having a structure in which both are covalently linked.
  • 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. [0339]) of the specification of 2015/004533 can be incorporated, and these contents are incorporated in the specification of the present application.
  • the following compound is mentioned as a preferable specific example. In the following compounds, anions and cations can be optionally exchanged, if possible.
  • the content of the photoacid generator in the resist composition is not particularly limited, but is preferably 5% by mass or more, preferably 9% by mass or more, based on the total solid content of the composition, in that the effect of the present invention is more excellent. More preferably, 15% by mass or more is further preferable.
  • the content is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
  • the photoacid generator may be used alone or in combination of two or more.
  • the resist composition may contain a solvent.
  • Solvents consist of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group.
  • the solvent may further contain components other than the components (M1) and (M2).
  • the present inventors have found that when such a solvent and the above-mentioned resin are used in combination, the coatability of the composition is improved and a pattern having a small number of development defects can be formed. Although the reason is not always clear, these solvents have a good balance of solubility, boiling point and viscosity of the above-mentioned resin, so that uneven film thickness of the composition film and generation of precipitates in spin coating can be suppressed. The present inventors believe that this is due to.
  • the component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA: propylene glycol monomethyl ether acetate), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, preferably propylene glycol.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA Monomethyl ether acetate
  • the component (M2) is preferably the following solvent.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferable.
  • the lactate ester is preferably ethyl lactate, butyl lactate, or propyl lactate.
  • the acetic acid ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl acetate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate.
  • alkoxypropionate ester is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP).
  • Chain ketones are 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone.
  • Acetoneacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, or methyl amyl ketone is preferred.
  • the cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.
  • the lactone is preferably ⁇ -butyrolactone.
  • the alkylene carbonate is preferably propylene carbonate.
  • the component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone, or propylene carbonate.
  • PGME propylene glycol monomethyl ether
  • ethyl lactate ethyl 3-ethoxypropionate
  • methyl amyl ketone cyclohexanone
  • butyl acetate pentyl acetate
  • ⁇ -butyrolactone propylene carbonate
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12 and even more preferably 7 to 10) and having a heteroatom number of 2 or less.
  • ester solvent having 7 or more carbon atoms and 2 or less heteroatomic atoms examples include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, and iso.
  • Examples thereof include isobutyl butyrate, heptyl propionate, butyl butanoate and the like, and isoamyl acetate is preferable.
  • the component (M2) is preferably a solvent having a flash point (hereinafter, also referred to as fp) of 37 ° C. or higher.
  • Such components (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), and methylamyl ketone (fp: 42 ° C.).
  • Cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C), or propylene carbonate (fp: 132 ° C).
  • °C is preferable.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferable, and propylene glycol monoethyl ether or ethyl lactate is even more preferable.
  • the "flash point” means a value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co., Ltd.
  • the solvent preferably contains the component (M1). It is more preferable that the solvent is substantially composed of only the component (M1) or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent more preferably contains both the component (M1) and the component (M2).
  • the mass ratio (M1 / M2) of the component (M1) to the component (M2) is preferably "100/0" to "0/10", more preferably “100/0” to "15/85", and ""100/0” to “40/60” are more preferable, and "100/0" to "60/40” are particularly preferable. That is, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more. 60/40 or more is more preferable. When such a configuration is adopted, the number of development defects can be further reduced.
  • the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.
  • the solvent may further contain components other than the components (M1) and (M2).
  • the content of the components other than the components (M1) and (M2) is preferably 5 to 30% by mass with respect to the total amount of the solvent.
  • the content of the solvent in the resist composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. By doing so, the coatability of the resist composition can be further improved.
  • the solid content means all components other than the solvent.
  • the solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the resist composition.
  • the resist composition may further contain an acid diffusion control agent.
  • the acid diffusion control agent acts as a quencher for trapping the acid generated from the photoacid generator, and plays a role of controlling the acid diffusion phenomenon in the resist film.
  • the acid diffusion control agent may be, for example, a basic compound.
  • the basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).
  • R 200 , R 201 and R 202 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 1 to 20 carbon atoms). Represents an aryl group (preferably 6 to 20 carbon atoms), and R 201 and R 202 may be bonded to each other to form a ring.
  • the alkyl group having a substituent is preferably 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.
  • 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 the general formula (A) and the general formula (E) are unsubstituted.
  • guanidine aminopyrrolidin, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin (alkyl group portion may be linear or branched chain, partly replaced with ether group and / or ester group.
  • the total number of all amino acids other than the hydrogen atom in the alkyl group portion is preferably 1 to 17), or piperidine or the like is preferred.
