WO2019167451A1 - Composition de résine sensible aux rayons actiniques ou au rayonnement, film sensible aux rayons actiniques ou au rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique - Google Patents

Composition de résine sensible aux rayons actiniques ou au rayonnement, film sensible aux rayons actiniques ou au rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique Download PDF

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Publication number
WO2019167451A1
WO2019167451A1 PCT/JP2019/000914 JP2019000914W WO2019167451A1 WO 2019167451 A1 WO2019167451 A1 WO 2019167451A1 JP 2019000914 W JP2019000914 W JP 2019000914W WO 2019167451 A1 WO2019167451 A1 WO 2019167451A1
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Prior art keywords
group
sensitive
radiation
general formula
atom
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PCT/JP2019/000914
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English (en)
Japanese (ja)
Inventor
暁 ▲高▼田
修平 山口
敦靖 野崎
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富士フイルム株式会社
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Priority to JP2020502845A priority Critical patent/JP7125470B2/ja
Publication of WO2019167451A1 publication Critical patent/WO2019167451A1/fr

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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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • 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 an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method.
  • a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption.
  • a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid.
  • PEB Post Exposure Bake
  • the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid.
  • development is performed using, for example, an alkaline solution.
  • an exposed part is removed and a desired pattern is obtained.
  • various alkali developers have been proposed.
  • this alkaline developer a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.
  • the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA).
  • high NA numerical aperture
  • an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
  • immersion liquid a liquid having a high refractive index
  • the present invention reduces both immersion defects and development defects while having a high followability of the immersion liquid to the exposure apparatus even if the scanning speed of the exposure is set to an extremely high speed (for example, 700 mm / second or more). It is an object to provide a possible actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method using the same. .
  • Actinic ray-sensitive or radiation-sensitive resin containing a resin (P) having a repeating unit represented by the following general formula (1), and a resin (A) having a group that is decomposed by the action of an acid to increase polarity Composition.
  • Z represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 11 OCH 2 —, or a group represented by R 12 OC ( ⁇ O) CH 2 —.
  • R 11 and R 12 each independently represents a monovalent substituent.
  • X represents an oxygen atom or a sulfur atom.
  • L represents a single bond or a (m + 1) -valent linking group.
  • R represents a group represented by the following formula (1-1).
  • m represents a positive integer. When m is 2 or more, the plurality of R may be the same as or different from each other. When L represents a single bond, m represents 1.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Z 2 is represented by a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 21 OCH 2 —, or R 22 OC ( ⁇ O) CH 2 —.
  • R 21 and R 22 each independently represents a monovalent substituent.
  • X 2 represents an oxygen atom or a sulfur atom.
  • R 2 represents a group represented by the following formula (1-1).
  • * Represents a bond to X 2.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • R 31 and R 32 each independently represents a monovalent substituent.
  • X 3 represents an oxygen atom or a sulfur atom.
  • L 3 represents a divalent linking group.
  • R 3 represents a group represented by the following formula (1-1).
  • Z 4 represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
  • X 4 represents an oxygen atom or a sulfur atom.
  • L 4 represents a divalent linking group.
  • R 4 represents a group represented by the following formula (1-1).
  • * represents a bond with —C ( ⁇ O) — or —O—.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • the resin (P) further has a repeating unit (a1) having an organic group having one or more CH 3 partial structures which is stable to an acid in a side chain portion.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
  • Za represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
  • Ra represents an alkyl group or a cycloalkyl group having one or more CH 3 partial structures and stable to an acid.
  • Zb represents a hydrogen atom, an alkyl group, a halogen atom, a group represented by R 61 OCH 2 —, or a group represented by R 62 OC ( ⁇ O) CH 2 —.
  • R 61 and R 62 each independently represent a monovalent substituent.
  • Rd represents an electron withdrawing group.
  • Zc represents a hydrogen atom, a halogen atom, or an alkyl group.
  • L 1 represents an alkylene group, a cycloalkylene group, or a group formed by combining these. If L 1 is present in plurality, a plurality of L 1 may be be the same or different from each other.
  • Re represents a divalent linking group.
  • n1 represents an integer of 0 to 5.
  • Xa represents an alkylene group, an oxygen atom, or a sulfur atom.
  • Rf represents an electron withdrawing group.
  • m1 represents an integer of 1 to 3.
  • both immersion defects and development defects are reduced while having high followability of the immersion liquid to the exposure apparatus.
  • a possible actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern forming method, and a method for producing an electronic device can be provided.
  • the description of group (atomic group) in this specification the description which has not described substitution and non-substitution includes what has a substituent with what does not have a 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” refers to a group containing at least one carbon atom.
  • the term “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB). : Electron Beam) or the like.
  • light means actinic rays or radiation.
  • exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams, and This includes drawing with particle beams such as ion beams.
  • “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-produced by Tosoh Corporation).
  • Actinic ray-sensitive or radiation-sensitive resin composition The actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a resist composition, which may be a positive resist composition or a negative resist composition.
  • the resist composition is preferably a mold type resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development, but is preferably a resist composition for alkali development.
  • the resist composition of the present invention is typically a chemically amplified resist composition.
  • the composition of the present invention components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described in detail.
  • composition of this invention contains resin (P) which has a repeating unit represented by following General formula (1).
  • Z represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 11 OCH 2 —, or a group represented by R 12 OC ( ⁇ O) CH 2 —.
  • R 11 and R 12 each independently represents a monovalent substituent.
  • X represents an oxygen atom or a sulfur atom.
  • L represents a single bond or a (m + 1) -valent linking group.
  • R represents a group represented by the following formula (1-1).
  • m represents a positive integer. When m is 2 or more, the plurality of R may be the same as or different from each other. When L represents a single bond, m represents 1.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • the resin (P) is preferably a hydrophobic resin.
  • hydrophobic resin (P) is resin different from resin (A).
  • the resin (P) is preferably designed to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film.
  • the repeating unit represented by the general formula (1) of the present invention has a group represented by the general formula (1-1).
  • a group represented by the following formula (a) (* represents a bond) is known, but the structure represented by the following formula (a) is not sufficient to impart hydrophobicity.
  • the scanning speed is extremely high, high followability of the immersion liquid with respect to the exposure apparatus tends not to be ensured.
  • the immersion in the exposure apparatus when the scanning speed is extremely high
  • the affinity for the alkaline developer is decreased on the contrary, so that development defects tend to be deteriorated.
  • the actinic ray-sensitive or radiation-sensitive composition contain a resin (P) having a repeating unit represented by the general formula (1) as a hydrophobic resin.
  • both immersion defects and development defects can be further reduced while having high followability of the immersion liquid to the exposure apparatus.
  • the group represented by the general formula (1-1) in the repeating unit represented by the general formula (1) gives an appropriate hydrophobic property to the resin (P), thereby making the exposure scan speed extremely high.
  • the following ability of the immersion liquid to the exposure apparatus is sufficient, and the occurrence of immersion defects can be reduced while the affinity of the resin (P) to the alkaline developer can be sufficiently provided. This is thought to be because the occurrence of development defects was also reduced.
  • Examples of the alkyl group for Z include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group).
  • a methyl group is preferred.
  • Examples of the alkoxy group for Z include an alkoxy group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms is preferable.
  • a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example, A fluorine atom or a chlorine atom is preferable.
  • the monovalent organic group as R 11 and R 12 is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and aryl. And a group (preferably having a carbon number of 6 to 10).
  • the monovalent substituent as R 11 and R 12 may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom. An atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), a carboxy group, and the like can be given.
