WO2019039290A1 - Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique, découpe de masque équipée d'un film de réserve, procédé de formation de motif destiné à une découpe de masque équipée d'un film de réserve - Google Patents

Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique, découpe de masque équipée d'un film de réserve, procédé de formation de motif destiné à une découpe de masque équipée d'un film de réserve Download PDF

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WO2019039290A1
WO2019039290A1 PCT/JP2018/029765 JP2018029765W WO2019039290A1 WO 2019039290 A1 WO2019039290 A1 WO 2019039290A1 JP 2018029765 W JP2018029765 W JP 2018029765W WO 2019039290 A1 WO2019039290 A1 WO 2019039290A1
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group
sensitive
resist film
radiation
compound
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PCT/JP2018/029765
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Japanese (ja)
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土村　智孝
一成 八木
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富士フイルム株式会社
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Priority to JP2019538063A priority Critical patent/JP6801115B2/ja
Publication of WO2019039290A1 publication Critical patent/WO2019039290A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D281/00—Heterocyclic compounds containing rings of more than six members having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D281/18—Eight-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms with nitro or nitroso radicals directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a method of manufacturing an electronic device, a mask blank with a resist film, and a pattern forming method of a mask blank with a resist film.
  • immersion liquid a liquid having a high refractive index
  • excimer laser light development of lithography using electron beams, X-rays, EUV (Extreme Ultra Violet) light and the like is also in progress.
  • chemically amplified resist compositions have been developed that are effectively sensitive to various actinic rays and radiation and that are excellent in sensitivity and resolution, and various compounds have been developed for the main component acid generator. ing.
  • Patent Document 1 discloses a photoresist composition containing a specific acid generator.
  • the present inventors prepared an actinic ray-sensitive or radiation-sensitive resin composition using the acid generator described in Patent Document 1, and a fine resist pattern with a narrow space width (for example, on the order of several tens of nm)
  • a fine resist pattern with a narrow space width (for example, on the order of several tens of nm)
  • the shape of a pattern may not satisfy
  • requirement namely, becomes shape other than a rectangle.
  • the said actinic-ray-sensitive or radiation-sensitive resin composition had the case where resolution and exposure latitude were inadequate.
  • an object of the present invention is to provide an actinic ray sensitive or radiation sensitive resin composition excellent in resolution, exposure latitude and pattern shape characteristics. Furthermore, according to the present invention, a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a method of forming a pattern, a method of manufacturing an electronic device, a mask blank with a resist film, and pattern formation of a mask blank with a resist film It also aims to provide a method.
  • An actinic ray-sensitive or radiation-sensitive resin composition containing a compound capable of generating an acid represented by the following general formula (I) upon irradiation with an actinic ray or radiation, and a resin.
  • A represents a non-aromatic heterocycle having at least one linking group represented by X.
  • Z represents a monovalent organic group or a hydrogen atom.
  • R represents a monovalent organic group.
  • n represents an integer of 0 or more.
  • M + represents a monovalent cation.
  • A represents a non-aromatic heterocycle having at least one linking group represented by X.
  • Z represents a monovalent organic group or a hydrogen atom.
  • R represents a monovalent organic group.
  • n represents an integer of 0 or more.
  • a mask blank with a resist film comprising: mask blanks; and the resist film according to the above [8] disposed on the mask blanks.
  • an actinic ray-sensitive or radiation-sensitive resin composition excellent in resolution, exposure latitude, and pattern shape characteristics. Furthermore, according to the present invention, a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, a method of manufacturing an electronic device, a mask blank with a resist film, and a mask blank with a resist film A pattern formation method can be provided.
  • the present invention will be described in detail.
  • embodiments of the present invention will be described in detail.
  • the notations not describing substitution and non-substitution include those having no substituent and those having 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).
  • actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc.
  • light means actinic rays or radiation.
  • exposure in the present specification means not only exposure by the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X rays, etc., but also electron beams. And, drawing by particle beam such as ion beam is also included in the exposure.