  • a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or a hydroxyl group and / Or an aniline derivative having an ether bond or the like is more preferable.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
  • Compounds having a diazabicyclo structure include, for example, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [ 5,4,0] Undeca-7-en and the like.
  • Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group.
  • triphenylsulfonium hydroxide tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxydo.
  • Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Can be mentioned.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
  • Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine, and (HO-C 2 H 4- OC 2 H 4 ). 2 N (-C 3 H 6 -O-CH 3 ) and the like can be mentioned.
  • Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
  • Preferred examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
  • amine compound for example, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom.
  • the amine compound preferably has an oxyalkylene group.
  • the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
  • 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 an oxyethylene group. Is more preferable.
  • ammonium salt compound examples include primary, secondary, tertiary and quaternary ammonium salt compounds, 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 oxyalkylene group.
  • the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
  • 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.
  • Oxyethylene groups are more preferred.
  • the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and among them, a halogen atom or a sulfonate is preferable.
  • the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom.
  • the sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms.
  • Examples of the organic sulfonate include an alkyl sulfonate having 1 to 20 carbon atoms and an aryl sulfonate.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, an aromatic ring 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 group, a naphthalene ring group, and an anthracene ring group.
  • the substituents that the benzene ring group, the naphthalene ring group, and the anthracene ring group can have are a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. preferable.
  • Examples of the linear or branched alkyl group and cycloalkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group and t-butyl group. Examples thereof include an n-hexyl group and a cyclohexyl group.
  • substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group and the like.
  • the amine compound having a phenoxy group 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 substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and the like. Examples thereof include an aryloxy group.
  • the substituent of the substituent may be any of 2 to 6 positions.
  • the number of substituents may be any of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
  • 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 oxyethylene. Groups are more preferred.
  • the amine compound having a phenoxy group is prepared by heating a primary or secondary amine having a phenoxy group and a haloalkyl ether to react, and then adding a strong base (for example, sodium hydroxide, potassium hydroxide, and tetraalkylammonium) to the reaction system. Etc.) is added, and the reaction product is further extracted with an organic solvent (for example, ethyl acetate, chloroform, etc.). Alternatively, it is obtained by heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal, adding an aqueous solution of a strong base to the reaction system, and further extracting the reaction product with an organic solvent. ..
  • a strong base for example, sodium hydroxide, potassium hydroxide, and tetraalkylammonium
  • the resist composition has a proton-accepting functional group as an acid diffusion control agent, and is decomposed by irradiation with active light or radiation to reduce or eliminate the proton-accepting property, or to change from the proton-accepting property to acidic. It may contain a compound that produces a modified compound (hereinafter, also referred to as compound (PA)).
  • the proton-accepting functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a macrocyclic structure. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to ⁇ -conjugation.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.
  • the compound (PA) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the 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.
  • a low molecular weight compound having a nitrogen atom and a group desorbed by the action of an acid can also be used as an acid diffusion control agent.
  • the low molecular weight compound is preferably an amine derivative having a group eliminated by the action of an acid on a nitrogen atom.
  • the group eliminated by the action of the acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group, and a carbamate group or a hemiaminol ether group is more preferable. preferable.
  • the molecular weight of the low molecular weight compound is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
  • the low molecular weight compound may have a carbamate group having a protecting group on the nitrogen atom.
  • the content of the acid diffusion control agent is preferably 0.001 to 15% by mass, preferably 0.01 to 8% by mass, based on the total solid content of the resist composition. More preferred.
  • the acid diffusion control agent may be used alone or in combination of two or more.
  • the resist composition contains a compound represented by the general formula (PB) as a photoacid generator, the compound represented by the general formula (PB) includes a structure having a function corresponding to an acid diffusion control agent. Therefore, it is also preferable that the resist composition does not substantially contain the acid diffusion control agent.
  • the fact that the acid diffusion control agent is substantially not contained means that the content of the acid diffusion control agent is 5% by mass or less with respect to the content of the compound represented by the general formula (PB). ..
  • the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and the molar ratio is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern over time from exposure to heat treatment.
  • the photoacid generator / acid diffusion control agent (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.
  • Examples of the acid diffusion control agent include the compounds described in paragraphs [0140] to [0144] of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). Can also be mentioned.
  • the resist composition may contain a hydrophobic resin different from the 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 are a uniform mixture of polar and non-polar substances. It does not have to contribute to.
  • the effects of adding the hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with respect to water, and suppressing outgas.
  • 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 to have two or more kinds. Further, the hydrophobic resin preferably has 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 chains. You may.
  • the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
  • the alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Further, it may have a substituent other than a fluorine atom.
  • the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.