  • Z is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, and even more preferably a hydrogen atom or a methyl group.
  • the alkyl group and alkoxy group as Z may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group. (Preferably having 1 to 4 carbon atoms) and a carboxy group.
  • X represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • the (m + 1) -valent linking group as L is preferably a divalent or trivalent linking group (in other words, m is preferably 1 or 2) and is a divalent linking group. Is more preferable (in other words, m is preferably 1).
  • the linking group as L is preferably a group consisting of an aliphatic group, an aromatic group, —O—, —C ( ⁇ O) —, —S—, or a combination of two or more thereof.
  • examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Can do.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the divalent aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group.
  • the divalent aromatic group examples include an aryl group. Of these, a phenylene group and a naphthylene group are preferable.
  • the divalent aromatic group may have a substituent, and examples thereof include an alkyl group in addition to the examples of the substituent in the divalent aliphatic group.
  • specific examples of the (m + 1) -valent linking group include groups obtained by removing any (m-1) hydrogen atoms from the specific examples of the divalent linking group described above. Can be mentioned.
  • L include, for example, the following linking groups, but are not limited thereto.
  • linking groups may further have a substituent.
  • Examples of the alkyl group for R 1 and R 1 ′ include, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and Pentyl group), and an alkyl group having 1 to 5 carbon atoms is preferable.
  • Examples of the cycloalkyl group represented by R 1 and R 1 ′ include cycloalkyl groups having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).
  • a cycloalkyl group having 5 to 10 carbon atoms is preferred.
  • the aryl group for R 1 and R 1 ′ include an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms (for example, a phenyl group or a naphthyl group) is preferable.
  • Each group of R 1 and R 1 ′ may further have a substituent.
  • substituents include a group having a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom (for example, an alkoxy group, an acyl group, etc. ), A group having a nitrogen atom (for example, an amino group, an alkylamino group, a dialkylamino group, etc.), and a fluorine atom and a chlorine atom are more preferable.
  • R 1 and R 1 ′ include a fluorinated alkyl group in which a hydrogen atom of the above alkyl group is substituted with a fluorine atom, and a fluorinated aryl group in which a hydrogen atom of the above aryl group is substituted with a fluorine atom.
  • a fluorinated alkyl group in which a hydrogen atom of the above alkyl group is substituted with a fluorine atom
  • a fluorinated aryl group in which a hydrogen atom of the above aryl group is substituted with a fluorine atom.
  • substitution with a fluorine atom may be for all hydrogen atoms or for some hydrogen atoms.
  • the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).
  • Z 2 is represented by a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 21 OCH 2 —, or R 22 OC ( ⁇ O) CH 2 —.
  • R 21 and R 22 each independently represents a monovalent substituent.
  • X 2 represents an oxygen atom or a sulfur atom.
  • R 2 represents a group represented by the following formula (1-1).
  • * Represents a bond to X 2.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • alkyl group, alkoxy group and halogen atom of Z 2 are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
  • R 21 and R 22 include a group represented by R 11 OCH 2 — as Z in the general formula (1), or a group represented by R 12 OC ( ⁇ O) CH 2 —.
  • Z 2 is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, still more preferably a hydrogen atom or a methyl group.
  • X 2 is preferably an oxygen atom.
  • Specific examples and preferred examples of R 2 are the same as those described for R in the general formula (1).
  • the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (3) or (4).
  • —CR bonded to the oxygen atom in the side chain of the repeating unit represented by the general formula (3) or —C ( ⁇ O) — in the side chain of the repeating unit represented by the following general formula (4) Since 1 R 1 ′ F is away from the main chain, the alkali developer tends to become familiar and the alkali reactivity of the ester moiety tends to increase. This is preferable because development defects tend to be further improved. Further, from the viewpoint of high followability of the immersion liquid with respect to the exposure apparatus and suppression of development defects, the repeating unit represented by the general formula (3) is more preferable.
  • Z 3 is represented by a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, a group represented by R 31 OCH 2 —, or R 32 OC ( ⁇ O) CH 2 —.
  • R 31 and R 32 each independently represents a monovalent substituent.
  • X 3 represents an oxygen atom or a sulfur atom.
  • L 3 represents a divalent linking group.
  • R 3 represents a group represented by the following formula (1-1).
  • Z 4 is represented by a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 41 OCH 2 —, or R 42 OC ( ⁇ O) CH 2 —.
  • R 41 and R 42 each independently represents a monovalent substituent.
  • X 4 represents an oxygen atom or a sulfur atom.
  • L 4 represents a divalent linking group.
  • R 4 represents a group represented by the following formula (1-1).
  • * Represents a bond with —C ( ⁇ O) — or —O—.
  • R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
  • alkyl group, alkoxy group and halogen atom of Z 3 are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
  • R 31 and R 32 include a group represented by R 11 OCH 2 — as Z in the general formula (1), or a group represented by R 12 OC ( ⁇ O) CH 2 —.
  • Z 3 is preferably a hydrogen atom, an alkyl group, or a halogen atom, more preferably a hydrogen atom, a methyl group, or a fluorine atom, and still more preferably a hydrogen atom or a methyl group.
  • X 3 is preferably an oxygen atom.
  • Specific examples and preferred examples of the divalent linking group as L 3 are the same as those described in L as the divalent linking group of the general formula (1).
  • L 3 and R 3 are not bonded to each other to form a ring.
  • alkyl group, alkoxy group and halogen atom of Z 4 are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
  • R 41 and R 42 include a group represented by R 11 OCH 2 — as Z in the general formula (1), or a group represented by R 12 OC ( ⁇ O) CH 2 —.
  • Z 4 is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, and even more preferably a hydrogen atom or a methyl group.
  • X 4 is preferably an oxygen atom.
  • Specific examples and preferred examples of the divalent linking group as L 4 are the same as those described in L as the divalent linking group of the general formula (1).
  • L 4 and R 4 are not bonded to each other to form a ring.
  • the content of the repeating unit represented by the general formula (1) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, based on all repeating units in the resin (P). 40 to 100 mol% is most preferable.
  • the content of the repeating unit represented by the general formula (1) is the total content of the resin (P). It is preferably 10 to 90 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 85 mol%, most preferably 40 to 85 mol%, based on the repeating unit.
  • X represents a halogen atom
  • Ph represents a phenyl group
  • the resin (P) preferably has a repeating unit (a1) having an organic group having one or more CH 3 partial structures which is stable to an acid in a side chain portion.
  • the resin (P) has the repeating unit (a1) having an organic group that is stable against acid in the side chain portion together with the repeating unit represented by the general formula (1).
  • the CH 3 partial structure possessed by the side chain moiety in the repeating unit (a1) (hereinafter also simply referred to as “side chain CH 3 partial structure”) has a CH 3 partial structure possessed by an ethyl group, a propyl group or the like. It is included.
  • a methyl group directly bonded to the main chain of the repeating unit (a1) (for example, ⁇ -methyl group of the repeating unit having a methacrylic acid structure) is unevenly distributed on the surface of the resin (P) due to the influence of the main chain. Therefore, it is not included in the CH 3 partial structure in the present invention.
  • the resin (P) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M).
  • R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
  • CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
  • R 11 is an ethyl group (CH 2 CH 3 )
  • R 11 to R 14 each independently represents a side chain portion.
  • R 11 to R 14 in the side chain portion include a hydrogen atom or a monovalent organic group.
  • the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
  • Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
  • the repeating unit (a1) is not particularly limited as long as it has an acid group in the side chain portion and has one or more CH 3 partial structures, but the following general formula (5) It is preferable that it is a repeating unit represented by these.