  • “to” is used in the meaning including the numerical values described before and after that as the lower limit value and the upper limit value.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) are standard polystyrene equivalent values determined from GPC (gel permeation chromatography) under the following conditions.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound capable of generating an acid represented by the general formula (I) described later upon irradiation with an actinic ray or radiation (hereinafter, also simply referred to as "acid generator"). And a resin.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in resolution and exposure latitude. Furthermore, the resist pattern produced by the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a rectangular cross-sectional shape when cut in the direction perpendicular to the substrate which is the lower layer of the resist pattern. That is, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is also excellent in pattern shape characteristics. The reason why the above-mentioned characteristics are excellent is not clear but is presumed as follows.
  • the acid represented by the general formula (I) has an increased interaction with the resin by having a nonaromatic heterocycle. Thereby, the diffusibility of the acid represented by general formula (I) is suppressed, and the penetration to the non-exposed area is reduced. As a result, it is estimated that the resolution and exposure latitude are excellent. Furthermore, since the acid represented by the general formula (I) has a high interaction with the resin, it easily disperses uniformly in the resist film (in other words, uneven distribution on the surface is suppressed). As a result, it is estimated that the pattern shape characteristics are excellent. From the same reason, it is presumed that the in-plane uniformity (CDU) of the line width formed in the resist film is also excellent.
  • CDU in-plane uniformity
  • the acid generator contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention generates an acid represented by the following general formula (I) upon irradiation with an actinic ray or radiation.
  • the acid generator may be in the form of a low molecular weight compound or in the form of a polymer.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.
  • the acid generator is in the form of a polymer, its structure is not particularly limited, and may be incorporated, for example, in a part of ⁇ resin (A)> described later.
  • the acid generator is in the form of a polymer
  • its weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 2,000, as the polystyrene conversion value by GPC (Gel Permeation Chromatography) method. It is 20,000.
  • A represents a non-aromatic heterocycle having at least one linking group represented by X.
  • Z represents a monovalent organic group or a hydrogen atom.
  • R represents a monovalent organic group.
  • n represents an integer of 0 or more.
  • non-aromatic heterocycle A the carbon number of the non-aromatic heterocycle represented by A (hereinafter also referred to as “non-aromatic heterocycle A”) is not particularly limited, and is, for example, 3 to 20, 4 to 15 is preferable, and 4 to 10 is more preferable.
  • the non-aromatic heterocycle A has a linking group represented by X (hereinafter also referred to as "linking group X").
  • the number of linking groups X in the nonaromatic heterocycle A is 1 or more, preferably 1 to 5, and more preferably 1 to 3.
  • Z represents a monovalent organic group or a hydrogen atom.
  • Examples of the monovalent organic group represented by Z include the same groups as the monovalent organic group represented by R in General Formula (I) described later, and among them, a linear alkyl group, a branched alkyl group and a cyclic alkyl group Are preferred, and linear alkyl groups such as methyl and ethyl are more preferred. As Z, a linear alkyl group or a hydrogen atom is preferable.
  • R represents a monovalent organic group.
  • the monovalent organic group represented by R is not particularly limited, and examples thereof include alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and tert-butoxy; and aryls such as phenoxy and p-tolyloxy.
  • a linear alkyl group and a branched alkyl group a cyclic alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group and an aryloxy group are preferable.
  • n represents an integer of 0 or more.
  • the integer represented by n is preferably 0 to 3, and more preferably 0 to 2.
  • the volume of the acid represented by formula (I) is preferably 240 ⁇ 3 or more, more preferably 300 ⁇ 3 or more, more preferably 350 ⁇ 3 or more, 400 ⁇ 3 or more and particularly preferable. From the viewpoint of solubility or the like in a solvent, the volume is preferably 2000 ⁇ 3 or less, more preferably 1500 ⁇ 3 or less.
  • the volume of acid is determined as follows using "WinMOPAC" manufactured by Fujitsu Limited.
  • each acid is input, and then, using this structure as an initial structure, the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method, and then these most stable stereochemistry
  • the "accessible volume" of each acid can be calculated by molecular orbital calculation using the PM3 method for the conformation. 1 ⁇ is 0.1 nm.
  • the compound capable of generating an acid represented by the general formula (I) upon irradiation with an actinic ray or radiation is not particularly limited in its structure, and is a compound having an ionic structure such as an onium salt such as sulfonium salt and iodonium salt, or Preferred are those having a nonionic compound structure such as oxime ester and imido ester.