  • the aryl group having a fluorine atom include 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 further have a substituent other than the fluorine atom. May be.
  • Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating unit exemplified in paragraph [0519] of US2012 / 0251948A1.
  • the hydrophobic resin may preferably contain a CH 3 partial structure side chain moiety.
  • CH 3 partial structure contained in the side chain portion in the hydrophobic resin an ethyl group, and is intended to include CH 3 partial structure a propyl group has.
  • the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the ⁇ -methyl group of the repeating unit having a methacrylic acid structure) contributes to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. small Therefore, not included in the CH 3 partial structures in the present invention.
  • the resins described in JP2011-24801A, JP2010-175859, and JP2012-032544 can also be preferably used.
  • the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resist composition. ..
  • the resist composition may contain a surfactant.
  • a surfactant is included, a pattern having better adhesion and fewer development defects can be formed.
  • the surfactant is preferably a fluorine-based and / or silicon-based surfactant.
  • Fluorine-based and / or silicon-based surfactants include, for example, the surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
  • Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431, and 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120, and 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.); Ftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF
  • the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). May be synthesized using. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991. In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
  • the resist composition comprises 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 carboxylic acid group. (Alicyclic or aliphatic compound) containing the above may be further contained.
  • the resist composition may further contain a dissolution inhibitory compound.
  • a dissolution inhibitory compound is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and its solubility in an organic developer is reduced.
  • the composition of the present invention relates to an actinic or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit substrate manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. It relates to a sensitive light-sensitive or radiation-sensitive resin composition used for producing a flat plate printing plate or an acid-curable composition.
  • the pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.
  • the present invention also relates to a sensitive light or radiation sensitive film (also referred to as a "resist film”) formed by the sensitive light or radiation composition of the present invention.
  • a sensitive light or radiation sensitive film also referred to as a "resist film”
  • Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate.
  • the thickness of this film is preferably 0.02 to 0.1 ⁇ m.
  • As a method of coating on the substrate it is applied on the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., but spin coating is preferable, and the number of rotations thereof is high. 1000-3000 rpm (rotations per minute) is preferable.
  • the coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes to form a thin film.
  • a silicon wafer can be used, and examples of the material to be the outermost layer include Si, SiO 2 , SiN, SiON, TiN, and the like.
  • WSi, BPSG, SOG, organic antireflection film and the like can be mentioned.
  • the procedure of the pattern forming method using the resist composition is not particularly limited, but it is preferable to have the following steps.
  • Step 1 Forming a resist film on a substrate using a resist composition
  • Step 2 Exposing the resist film (preferably with electron beam (EB) or EUV light)
  • Step 3 Using a developing solution , Step of developing the exposed resist film and forming a pattern
  • EB electron beam
  • Step 3 Using a developing solution , Step of developing the exposed resist film and forming a pattern
  • Step 1 is a step of forming a resist film on the substrate using the resist composition.
  • the definition of the resist composition is as described above.
  • Examples of the method of forming a resist film on a substrate using a resist composition include a method of applying a resist composition on a substrate. It is preferable to filter the resist composition as necessary before coating.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, still more preferably 0.03 ⁇ m or less.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the resist composition can be 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 or coater.
  • the coating method is preferably spin coating using a spinner.
  • the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
  • the substrate may be dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the resist film.
  • drying method examples include a method of heating and drying.
  • the heating can be carried out by a means provided in a normal exposure machine and / or a developing machine, and may be carried out by using a hot plate or the like.
  • the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, still more preferably 80 to 130 ° C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, still more preferably 60 to 600 seconds.
  • the film thickness of the resist film is not particularly limited, but 10 to 65 nm is preferable, and 15 to 50 nm is more preferable, from the viewpoint of being able to form a fine pattern with higher accuracy.
  • a top coat may be formed on the upper layer of the resist film by using the top coat composition. It is preferable that the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film. Further, it is preferable to dry the resist film before forming the top coat. Next, the topcoat composition can be applied onto the obtained resist film by the same means as in the method for forming the resist film, and further dried to form a topcoat.
  • the film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.
  • the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method.
  • the top coat is based on the description in paragraphs [0072] to [0082] of JP-A-2014-059543. Can be formed.
  • the basic compound that can be contained in the top coat include basic compounds that may be contained in the resist composition described later.
  • the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
  • Step 2 is a step of exposing the resist film (preferably with an electron beam (EB) or EUV light).
  • the exposure method include a method of irradiating the formed resist film with an electron beam (EB) or EUV light through a predetermined mask.
  • the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, still more preferably 80 to 130 ° C.
  • the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.
  • the heating can be carried out by means provided in a normal exposure machine and / or a developing machine, and may be carried out by using a hot plate or the like. This process is also called post-exposure baking.
  • Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern.
  • the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).
  • 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), and 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). ), A method of spraying the developer on the surface of the substrate (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic discharge method). ). Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.
  • the development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • alkaline aqueous solution containing alkali is not particularly limited, and for example, a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a cyclic amine, or the like can be used.
  • Examples include alkaline aqueous solutions containing.
  • the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • An appropriate amount of alcohols, surfactants and the like may be added to the alkaline developer.
  • the alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually 10.0 to 15.0.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. It is preferable to have it.
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone.
  • Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl.
  • examples thereof include butyl, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
  • the alcohol solvent for example, the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167A1 can be used. ..
  • 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% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developing solution. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
  • the pattern forming method preferably includes a step of washing with a rinsing solution after the step 3.
  • Examples of the rinsing solution used in the rinsing step after the step of developing with an alkaline developer include pure water. An appropriate amount of surfactant may be added to pure water. An appropriate amount of surfactant may be added to the rinse solution.
  • the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used.
  • a rinsing solution a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Is preferable.
  • the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include those similar to those described in the developing solution containing an organic solvent.
  • the method of the rinsing process is not particularly limited, for example, a method of continuously discharging the rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the surface of a substrate (spray method).
  • the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. In addition, this step has the effect of smoothing the resist pattern and improving the surface roughness of the pattern.
  • the heating step after the rinsing step is usually performed at 40 to 250 ° C. (preferably 90 to 200 ° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
  • the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form the pattern on the substrate.
  • the processing method of the substrate (or the underlayer film and the substrate) is not particularly limited, but the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to obtain the substrate.
  • the method of forming the pattern is preferable.
  • the dry etching may be one-step etching or multi-step etching. When the etching is an etching consisting of a plurality of stages, the etching of each stage may be the same process or different processes.
  • etching any known method can be used for etching, and various conditions and the like are appropriately determined according to the type and application of the substrate.
  • the Bulletin of the International Society of Optical Engineering (Proc. Of SPIE) Vol. Etching can be performed according to 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, and the like. It is also possible to follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Published Publisher: SEMI Japan". Of these, oxygen plasma etching is preferable for dry etching.
  • the resist composition and various materials used in the pattern forming method of the present invention are made of metal or the like. It is preferable that it does not contain impurities.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppt or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
  • examples of the metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, etc. W, Zn and the like can be mentioned.
  • Examples of the method for removing impurities such as metals from various materials include filtration using a filter.
  • the filter pore size is preferably less than 100 nm, more preferably 10 nm or less, and even more preferably 5 nm or less.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the filter may be composed of a composite material in which the above filter material and an ion exchange medium are combined.
  • a filter that has been pre-cleaned with an organic solvent may be used.
  • Filter In the filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
  • the step of filtering the various materials a plurality of times may be a circulation filtration step.
  • a polyethylene filter having a pore diameter of 50 nm, a nylon filter having a pore diameter of 10 nm, and a polyethylene filter having a pore diameter of 3 nm in a permutation and perform circulation filtration 10 times or more.
  • the inside of the resist composition manufacturing apparatus is preferably gas-replaced with an inert gas such as nitrogen. This makes it possible to suppress the dissolution of an active gas such as oxygen in the resist composition.
  • the resist composition is filtered through a filter and then filled in a clean container.
  • the resist composition filled in the container is preferably stored in a refrigerator. As a result, performance deterioration over time is suppressed.
  • the shorter the time from the completion of filling the composition into the container to the start of refrigerated storage is preferably, generally within 24 hours, preferably within 16 hours, more preferably within 12 hours, and 10 Within hours is even more preferred.
  • the storage temperature is preferably 0 to 15 ° C, more preferably 0 to 10 ° C, and even more preferably 0 to 5 ° C.
  • a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material having a low metal content as a raw material constituting various materials, and a filter filtration of the raw materials constituting various materials are performed. Examples thereof include a method of performing the distillation and a method of performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
  • impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination.
  • a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.
  • an inorganic adsorbent such as silica gel and zeolite
  • an organic adsorbent such as activated carbon
  • Conductive compounds are added to organic treatment liquids such as rinse liquids to prevent damage to chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. You may.
  • the conductive compound is not particularly limited, and examples thereof include methanol.
  • the amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, in terms of maintaining preferable development characteristics or rinsing characteristics.
  • Examples of the chemical solution piping include various piping coated with SUS (stainless steel), antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perflooloalkoxy resin, etc.). Can be used.
  • antistatic treated polyethylene, polypropylene, or fluororesin polytetrafluoroethylene, perflooloalkoxy resin, etc.