  • Za represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
  • Ra represents an alkyl group or a cycloalkyl group having one or more CH 3 partial structures and stable to an acid.
  • the alkyl group or cycloalkyl group that is stable to an acid does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group).
  • An alkyl group or a cycloalkyl group is preferable.
  • the alkyl group of Za is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is more preferable.
  • a halogen atom of Za a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.
  • Ra includes an alkyl group or a cycloalkyl group having one or more CH 3 partial structures.
  • the above cycloalkyl group may further have an alkyl group as a substituent.
  • Ra is preferably an unsubstituted alkyl group or an unsubstituted cycloalkyl group substituted with an alkyl group.
  • the alkyl group or cycloalkyl group having one or more CH 3 partial structures as Ra and stable to an acid preferably has 2 to 10 CH 3 partial structures, preferably 2 to 8 It is more preferable to have no more.
  • the repeating unit (a1) is preferably an acid-stable (non-acid-decomposable) repeating unit.
  • the repeating unit (a1) is a repeating unit having no group that decomposes by the action of an acid to generate a polar group. Preferably there is.
  • the content of the repeating unit (a1) is preferably 10 to 90 mol%, preferably 10 to 80 mol%, based on all repeating units in the resin (P). More preferred is 15 to 60 mol%.
  • TMS represents a trimethylsilyl group.
  • the resin (P) has a repeating unit (a2) having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
  • the resin (P) has the repeating unit (a2) together with the repeating unit represented by the general formula (1), it is possible to further improve the affinity of the resist film to the alkaline developer during development, and development defects Tends to be further reduced.
  • the repeating unit (a2) is not particularly limited as long as it is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, but is represented by the following general formula (6) or (7). It is preferably a repeating unit.
  • Zb represents a hydrogen atom, an alkyl group, a halogen atom, a group represented by R 61 OCH 2 —, or a group represented by R 62 OC ( ⁇ O) CH 2 —.
  • R 61 and R 62 each independently represent a monovalent substituent.
  • Rd represents an electron withdrawing group.
  • Zc represents a hydrogen atom, a halogen atom, or an alkyl group.
  • L 1 represents an alkylene group, a cycloalkylene group, or a group formed by combining these. If L 1 is present in plurality, a plurality of L 1 may be be the same or different from each other.
  • Re represents a divalent linking group.
  • n1 represents an integer of 0 to 5.
  • Xa represents an alkylene group, an oxygen atom, or a sulfur atom.
  • Rf represents an electron withdrawing group.
  • m1 represents an integer of 1 to 3.
  • alkyl group for Zb examples include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group).
  • a methyl group is preferred.
  • a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.
  • Zb is preferably a fluorine atom, a chlorine atom, a methyl group or a hydrogen atom, more preferably a fluorine atom or a methyl group.
  • the monovalent organic group as R 61 and R 62 is not particularly limited, and examples thereof include alkyl groups (preferably having 1 to 4 carbon atoms), cycloalkyl groups (preferably having 6 to 10 carbon atoms), and aryl groups. And a group (preferably having a carbon number of 6 to 10).
  • the monovalent substituent as R 11 and R 12 may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom. An atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), a carboxy group, and the like can be given.
  • the electron withdrawing group as Rd is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond.
  • n ew is the number of repeating linking groups represented by —C (R ew1 ) (R ew2 ) —, and represents an integer of 0 or 1. When n ew is 0, it represents a single bond, indicating that Y ew1 is directly bonded.
  • Y ew1 represents a halogen atom, a cyano group, a nitro group, an aryl group substituted with a halo (cyclo) alkyl group, a haloaryl group, or a haloalkyl group represented by -C (R f1 ) (R f2 ) -R f3 described later , An oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and combinations thereof.
  • n ew is 1.
  • R ew1 and R ew2 each independently represent an arbitrary substituent, such as a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms) or an aryl group ( Preferably, it represents 6 to 10 carbon atoms. At least two of R ew1 , R ew2 and Y ew1 may be connected to each other to form a ring.
  • the “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated
  • the “haloaryl group” represents an aryl group that is at least partially halogenated.
  • Y ew1 is preferably a halogen atom, a halo (cyclo) alkyl group represented by —C (R f1 ) (R f2 ) —R f3 , an haloaryl group, or an aryl group substituted with a haloalkyl group.
  • R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group.
  • R f2 and R f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R f2 and R f3 may be linked to form a ring.
  • Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably R f2 and R f3 are (halo) alkyl groups. Or a (halo) cycloalkyl group. More preferably, R f2 represents the same group as R f1 or is linked to R f3 to form a ring. Examples of the ring formed by connecting R f2 and R f3 include a (halo) cycloalkyl ring.
  • the (halo) alkyl group in R f1 to R f3 may be linear or branched, and the linear (halo) alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, For example, methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decanyl group and the like, and groups in which these are halogenated can be mentioned.
  • the branched (halo) alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, isohexyl group, Examples thereof include a t-hexyl group, an isoheptyl group, a t-heptyl group, an isooctyl group, a t-octyl group, an isononyl group, a t-decanoyl group, and a group in which these are halogenated.
  • the (halo) cycloalkyl group in R f1 to R f3 or in the ring formed by linking R f2 and R f3 may be monocyclic or polycyclic.
  • the (halo) cycloalkyl group may be a bridged type. That is, in this case, the (halo) cycloalkyl group may have a bridged structure.
  • the monocyclic type a (halo) cycloalkyl group having 3 to 8 carbon atoms is preferable.
  • Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and (halo) cycloalkyl groups having 6 to 20 carbon atoms are preferable, for example, (halo) adamantyl groups, (Halo) norbornyl group, (halo) isobornyl group, (halo) camphanyl group, (halo) dicyclopentyl group, (halo) ⁇ -pinel group, (halo) tricyclodecanyl group, (halo) tetocyclododecyl group, Mention may be made of (halo) androstanyl groups.
  • Examples of these (halo) cycloalkyl groups include those represented by the following formula and groups in which they are halogenated. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group.
  • an adamantyl group More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.
  • substituent for these alicyclic moieties include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.
  • the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group.
  • Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).
  • R f2 and R f3 or (halo) cycloalkyl group in the ring and R f2 and R f3 is formed by connecting is represented by more preferably -C (n) F (2n- 2) H A fluorocycloalkyl group is mentioned.
  • the number n of carbon atoms is not particularly limited, but preferably 5 to 13 and more preferably 6.
  • Examples of the (per) haloaryl group in Y ew1 or R f1 include a perfluoroaryl group represented by —C (n) F (n ⁇ 1) .
  • the number n of carbon atoms is not particularly limited, but preferably 5 to 13 and more preferably 6.
  • Examples of the haloalkyl group in the aryl group substituted with the haloalkyl group in Y ew1 include a haloalkyl group in a halo (cyclo) alkyl group represented by —C (R f1 ) (R f2 ) —R f3 .
  • the aryl group in the aryl group substituted with the haloalkyl group in Y ew1 is not particularly limited, and examples thereof include an aryl group having 6 to 10 carbon atoms (not including the carbon number of the haloalkyl group).
  • the ring that may be formed by connecting at least two of R ew1 , R ew2 and Y ew1 to each other is preferably a cycloalkyl group or a heterocyclic group.
  • Each group and each ring constituting the partial structure represented by the above formula (EW) described above may further have a substituent.