  • the onium salt is more preferably a sulfonium salt.
  • the compound capable of generating an acid represented by the general formula (I) upon irradiation with an actinic ray or radiation is preferably a compound represented by the following general formula (IA).
  • M + represents a monovalent cation.
  • A represents a non-aromatic heterocycle having at least one linking group represented by X.
  • Z represents a monovalent organic group or a hydrogen atom.
  • R represents a monovalent organic group.
  • n represents an integer of 0 or more.
  • A, R and n, and X and Z in the general formula (IA) have the same meanings as A, R and n, and X and Z described in the general formula (I).
  • Examples of the monovalent cation represented by M + in the general formula (IA) include cations represented by the following general formulas (ZI) and (ZII).
  • Each of R 201 , R 202 and R 203 independently represents an organic group.
  • the carbon number of the organic group as R 201 , R 202 and R 203 is generally 1 to 30, preferably 1 to 20.
  • Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by bonding of two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group).
  • the acid generator may be a compound having a plurality of structures represented by general formula (ZI).
  • ZI general formula
  • at least one of R 201 to R 203 in the compound represented by General Formula (ZI) is a single bond or at least one of R 201 to R 203 in another compound represented by General Formula (ZI) It may be a compound having a structure linked via a linking group.
  • the generated acid has a pKa of -1 or less.
  • the organic group represented by R 201 , R 202 and R 203 includes an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (carbon 3 to 15 are preferable) and the like. At least one of R 201 , R 202 and R 203 is preferably an aryl group, and more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group and the like, heteroaryl groups such as an indole residue and a pyrrole residue are also possible.
  • These aryl group, alkyl group and cycloalkyl group as R 201 , R 202 and R 203 may further have a substituent.
  • substituents include a halogen atom such as nitro group and fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3 to 15).
  • An aryl group preferably having a carbon number of 6 to 14
  • an alkoxycarbonyl group preferably having a carbon number of 2 to 7
  • an acyl group preferably having a carbon number of 2 to 12
  • an alkoxycarbonyloxy group preferably having a carbon number of 2 to 7 and the like, but not limited thereto.
  • R 201 , R 202 and R 203 may be bonded via a single bond or a linking group.
  • the linking group includes, but is not limited to, an alkylene group (preferably having a carbon number of 1 to 3), -O-, -S-, -CO-, and -SO 2- .
  • R 201 , R 202 and R 203 is not an aryl group, paragraphs 0046 and 0047 of JP-A 2004-233661, paragraphs 0040 to 0046 of JP-A 2003-35948, and the like Compounds exemplified as Formulas (I-1) to (I-70) in Patent Application Publication No.
  • R 1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group
  • R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R 2 and R 3 may combine with each other to form a ring
  • R 1 and R 2 may be linked to each other to form a ring
  • Each of R x and R y independently is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group.
  • R x and R y may be linked to each other to form a ring, and the ring structure contains an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond or an amide bond It is also good.
  • the alkyl group as R 1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.
  • Examples thereof include linear alkyl groups such as groups, and branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.
  • the alkyl group of R 1 may have a substituent, and as the alkyl group having a substituent, a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group Etc.
  • the cycloalkyl group as R 1 is preferably a cycloalkyl group having a carbon number of 3 to 20, and may have an oxygen atom or a sulfur atom in the ring. Specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group etc. can be mentioned.
  • the cycloalkyl group of R 1 may have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.
  • the alkoxy group as R 1 is preferably an alkoxy group having 1 to 20 carbon atoms. Specifically, a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group, and an n-butyloxy group can be mentioned.
  • the alkoxy group of R 1 may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.
  • the cycloalkoxy group as R 1 is preferably a cycloalkoxy group having a carbon number of 3 to 20, and examples thereof include a cyclohexyloxy group, a norbornyloxy group, and an adamantyloxy group.
  • the cycloalkoxy group of R 1 may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.
  • the aryl group as R 1 is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group.
  • the aryl group of R 1 may have a substituent, and preferred examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group and an arylthio group. .
  • the substituent is an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, the same as the alkyl group as R 1 described above, a cycloalkyl group, an alkoxy group and a cycloalkoxy group can be mentioned.