  • a method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention.
  • Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808.
  • SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement" can be mentioned.
  • the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, still more preferably 1.7 or less. ..
  • the pattern to be formed is a trench pattern or a contact hole pattern
  • the aspect ratio obtained by dividing the pattern height by the trench width or the hole diameter is preferably 4.0 or less, preferably 3.5. The following is more preferable, and 3.0 or less is further preferable.
  • the pattern forming method of the present invention can also be used for guide pattern forming in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Page 4815-4823).
  • DSA Directed Self-Assembly
  • the pattern formed by the above method can be used as, for example, the core material (core) of the spacer process disclosed in Japanese Patent Application Laid-Open No. 3-270227 and Japanese Patent Application Laid-Open No. 2013-164509.
  • the present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is suitably mounted on an electric electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).
  • the precipitated polymer was filtered, and the filtered polymer was washed with 195 g of the above-mentioned mixed solvent of n-heptane and ethyl acetate.
  • the washed polymer was air-dried at 40 ° C. to obtain 10.0 g of resin (A-1).
  • the weight average molecular weight by GPC was 13000, and the molecular weight dispersion (Mw / Mn) was 1.95.
  • the resin (A) shown in Table 1 was synthesized in the same manner as in the above synthesis example of the resin A-1 except that the monomer used was changed.
  • the composition ratio (molar ratio) of the resin (A) was calculated by 1 H-NMR or 13 C-NMR measurement.
  • the weight average molecular weight (Mw: polystyrene conversion) and the dispersity (Mw / Mn) of the resin (A) were calculated by GPC (solvent: THF) measurement.
  • Table 1 shows the composition ratio (molar ratio) of the repeating unit, the content (molar ratio) of the repeating unit having an aromatic group, the weight average molecular weight, and the dispersity of each resin.
  • the repeating unit 1 corresponds to the repeating unit (a1).
  • the resins (RA-1) to (RA-4) are not the resins (A), they are listed in Table 1 for convenience.
  • the repeating units of each resin (A-1 to A-47, RA-1 to RA-4) are shown below.
  • the structure of the hydrophobic resin (E) (resin E-1) is shown below.
  • the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the hydrophobic resin E-1 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
  • the composition ratio (molar ratio) of the resin was measured by 13 C-NMR.
  • the hydrophobic resin E-1 had a weight average molecular weight (Mw) of 15,000, a dispersity (Mw / Mn) of 1.50, and a composition ratio of 50/50 in terms of molar ratio.
  • the underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm.
  • the resist composition shown in Table 3 (see Table 2 for the composition of the resist composition) was applied thereto, and the mixture was baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
  • an EUV exposure device Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech
  • pattern irradiation was performed on the silicon wafer having the obtained resist film.
  • the resist film after exposure was baked at 90 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.
  • the resist composition of the present invention can reduce the collapse front width, increase the bridge front width, have an excellent resolution margin, and further provide roughness when a pattern is formed by organic solvent development. It was confirmed that the performance was excellent. On the other hand, the resist compositions of Comparative Examples had insufficient performance.
  • the underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm.
  • the resist composition shown in Table 4 (see Table 2 for the composition of the resist composition) was applied thereto, and the mixture was baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
  • an EUV exposure device Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech
  • pattern irradiation was performed on the silicon wafer having the obtained resist film. It was.
  • the resist film after exposure was baked at 90 ° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, this was spin-dried to obtain a positive pattern. Roughness performance, collapse front width, bridge front width, and resolution margin were evaluated in the same manner as described above.
  • the resist composition of the present invention can reduce the collapse front width, increase the bridge front width, have an excellent resolution margin, and further provide roughness performance when a pattern is formed by alkaline development. It was confirmed that it was excellent. On the other hand, the resist compositions of Comparative Examples had insufficient performance.
  • the resist composition of the present invention can reduce the collapse front width, increase the bridge front width, have an excellent resolution margin, and further provide roughness performance when a pattern is formed by alkaline development. It was confirmed that it was excellent. On the other hand, the resist compositions of Comparative Examples had insufficient performance.
  • a sensitive light-sensitive or radiation-sensitive resin composition capable of reducing the collapse front width, increasing the bridge front width, excellent resolution margin, and forming a pattern excellent in roughness performance. can do. Further, according to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin film, a pattern forming method, and a method for manufacturing an electronic device with respect to the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. ..

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PCT/JP2020/035312 2019-09-30 2020-09-17 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び、電子デバイスの製造方法 WO2021065549A1 (ja)

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WO2024084970A1 (ja) * 2022-10-21 2024-04-25 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法

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