  • the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, Bromine, iodine), nitro group, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and other alkyl groups, methoxy group, ethoxy group, hydroxyethoxy Group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group, Aralkyl groups such as cumyl groups, aralkyloxy groups, formyl
  • Rd is preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, and more preferably an alkyl group substituted with a halogen atom (haloalkyl group). Preferably, it is a fluoroalkyl group.
  • the alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • Rd is an atomic group represented by —C (R ′ 1 ) (R ′ f1 ) (R ′ f2 ) or —C (R ′ 1 ) (R ′ 2 ) (R ′ f1 ) It is preferable that
  • R ′ 1 and R ′ 2 each independently represent a hydrogen atom or an alkyl group that is not substituted (preferably unsubstituted) with an electron-withdrawing group.
  • R ′ f1 and R ′ f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group.
  • the alkyl group as R ′ 1 and R ′ 2 may be linear or branched, and preferably has 1 to 6 carbon atoms.
  • the perfluoroalkyl group as R ′ f1 and R ′ f2 may be linear or branched, and preferably has 1 to 6 carbon atoms.
  • Rd Preferable specific examples of Rd include —CF 3 , —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —CF (CF 3 ) 2 , —CF (CF 3 ) C 2 F 5 , — CF 2 CF (CF 3 ) 2 , —C (CF 3 ) 3 , —C 5 F 11 , —C 6 F 13 , —C 7 F 15 , —C 8 F 17 , —CH 2 CF 3 , —CH 2 C 2 F 5 , —CH 2 C 3 F 7 , —CH (CF 3 ) 2 , —CH (CF 3 ) C 2 F 5 , —CH 2 CF (CF 3 ) 2 , —CH 2 CN, etc.
  • —CF 3 , —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —CH 2 CF 3 , —CH 2 C 2 F 5 , —CH 2 C 3 F 7 , —CH (CF 3) 2, -CH 2 CN are preferred, -CH 2 CF 3, -CH 2 C 2 F 5, -CH 2 C 3 F , -CH (CF 3) 2, -CH 2 CN , more preferably, -CH 2 C 2 F 5, -CH (CF 3) 2, more preferably -CH 2 CN, -CH 2 C 2 F 5, - CH (CF 3 ) 2 is particularly preferred.
  • alkyl group of Zc are the same as those described for the alkyl group as Zb in the general formula (1).
  • Specific examples and preferred examples of the halogen atom for Zc are the same as those described for the halogen atom as Zb in the general formula (1).
  • Zc is preferably a fluorine atom, a chlorine atom, a methyl group or a hydrogen atom, more preferably a fluorine atom or a methyl group.
  • the alkylene group and cycloalkylene group of L 1 may have a substituent.
  • the alkylene group in L 1 is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
  • a preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group.
  • an alkylene group is more preferable, and a methylene group is particularly preferable.
  • the divalent linking group as Re is, for example, a single bond, an ether bond, an ester bond, an amide bond, a urethane bond (—O—C ( ⁇ O) —NR— or —NR—C ( ⁇ O) —O—). Or a urea bond (group represented by —NR—C ( ⁇ O) —NR—).
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently.
  • Re is preferably a single bond or an ester bond.
  • N1 represents an integer of 0 to 5, preferably an integer of 0 to 1.
  • alkylene group for Xa examples include alkylene groups having 1 to 2 carbon atoms, and a methylene group is preferred.
  • Xa is preferably an alkylene group.
  • Rf represents an electron withdrawing group.
  • the electron withdrawing group of Rf is preferably a group represented by the following general formula (A).
  • Y represents a group that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer.
  • E represents a monovalent group.
  • Y includes carboxylic acid ester group: —COO— or OCO—, acid anhydride group: —C (O) OC (O) —, acid imide group: —NHCONH—, carboxylic acid thioester group: —COS—, carbonic acid
  • An ester group: —OC (O) O—, a sulfate ester group: —OSO 2 O—, and a sulfonate ester group: —SO 2 O— can be mentioned, and a carboxylic ester group is preferred.
  • E is not particularly limited as long as the group represented by the general formula (A) is a group that is electron withdrawing, but is preferably a partial structure represented by the above formula (EW). It is preferable that E is an electron-attracting group because the group represented by the general formula (A) is decomposed by the action of an alkali developer, and the solubility in the alkali developer tends to further increase. . E is preferably the same as that described in the partial structure represented by the above formula (EW) as the electron-withdrawing group of Rd.
  • the content of the repeating unit (a2) is preferably 10 to 90 mol%, more preferably 15 to 80 mol%, based on all repeating units in the resin (P). More preferred is 20 to 80 mol%.
  • repeating unit (a2) Preferred specific examples of the repeating unit (a2) are listed below. Note that the present invention is not limited to this.
  • the resin (P) can further have a repeating unit (a3) as long as the effects of the present invention are not impaired.
  • a repeating unit (a3) it does not specifically limit as a further repeating unit (a3),
  • the repeating unit which has a polar group can be mentioned.
  • the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
  • Preferred specific examples of the further repeating unit (a3) are listed below. Note that the present invention is not limited to this.
  • the resin (P) contains the repeating unit ( It is more preferable to have a1) and the repeating unit (a2).
  • the repeating unit represented by the general formula (1) may or may not be a repeating unit having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
  • the repeating unit represented by the general formula (1) may be the same as or different from the repeating unit represented by the general formula (a2).
  • the repeating unit represented by the general formula (1) is a repeating unit having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer
  • the general formula ( An embodiment in which the repeating unit represented by 3) or (4) corresponds to a repeating unit having a group that increases the solubility in an alkali developer is mentioned.
  • the weight average molecular weight (Mw) of the resin (P) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 as a polystyrene conversion value by GPC method. ⁇ 15,000.
  • Mw weight average molecular weight
  • Another particularly preferable form of the weight average molecular weight of the resin (P) is 3,000 to 9,500 in terms of polystyrene by GPC method.
  • the dispersity (molecular weight distribution) (hereinafter also referred to as Mw / Mn or Pd) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to Those in the range of 2.0 are used.
  • Mw / Mn or Pd molecular weight distribution
  • the resin (P) is naturally low in impurities such as metals, and the residual monomer and oligomer components are preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and 0 to 1%. Mass% is even more preferred. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained.
  • the resin (P) is shown in the table below, but the present invention is not limited to these.
  • the composition ratio of the repeating units indicates a molar ratio.
  • the repeating unit in the composition described in the following table will be described later (Ph represents a phenyl group, and TMS represents a trimethylsilyl group).
  • Resin (P) can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like.
  • an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
  • the concentration of the reaction product is 5 to 50% by mass, preferably 10 to 45% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 40 ° C. to 100 ° C.
  • Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. In a solid state such as reprecipitation method by removing the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.
  • the content of the resin (P) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.01 to 10% by mass based on the total solid content of the actinic ray- or radiation-sensitive resin composition, More preferably, it is 0.1 to 10% by mass, still more preferably 0.1 to 9% by mass, and particularly preferably 0.5 to 8% by mass.
  • resin (P) may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin (P) together, it is preferable that total content is in the said range.
  • the dynamic receding contact angle of water on the actinic ray-sensitive or radiation-sensitive film (temperature: 23 ° C., relative humidity: 45%) is determined by scanning exposure. Assuming that the speed is an ultra-high speed (for example, 700 mm / second or more), it is preferably 80 ° or more, and more preferably 85 ° or more.
  • the water dynamic receding contact angle is typically 90 ° or less. Such a dynamic receding contact angle of water can be suitably achieved, for example, by setting the content of the resin (P) within the above range.