  • the alkenyl group as R 1 includes a vinyl group and an allyl group.
  • R 2 and R 3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R 2 and R 3 may combine with each other to form a ring.
  • at least one of R 2 and R 3 represents an alkyl group, a cycloalkyl group, and an aryl group.
  • Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R 2 and R 3 include the same as the specific examples and preferred examples described above for R 1 .
  • the total number of carbon atoms contributing to the ring formation included in R 2 and R 3 is preferably 4 to 7, 4 or 5 Is particularly preferred.
  • R 1 and R 2 may be linked to each other to form a ring.
  • R 1 is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent)
  • R 2 has 1 to 4 carbon atoms preferably (preferably methylene group or ethylene group) alkylene group is preferable as the substituent include those similar to the substituent which may be aryl groups have as R 1 described above.
  • R 1 is a vinyl group and R 2 is an alkylene group having 1 to 4 carbon atoms.
  • the alkyl group represented by R x and R y is preferably an alkyl group having 1 to 15 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group , Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and And eicosyl groups.
  • the cycloalkyl group represented by Rx and Ry is preferably a cycloalkyl group having a carbon number of 3 to 20, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group. it can.
  • the alkenyl group represented by Rx and Ry is preferably an alkenyl group of 2 to 30, and examples thereof include a vinyl group, an allyl group and a styryl group.
  • the aryl group represented by Rx and Ry is, for example, preferably an aryl group having a carbon number of 6 to 20, and specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthyrenyl group, a phenanthrenyl group, a penalenyl group, a fe
  • Examples include a nathracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a benzopyrenyl group.
  • it is a phenyl group or a naphthyl group, more preferably a phenyl group.
  • alkyl group moiety of the 2-oxoalkyl group and the alkoxycarbonylalkyl group represented by Rx and Ry include, for example, those listed above as Rx and Ry .
  • Examples of the cycloalkyl group moiety of the 2-oxocycloalkyl group and the alkoxycarbonylcycloalkyl group represented by Rx and Ry include, for example, those listed above as Rx and Ry .
  • the cation represented by general formula (ZI-3) is preferably a cation represented by the following general formulas (ZI-3a) and (ZI-3b).
  • R 1 , R 2 and R 3 are as defined in the above general formula (ZI-3).
  • Y represents an oxygen atom, a sulfur atom or a nitrogen atom, preferably an oxygen atom or a nitrogen atom.
  • m, n, p and q mean an integer, preferably 0 to 3, more preferably 1 to 2, and still more preferably 1.
  • the alkylene group which links S + and Y may have a substituent, and preferred examples of the substituent include an alkyl group.
  • R 5 represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom.
  • R 5 is preferably a group containing an electron withdrawing group, and more preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group.
  • Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include the same as the specific examples and preferred examples described above for R 1 in the general formula (ZI-3).
  • * represents a bond connecting to a nitrogen atom as Y in the compound represented by General Formula (ZI-3a).
  • R 5 is preferably a group represented by —SO 2 —R 4 .
  • R 4 represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R 4 include the same as the specific examples and preferred examples described above for R 1 .
  • the cation represented by general formula (ZI-3) is particularly preferably a cation represented by the following general formulas (ZI-3a ') and (ZI-3b').
  • R 1 , R 2 , R 3 , Y and R 5 are as defined in the general formulas (ZI-3a) and (ZI-3b). It is.
  • 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 each independently has 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 group having a cycloalkyl group.
  • R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group.
  • Two R 15 s may be bonded to each other to form a ring, and the atoms constituting the ring may contain heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent. l represents an integer of 0 to 2; r represents an integer of 0 to 8;
  • the alkyl group of R 13 , R 14 and R 15 is linear or branched and is preferably one having 1 to 10 carbon atoms.
  • the alkoxy group of R 13 and R 14 is linear or branched and is preferably one having 1 to 10 carbon atoms.
  • the alkoxycarbonyl group of R 13 and R 14 is linear or branched and is preferably one having 2 to 11 carbon atoms.
  • alkyl group of the alkylcarbonyl group of R 14 examples include the same specific examples as the alkyl group as R 13 to R 15 described above.