  • the composition of the present invention may contain a hydrophobic resin (P ′) different from the resin (P). If the hydrophobic resin (P ′) does not have the repeating unit represented by the general formula (1), the hydrophobic resin (P ′) may have the above-described repeating unit that the resin (P) may have.
  • the preferred range of the content of these repeating units based on all repeating units of the hydrophobic resin (P ′) is the same as the above-described range in the resin (P).
  • the preferable range of the weight average molecular weight of the resin (P ′), the dispersity, and the content based on the total solid content of the composition of the present invention is the same as the above-described range in the resin (P).
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin having a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid and increases in polarity (hereinafter referred to as “acid-decomposable group” Or “resin (A)”.
  • acid-decomposable group a group that is decomposed by the action of an acid and increases in polarity
  • acid-decomposable group or “resin (A)”.
  • the pattern forming method of the present invention typically, when an alkaline developer is employed as the developer, a positive pattern is suitably formed, and when an organic developer is employed as the developer.
  • the negative pattern is preferably formed.
  • the acid-decomposable group preferably has a structure in which a polar group is protected with a group capable of decomposing and leaving by the action of an acid (leaving group).
  • polar groups carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Acid groups (groups dissociating in an aqueous 2.38 mass
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Excludes aliphatic alcohols substituted with sexual groups (for example, hexafluoroisopropanol groups).
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
  • Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
  • a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).
  • Examples of the group (leaving group) leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), and — And C (R 01 ) (R 02 ) (OR 39 ).
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, and octyl group.
  • the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
  • the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • a cycloalkyl group having 6 to 20 carbon atoms is preferable.
  • the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • the aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • the ring formed by combining R 36 and R 37 with each other is preferably a cycloalkyl group (monocyclic or polycyclic).
  • cycloalkyl group a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. .
  • a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal ester group or a tertiary alkyl ester group is more preferable.
  • the resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.
  • Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be bonded to form a ring structure, or may not be formed.
  • Examples of the divalent linking group for T include an alkylene group, an arylene group, —COO—Rt—, —O—Rt—, and the like.
  • Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
  • T is preferably a single bond or —COO—Rt—.
  • Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH 2 —, — (CH 2 ) 2 —, or — (CH 2 ) 3 —. More preferably, T is a single bond.
  • Xa 1 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • the alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
  • the alkyl group of Xa 1 is preferably a methyl group.
  • the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like are preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • a part of the carbon-carbon bond may be a double bond.
  • Examples of the cycloalkyl group represented by Rx 1 , Rx 2 and 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, an adamantyl group, and the like.
  • the polycyclic cycloalkyl group is preferable.
  • the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, a norbornane ring, a tetracyclo ring, or the like.
  • a polycyclic cycloalkyl ring such as a decane ring, a tetracyclododecane ring and an adamantane ring is preferred.
  • a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable.
  • the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 the structures shown below are also preferable.
  • the resin (A) preferably has a repeating unit described in paragraphs ⁇ 0336> to ⁇ 0369> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group.
  • Resin (A) is decomposed by the action of an acid described in paragraphs ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group. You may have a repeating unit containing the group which produces
  • Resin (A) may contain one type of repeating unit having an acid-decomposable group, or two or more types in combination.
  • the content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable.
  • Resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
  • Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
  • lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) More preferably, it has a repeating unit.
  • a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21) and (SL1-1).
  • the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups.
  • n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. A plurality of substituents (Rb 2 ) may be bonded to form a ring.
  • the repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).
  • A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
  • n is the number of repetitions of the structure represented by —R 0 —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
  • R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof.
  • each R 0 independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
  • Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
  • each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
  • R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
  • R 7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
  • the alkylene group or cycloalkylene group of R 0 may have a substituent.
  • Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
  • the following monomers are also suitably used as the raw material for the resin (A).
  • the resin (A) may have a repeating unit having a carbonate structure.
  • the carbonate structure is preferably a cyclic carbonate structure.
  • the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
  • R A 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.
  • R A 2 represents a substituent.
  • R A 2 each independently represents a substituent when n is 2 or more.
  • A represents a single bond or a divalent linking group.
  • Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
  • the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and paragraphs ⁇ 0370> to ⁇ 0414> of US Patent Application Publication No. 2016 / 0070167A1. It is also preferable to have the repeating unit described in 1.
  • Resin (A) may contain one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more kinds in combination.
  • the total (when there are a plurality of repeating units having at least one kind) is preferably 5 to 70 mol%, and preferably 10 to 65 mol%, based on all the repeating units of the resin (A). More preferably, it is more preferably 20 to 60 mol%.
  • the resin (A) preferably has a repeating unit having a polar group.
  • the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
  • the repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
  • the repeating unit which has a polar group does not have an acid-decomposable group.
  • the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.
  • Resin (A) may contain the repeating unit which has a polar group individually by 1 type, and may contain 2 or more types together.
  • the content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
  • Resin (A) can further have a repeating unit having neither an acid-decomposable group nor a polar group.
  • the repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure.
  • Examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating units described in paragraphs ⁇ 0236> to ⁇ 0237> of US Patent Application Publication No. 2016 / 0026083A1.
  • Preferred examples of the monomer corresponding to the repeating unit having neither an acid-decomposable group nor a polar group are shown below.
  • Resin (A) may contain the repeating unit which has neither an acid-decomposable group nor a polar group individually by 1 type, and may contain 2 or more types together.
  • the content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units in the resin (A). 5 to 25 mol% is more preferable.
  • Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units.
  • various repeating structural units can be included. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a monomer.
  • the monomer examples include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Can be mentioned. In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized. In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.
  • the resin (A) preferably has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group in all the repeating units of the resin (A) is preferably 5 mol% or less, more preferably 3 mol% or less, ideally Is more preferably 0 mol%, that is, it does not have a repeating unit having an aromatic group.
  • the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • all of the repeating units are composed of (meth) acrylate-based repeating units.
  • all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
  • the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the resin (A).
  • the resin (A) preferably contains a repeating unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) contains a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit and a hydroxystyrene (meth) acrylate repeating unit.
  • the resin (A) is a group (leaving group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed and eliminated by the action of an acid.
  • the content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all repeating units in the resin (A). 50 to 100 mol% is more preferable.
  • the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and more preferably 3,000 to 11,000. Particularly preferred.
  • the degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. preferable.
  • Resin (A) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the resin (A) in the total solid content of the composition of the present invention is generally 20% by mass or more. 40 mass% or more is preferable, 60 mass% or more is more preferable, and 70 mass% or more is still more preferable. Although an upper limit in particular is not restrict
  • the composition of the present invention typically contains a photoacid generator (hereinafter also referred to as “photoacid generator (C)”).
  • the photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
  • produces an organic acid by irradiation of actinic light or a radiation is preferable.
  • Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
  • photoacid generator known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof.
  • known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof.
  • Paragraphs ⁇ 0125> to ⁇ 0319> of US Patent Application Publication No. 2016 / 0070167A1 Paragraphs ⁇ 0086> to ⁇ 0094> of US Patent Application Publication No. 2015 / 0004544A1
  • US Patent Application Publication No. 2016 / 0237190A1 known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification can be suitably used as the photoacid generator (C).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. it can.
  • Z ⁇ represents an anion.
  • the photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), and at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded through a linking group.
  • Compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
  • R 201 to R 203 may be an aryl group
  • a part of R 201 to R 203 may be an aryl group
  • the rest may be an alkyl group or a cycloalkyl group.
  • arylsulfonium compound examples include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
  • the aryl group of the arylsulfonium compound 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, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
  • the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group optionally contained in the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.
  • a group is preferred, 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 cycloalkyl group of R 201 to R 203 are each independently an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having a carbon number) 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted.
  • Compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring 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, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, Or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
  • the alkyl group and cycloalkyl group represented by R 201 to R 203 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • the compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.
  • R 1c to R 5c each independently represents 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 cyclo Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group; R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
  • R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
  • 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 bonded to form a ring structure.
  • the ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings.
  • Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.
  • 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 a butylene group and a pentylene group.
  • the group formed by combining 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.
  • Zc - represents an anion.
  • the compound (ZI-4) is represented by the following general formula (ZI-4).
  • l represents an integer of 0 to 2.
  • r represents an integer of 0 to 8.
  • R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
  • R 14 represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent.
  • R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
  • Two R 15 may be bonded to each other to form a ring.
  • the ring skeleton may contain an oxygen atom or a heteroatom such as a nitrogen atom.
  • Z ⁇ represents an anion.
  • the alkyl groups of R 13 , R 14 and R 15 are linear or branched and preferably have 1 to 10 carbon atoms, and may be a methyl group, an ethyl group, n- A butyl group or a t-butyl group is more preferable.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group for R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group represented by R 204 to R 207 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group represented by R 204 to R 207 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group and pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 3 carbon atoms). 15), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
  • Z ⁇ represents an anion.
  • the anion represented is preferred.
  • o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
  • L represents a divalent linking group, and when there are a plurality of L, Ls may be the same or different.
  • W represents an organic group containing a cyclic structure.
  • o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf is more preferably a fluorine atom or CF 3 . In particular, it is preferable that both Xf are fluorine atoms.
  • R 4 and R 5 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4 and R 5 , they may be the same or different.
  • the alkyl group as R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
  • R 4 and R 5 are preferably a hydrogen atom.
  • Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).
  • L represents a divalent linking group, and when there are a plurality of L, Ls may be the same or different.
  • the divalent linking group include —COO — (— C ( ⁇ O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and combinations thereof And divalent linking groups.
  • —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO 2 —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
  • W represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic.
  • the polycyclic type can suppress acid diffusion more.
  • the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • heterocyclic ring examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • lactone ring and sultone ring examples include the lactone structure and sultone structure exemplified in the aforementioned resin.
  • a heterocyclic ring in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
  • the cyclic organic group may have a substituent.
  • substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic).
  • alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
  • a cycloalkyl group monocyclic, polycyclic or spirocyclic.
  • Well preferably having 3 to 20 carbon atoms
  • aryl group preferably having 6 to 14 carbon atoms
  • hydroxyl group alkoxy group
  • ester group amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid
  • An ester group is mentioned.
  • the carbon constituting the cyclic organic group may be a carbonyl carbon.
  • Formula (3) As the anion represented by, SO 3 - -CF 2 -CH 2 -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) q'-W, SO 3 - -CF 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, SO 3 - -CF 2- CH (CF 3 ) —OCO— (L) q′—W is preferred.
  • L, q, and W are the same as those in the general formula (3).
  • q ′ represents an integer of 0 to 10.
  • X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
  • X B1 and X B2 are preferably hydrogen atoms.
  • X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
  • at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom
  • both X B3 and X B4 are a monovalent organic group having a fluorine atom or a fluorine atom. Is more preferable.
  • both X B3 and X B4 are alkyl groups substituted with fluorine.
  • L, q and W are the same as those in the general formula (3).
  • the anion represented is preferred.
  • each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • Xb each independently represents an organic group having no hydrogen atom or fluorine atom.
  • Z in the general formula (ZI) -, Z in the general formula (ZII) -, Zc in formula (ZI-3) -, and Z in the general formula (ZI-4) - may be a benzenesulfonic acid anion Often, a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group is preferred.
  • Ar represents an aryl group, and may further have a substituent other than the sulfonate anion and the — (DB) group. Further, examples of the substituent that may be included include a fluorine atom and a hydroxyl group.
  • N represents an integer of 0 or more.
  • n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.
  • D represents a single bond or a divalent linking group.
  • the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group composed of a combination of two or more thereof.
  • B represents a hydrocarbon group
  • D is a single bond and B is an aliphatic hydrocarbon structure.
  • B is more preferably an isopropyl group or a cyclohexyl group.
  • Any of the above cations and anions can be used in combination as a photoacid generator.
  • the acid generator may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
  • the photoacid generator is preferably in the form of a low molecular compound.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
  • the acid generator When the acid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or in a resin different from the resin (A).
  • An acid generator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the acid generator in the composition is preferably 0.1 to 35% by mass, and preferably 0.5 to 25% by mass based on the total solid content of the composition. More preferred is 3 to 20% by mass, still more preferred is 3 to 15% by mass.
  • the content of the acid generator contained in the composition when there are plural kinds, the total thereof) Is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.
  • the composition of the present invention preferably contains an acid diffusion controller (D).
  • the acid diffusion controller (D) acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. .
  • a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a weak acid relative to an acid generator, a nitrogen atom And a low molecular compound (DD) having a group capable of leaving by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation moiety, or the like can be used as an acid diffusion controller.
  • a known acid diffusion controller can be used as appropriate.
  • the basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group. (Preferably having 3 to 20 carbon atoms) or an aryl group (6 to 20 carbon atoms).
  • R 201 and R 202 may combine with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
  • 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.
  • the alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.
  • guanidine As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like are preferable, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, or the like is more preferable.
  • a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (DB)”) has a proton acceptor functional group, and has an actinic ray or It is a compound that decomposes upon irradiation with radiation and whose proton acceptor property is lowered, disappears, or changes from proton acceptor property to acidity.
  • the proton acceptor functional group is a functional group having an electron or a group capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.
  • the compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is reduced or lost, or 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 acid property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
  • the acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa ⁇ 1, more preferably ⁇ 13 ⁇ pKa ⁇ 1, and ⁇ 13 ⁇ pKa. ⁇ -3 is more preferred.
  • the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). It shows that acid strength is so large that the value of acid dissociation constant pKa is low.
  • the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution.
  • the following software package 1 can be used to calculate a value based on a Hammett substituent constant and a database of known literature values.
  • the values of pKa described in this specification all indicate values obtained by calculation using this software package.
  • an onium salt (DC) that is a weak acid relative to the acid generator can be used as an acid diffusion controller.
  • DC an onium salt
  • an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, it is generated from the acid generator by irradiation with actinic rays or radiation.
  • an onium salt having an unreacted weak acid anion a weak acid is released by salt exchange to yield an onium salt having a strong acid anion.
  • the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
  • the onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).
  • R 51 represents a hydrocarbon group which may have a substituent
  • Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
  • R 52 is an organic group
  • Y 3 is a linear, branched or cyclic alkylene group or an arylene group
  • Rf is a fluorine atom.
  • Each of the M + is independently an ammonium cation, a sulfonium cation or an iodonium cation.
  • sulfonium cation or iodonium cation represented by M + include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).
  • An onium salt (DC) that is a weak acid relative to an acid generator has a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond (Hereinafter also referred to as “compound (DCA)”).
  • the compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).
  • R 1 , R 2 , and R 3 each independently represent a substituent having 1 or more carbon atoms.
  • L 1 represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
  • -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, and -N.
  • R 4 has a carbonyl group (—C ( ⁇ O) —), a sulfonyl group (—S ( ⁇ O) 2 —), and a sulfinyl group (—S ( ⁇ O) — at the linking site with the adjacent N atom.