  • the alkyl sulfonyl group and the cycloalkyl sulfonyl group of R 14 are linear, branched or cyclic, and those having 1 to 10 carbon atoms are preferable.
  • Examples of the substituent which each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyl group An oxy group etc. can be mentioned.
  • a halogen atom for example, a fluorine atom
  • a 5- or 6-membered ring formed by two R 15 together with a sulfur atom in the general formula (ZI-4) is particularly preferable.
  • a 5-membered ring ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring
  • a 5-membered ring ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring
  • a 5-membered ring ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring
  • the divalent R 15 may have a substituent, and examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group and an alkoxycarbonyl group. Groups, and alkoxycarbonyloxy groups etc. can be mentioned.
  • a plurality of substituents for the above ring structure may be present, and they may combine with each other to form a ring.
  • R 15 in the general formula (ZI-4) a methyl group, an ethyl group, a naphthyl group, and a divalent group in which two R 15 bonds to each other to form a tetrahydrothiophene ring structure with a sulfur atom are preferable
  • Particularly preferred is a divalent group in which two R 15 bonds together to form a tetrahydrothiophene ring structure with a sulfur atom.
  • the substituent which R 13 and R 14 may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (in particular, a fluorine atom).
  • l 0 or 1 is preferable, and 1 is more preferable.
  • r an integer of 0 to 2 is preferable.
  • each of R 204 and R 205 independently represents an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 are the same as the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
  • the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group of R 204 and R 205 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 of R 204 and R 205 are preferably linear or branched alkyl groups having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon There can be mentioned cycloalkyl groups (cyclopentyl group, cyclohexyl group, norbornyl group) of the formulas 3 to 10.
  • the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have a substituent.
  • substituent which the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include the aryl group of R 201 to R 203 in the compound (ZI) described above, an alkyl group, and Examples thereof include those which the cycloalkyl group may have, such as an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms) And an alkoxy group (for example, having a carbon number of 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group.
  • the specific example of a cation represented by general formula (ZII) is shown.
  • A represents a sulfur atom.
  • R represents an aryl group.
  • R N represents an aryl group substituted with a proton acceptor functional group.
  • the proton acceptor functional group is a functional group having an electrostatic interaction with a proton or a functional group having an electron, and for example, a functional group having a macrocyclic structure such as cyclic polyether or ⁇ conjugated
  • the nitrogen atom having a noncovalent electron pair not contributing to the ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
  • Examples of preferable partial structures of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
  • the compound (PA) having a proton acceptor functional group is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is reduced, eliminated, or changed from proton acceptor property to acidity.
  • the reduction in proton acceptor property, disappearance, or change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of a proton to the proton acceptor functional group, Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
  • General formula (7) is shown. In the following general formula, Et represents an ethyl group.
  • the compound capable of generating an acid represented by the general formula (I) upon irradiation with an actinic ray or radiation may have a nonionic compound structure, for example,
  • the compounds represented by formulas (ZV) and (ZVI) can be mentioned.
  • Each of R 209 and R 210 independently represents an alkyl group, a cycloalkyl group, a cyano group or an aryl group.
  • the aryl group, alkyl group and cycloalkyl group of R 209 and R 210 are the same as the respective groups described as the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) is there.
  • the aryl group, alkyl group and cycloalkyl group of R 209 and R 210 may have a substituent. As this substituent, the same as the substituent which the aryl group of R 201 to R 203 in the above-mentioned compound (ZI), the alkyl group and the cycloalkyl group may have can be mentioned.
  • a ' represents an alkylene group, an alkenylene group or an arylene group.
  • the alkylene group as A ′ may have a substituent, and preferably has 1 to 8 carbon atoms, for example, methylene, ethylene, propylene, butylene, hexylene, octylene and the like be able to.
  • the alkenylene group as A ′ may have a substituent, and preferably has 2 to 6 carbon atoms, such as an ethenylene group, a propenylene group, and a butenylene group.
  • the arylene group as A ′ may have a substituent and preferably has a carbon number of 6 to 15, and examples thereof include a phenylene group, a tolylene group, and a naphthylene group.