  • R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure.
  • R 1 to R 3 may be combined to represent one divalent substituent and may be bonded to the N atom by a double bond.
  • Examples of the substituent having 1 or more carbon atoms in R 1 to R 3 include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned.
  • An alkyl group, a cycloalkyl group, or an aryl group is preferable.
  • L 1 as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more thereof.
  • a low molecular compound (DD) having a nitrogen atom and a group capable of leaving by the action of an acid has a group leaving on the nitrogen atom by the action of an acid. It is preferable that it is an amine derivative having.
  • the group capable of leaving by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.
  • the molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
  • Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group can be represented by the following general formula (d-1).
  • each Rb independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably a carbon atom).
  • Rb may be connected to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
  • a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
  • Rb a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alk
  • Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
  • Examples of the ring formed by connecting two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
  • Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structures disclosed in paragraph ⁇ 0466> of US Patent Publication US2012 / 0135348A1. .
  • the compound (DD) preferably has a structure represented by the following general formula (6).
  • l represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • l 2
  • two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
  • This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
  • Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
  • the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb.
  • a good group may be substituted with the same group as described above.
  • Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group examples include the same groups as those described above for Rb. It is done.
  • Specific examples of the particularly preferable compound (DD) in the present invention include compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto. is not.
  • the onium salt compound (DE) having a nitrogen atom in the cation part is preferably a compound having a basic site containing a nitrogen atom in the cation part.
  • the basic moiety is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.
  • a preferred specific structure of the compound (DE) includes, but is not limited to, the compound disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015 / 03009408A1.
  • the acid diffusion controller (D) may be used alone or in combination of two or more.
  • the content of the acid diffusion controller (D) in the composition (when there are a plurality of types) is preferably 0.1 to 10% by mass, based on the total solid content of the composition, preferably 0.1 to 5 mass% is more preferable.
  • the composition of the present invention usually contains a solvent.
  • a known resist solvent can be appropriately used.
  • paragraphs ⁇ 0665> to ⁇ 0670> of U.S. Patent Application Publication No. 2016 / 0070167A1 paragraphs ⁇ 0210> to ⁇ 0235> of U.S. Patent Application Publication No. 2015 / 0004544A1, and Patent Publication No. 2016 / 0237190A1.
  • Known solvents disclosed in paragraphs ⁇ 0424> to ⁇ 0426> of the specification and paragraphs ⁇ 0357> to ⁇ 0366> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used.
  • Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples thereof include an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
  • a monoketone compound preferably having 4 to 10 carbon atoms
  • the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure may be used as an organic solvent, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group.
  • the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group the above-mentioned exemplary compounds can be selected as appropriate, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or alkyl lactate, and propylene glycol monomethyl ether. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferable.
  • alkylene glycol monoalkyl ether acetate alkyl alkoxypropionate
  • a monoketone compound which may contain a ring alkyl alkoxypropionate
  • a monoketone compound which may contain a ring alkyl acetate, etc.
  • propylene glycol monomethyl Ether acetate PGMEA
  • ethyl ethoxypropionate 2-heptanone
  • ⁇ -butyrolactone cyclohexanone
  • cyclopentanone or butyl acetate propylene glycol monomethyl ether acetate
  • ⁇ -butyrolactone propylene glycol monomethyl ether acetate
  • ethyl ethoxypropionate cyclohexanone
  • More preferred is cyclopentanone or 2-heptanone.
  • propylene carbonate is also preferable.
  • the mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable.
  • a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable from the viewpoint of coating uniformity.
  • the solvent preferably contains propylene glycol monomethyl ether acetate, may be a propylene glycol monomethyl ether acetate single solvent, or may be two or more mixed solvents containing propylene glycol monomethyl ether acetate.
  • the composition of the present invention may or may not contain a surfactant.
  • a surfactant a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) ) Is preferred.
  • composition of the present invention contains a surfactant
  • a surfactant when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is possible to obtain a resist pattern with good sensitivity and resolution and less adhesion and development defects. it can.
  • the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
  • surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 can also 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, and 0.0005 to 1% by mass with respect to the total solid content of the composition. More preferred.
  • the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin is increased. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.
  • composition of the present invention may further contain an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator, or the like.
  • the film thickness of the actinic ray-sensitive film or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, and more preferably 85 nm or less, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property.
  • the solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass.
  • the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
  • the composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate).
  • the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and further preferably 0.03 ⁇ m or less.
  • This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • a cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered.
  • the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.
  • the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that changes its properties upon reaction with irradiation with actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition.
  • the resist pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, a MEMS (Micro Electro Mechanical Systems), and the like.
  • the present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition.
  • the pattern formation method of this invention is demonstrated.
  • the actinic ray-sensitive or radiation-sensitive film (typically a resist film) of the present invention will also be described.
  • the pattern forming method of the present invention includes (i) a step of forming an actinic ray-sensitive or radiation-sensitive film on a support with the above-described actinic ray-sensitive or radiation-sensitive resin composition (film formation step), (ii) ) A step of exposing the actinic ray-sensitive or radiation-sensitive film to an actinic ray or radiation (exposure step); and (iii) an actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation. A step of developing using the developer (developing step).
  • the pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.
  • the exposure method in the exposure step is preferably immersion exposure.
  • the pattern forming method of the present invention preferably includes (ii) a pre-heating (PB) step before the exposure step.
  • the pattern forming method of the present invention preferably includes (v) a post-exposure bake (PEB) step after (ii) the exposure step and before (iii) the development step.
  • the pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
  • the pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
  • the pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.
  • the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by a generally known method.
  • a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film
  • SOG Spin On Glass
  • SOC Spin On Carbon
  • antireflection film is formed between the actinic ray-sensitive or radiation-sensitive film and the support. May be.
  • As the resist underlayer film a known organic or inorganic material can be appropriately used.
  • a protective film (topcoat) may be formed on the actinic ray-sensitive or radiation-sensitive film.
  • a known material can be appropriately used.
  • composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used.
  • a composition for protective film formation what contains the acid diffusion control agent mentioned above is preferable.
  • a protective film may be formed on the actinic ray-sensitive or radiation-sensitive film containing the hydrophobic resin described above.
  • the support is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, or a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes.
  • a substrate can be used.
  • Specific examples of the support include inorganic substrates such as silicon, SiO 2 , and SiN.
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. in both (iv) the preheating step and (v) the post-exposure heating step.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
  • the heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.
  • the wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm.
  • KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc.
  • KrF excimer laser, ArF excimer laser, EUV or electron beam is preferred.
  • an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used, but an alkali developer is preferably used.
  • the alkaline developer a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used.
  • an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine can also be used. It can be used.
  • the alkaline developer may contain an appropriate amount of alcohol and / or surfactant.
  • the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually 10-15.
  • the development time using an alkali developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably there is.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvents 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, diethylene glycol monoethyl.
  • Examples include butyl, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
  • 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, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.
  • the content of the organic solvent in the organic developer is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass with respect to the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
  • the organic developer can contain an appropriate amount of a known surfactant as required.
  • the surfactant content is usually from 0.001 to 5 mass%, preferably from 0.005 to 2 mass%, more preferably from 0.01 to 0.5 mass%, based on the total amount of the developer.
  • the organic developer may contain the acid diffusion control agent described above.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time (paddle method), a substrate A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method) is applied.
  • dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
  • paddle method a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time
  • a substrate A method of spraying the developer on the surface spray method
  • a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed dynamic dispensing method
  • a step of developing using an alkaline aqueous solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined.
  • alkali developing step alkaline aqueous solution
  • organic solvent developing step organic solvent developing step
  • pure water can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer.
  • Pure water may contain an appropriate amount of a surfactant.
  • a process for removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid may be added.
  • a heat treatment may be performed in order to remove moisture remaining in the pattern.
  • the rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent 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 rinse liquid a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. It is preferable. Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described in the developer containing an organic solvent.
  • a rinse liquid containing a monohydric alcohol is more preferable.
  • Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl carbinol.
  • Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol. .
  • a plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
  • the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
  • the rinse solution may contain an appropriate amount of a surfactant.
  • the substrate that has been developed using the organic developer is washed with a rinse containing an organic solvent.
  • the method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), or the like can be applied.
  • the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C.
  • the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention preferably does not contain impurities such as metal components, isomers, and residual monomers.
  • the content of these impurities contained in the above various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not (less than the detection limit of the measuring device). Is particularly preferred.
  • Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, 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 a plurality of times may be a circulating filtration step.
  • the filter is preferably a filter with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
  • impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • the adsorbent a known adsorbent can be used.
  • an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
  • Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
  • a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
  • a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned.
  • Preferable conditions for filtration are the same as those described above.
  • a method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
  • a method for improving the surface roughness of the pattern for example, a method of treating a resist pattern by plasma of hydrogen-containing gas disclosed in US Patent Application Publication No. 2015/0104957 can be cited.
  • Japanese Patent Application Publication No. 2004-235468 JP 2004-2354608
  • US Patent Application Publication No. 2010/0020297 Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Known methods such as those described in “Enhancement” may be applied.
  • the resist pattern formed by the above-described method is, for example, a spacer disclosed in Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a process core.
  • the present invention also relates to an electronic device manufacturing method including the pattern forming method described above.
  • the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.). Is done.
  • an electric / electronic device for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.
  • the reaction mixture was allowed to cool and then added dropwise over 20 minutes to a mixture of 900 ml of methanol / 100 ml of water.
  • the precipitated powder was collected by filtration and dried, yielding 19 g of Resin (P-77).
  • the weight average molecular weight of the obtained resin was 7000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.
  • Resins (P-1) to (P-160) listed above were synthesized in the same manner as resin (P-77).
  • resins (S-1) to (S-4) were synthesized in the same manner.
  • composition ratios (molar ratios), weight average molecular weights, and dispersities of the resins (P-1) to (P-160) are as described above.
  • composition ratios (molar ratios), weight average molecular weights, and dispersities of the resins (S-1) to (S-4) are as follows.
  • Resin (1) The weight average molecular weight of the obtained resin was 8800 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.9.
  • another resin (A) shown below was synthesized.
  • the structure of the acid-decomposable resin (A) used in the examples is shown below.
  • Table 2 below shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), weight average molecular weight (Mw), and dispersity (Mw / Mn).
  • the development residue (scum) in a resist pattern with a line width of 75 nm was observed using a scanning electron microscope (S-9220 manufactured by Hitachi). A was a residue that did not occur at all, A was a residue that was severely generated, The middle was B and C (B has less residue than C). At that time, the exposure scan speed was 700 mm / s.
  • a defect inspection apparatus KLA2360 (trade name) manufactured by KLA Tencor Co., Ltd. for a pattern (exposure scan speed is 700 mm / s) formed on a silicon wafer (12-inch diameter) as described above.
  • the pixel size of the defect inspection device is set to 0.16 ⁇ m
  • the threshold value is set to 20
  • measurement is performed in a random mode to detect a development defect extracted from a difference caused by superimposition of the comparison image and the pixel unit.
  • the number of development defects per unit area (pieces / cm 2) was calculated. One inch is 0.0254 m.
  • a value of less than 0.5 was designated as A, 0.5 or more and less than 0.7 as B, 0.7 or more and less than 1.0 as C, and 1.0 or more as D. A smaller value indicates better performance.
  • DRCA Dynamic receding contact angle
  • the prepared resist composition was applied on a silicon wafer (8-inch diameter), and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 120 nm.
  • the receding contact angle of water droplets was measured by the expansion / contraction method of a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).
  • An initial droplet size of 35 ⁇ L was sucked at a speed of 6 ⁇ L / sec for 5 seconds, and a value with a stable dynamic contact angle during suction was defined as a receding contact angle.
  • the measurement environment is 23 ° C. and relative humidity 45%. The larger the receding contact angle value, the higher the water followability with respect to the ultra high scanning speed.
  • the photoacid generator, acid diffusion controller, resin (P ′), surfactant, and solvent in Table 3 are as follows.
  • Bu represents a butyl group.
  • W-1 Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
  • W-2 Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
  • W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon-based)
  • W-4 Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
  • W-6 PF6320 (manufactured by OMNOVA, fluorine-based)
  • SL-1 Cyclohexanone
  • SL-2 Propylene glycol monomethyl ether acetate
  • SL-3 Ethyl lactate
  • SL-4 Propylene glycol monomethyl ether
  • SL-5 ⁇ -butyrolactone
  • SL-6 Propylene carbonate
  • the example using the composition containing the resin (P) has an ultra-high scanning speed (700 mm / s) compared to the comparative example using the composition not containing the resin (P). ), It was possible to reduce both immersion defects and development defects while having high followability of the immersion liquid to the exposure apparatus.

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  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne : une composition de résine sensible aux rayons actiniques ou au rayonnement qui présente des performances de suivi d'immersion dans le liquide qui sont élevées pour un dispositif d'exposition, même lorsque le taux de balayage d'exposition est extrêmement élevé (700 mm/sec ou plus, par exemple), et qui peut réduire à la fois les défauts d'immersion dans le liquide et les défauts de développement ; et un film sensible aux rayons actiniques ou au rayonnement, un procédé de formation de motif et un procédé de production de dispositif électronique l'utilisant. Cette composition de résine sensible aux rayons actiniques ou au rayonnement contient une résine (P) ayant un motif récurrent représenté par la formule générale (1) et une résine (A) ayant un groupe qui est décomposé et qui fait augmenter la polarité grâce à un acide agissant sur lui. Dans la formule générale (1), Z représente un atome d'hydrogène, un groupe alcoxy, un atome d'halogène, un groupe représenté par R11OCH2- ou un groupe représenté par R12OC(=O)CH2-. R11 et R12 représentent indépendamment un substituant monovalent. X représente un atome d'oxygène ou un atome de soufre. L représente une liaison simple ou un groupe de liaison à valence (m + 1). R représente un groupe spécifique. m représente un nombre entier positif. Lorsque m vaut 2 ou plus, les nombreux R peuvent être identiques ou différents les uns des autres. Lorsque L représente une liaison simple, m vaut 1.
PCT/JP2019/000914 2018-02-28 2019-01-15 Composition de résine sensible aux rayons actiniques ou au rayonnement, film sensible aux rayons actiniques ou au rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique WO2019167451A1 (fr)

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JP2001154362A (ja) * 1999-11-29 2001-06-08 Central Glass Co Ltd ポジ型レジスト組成物およびパターン形成方法
JP2004102019A (ja) * 2002-09-11 2004-04-02 Fuji Photo Film Co Ltd ポジ型レジスト組成物
JP2005036160A (ja) * 2003-07-18 2005-02-10 Asahi Glass Co Ltd 含フッ素樹脂、感光性樹脂組成物及びフォトレジスト
JP2013040320A (ja) * 2011-01-26 2013-02-28 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
JP2012177101A (ja) * 2011-02-03 2012-09-13 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
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