  • a ′ may have, for example, those having an active hydrogen such as a cycloalkyl group, an aryl group, an amino group, an amido group, an ureido group, a urethane group, a hydroxy group and a carboxy group, and further , Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group etc.) And acyloxy group (such as acetoxy group, propanoyloxy group and benzoyloxy group), alkoxycarbonyl group (such as methoxycarbonyl group, ethoxycarbonyl group, and propoxycarbonyl group), cyano group, and nitro group.
  • the arylene group may further include an alkyl group,
  • Rz represents a structure in which H of the acid represented by the general formula (I) is dissociated, and is represented by the following general formula (IS).
  • * Represents a binding site to a compound residue represented by General Formula (ZV) or (ZVI).
  • A represents a non-aromatic heterocycle having at least one linking group represented by X.
  • Z represents a monovalent organic group or a hydrogen atom.
  • R represents a monovalent organic group.
  • n represents an integer of 0 or more.
  • A, R and n, and X and Z in the general formula (IS) have the same meanings as A, R and n, and X and Z described in the general formula (I).
  • the method for synthesizing the compound capable of generating the acid represented by the general formula (I) upon irradiation with an actinic ray or radiation can be synthesized by a known synthesis method.
  • composition of this invention can be used individually by 1 type or in combination of 2 or more types of compounds (acid generator (I)) which generate
  • composition of the present invention may be used in combination with the acid generator (I) described above and an acid generator other than the acid generator (I).
  • acid generators other than the acid generator (I) it is used as a photoinitiator for photo cationic polymerization, a photoinitiator for photo radical polymerization, a photo decolorizing agent for dyes, a photo-discoloring agent, or a micro resist, etc.
  • Known compounds which generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.
  • diazonium salts for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfones, disulfones, or o-nitrobenzyl sulfonates can be mentioned.
  • the content of the acid generator in the composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive composition. It is 18% by mass, more preferably 5 to 18% by mass.
  • the total content of the photoacid generators is preferably in the above range.
  • the resin (A) is, for example, a resin whose polarity is changed by the action of an acid.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains, as the resin (A), a resin (hereinafter also referred to as "resin (A1)") having a group capable of decomposing by the action of an acid, Or it is preferable that it is an aspect in any one of containing resin (Hereafter, it is also mentioned “resin (A2).”) Which has phenolic hydroxyl group as resin (A).
  • the resin (A1) is a resin in which the solubility in an alkali developer is increased by the action of an acid, or the solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid.
  • At least one of the side chains has a group which is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as "acid-degradable group").
  • the alkali-soluble group include a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
  • resin (A1) has a repeating unit which has the acid-degradable group mentioned above.
  • the repeating unit having an acid decomposable group is preferably a repeating unit represented by the following general formula (AI).
  • Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
  • T represents a single bond or a divalent linking group.
  • Each of Rx 1 to Rx 3 independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx 1 to Rx 3 may be combined to form a cycloalkyl group (monocyclic or polycyclic).
  • alkyl group which may be substituted and represented by Xa 1 examples include, for example, a methyl group or a group represented by —CH 2 —R 11 .
  • R 11 represents a halogen atom (such as fluorine atom), a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms Is an alkyl group, more preferably a methyl group.
  • Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • Examples of the divalent linking group of T include an alkylene group, -COO-Rt- group, and -O-Rt- group.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a -COO-Rt- group.
  • Rt is preferably an alkylene group having a carbon number of 1 to 5, and more preferably a -CH 2 -group, a-(CH 2 ) 2 -group or a-(CH 2 ) 3 -group.
  • an alkyl group having a carbon number of 1 to 4 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group is preferred. preferable.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like. And polycyclic cycloalkyl groups are preferred.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododeca group and the like.
  • Nyl group and polycyclic cycloalkyl group such as adamantyl group are preferable. More preferred is a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
  • the above cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group May be replaced by
  • Rx 1 is a methyl group or an ethyl group
  • Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group is preferable.
  • Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), and carboxy Groups, alkoxycarbonyl groups (having 2 to 6 carbon atoms), and the like, and preferably 8 or less carbon atoms.
  • the content as a total of repeating units having an acid decomposable group is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, based on all repeating units in the resin (A1). It is more preferable that the content be up to 80 mol%.
  • Rx, Xa 1 represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH.
  • Each of Rxa and Rxb represents an alkyl group having 1 to 4 carbon atoms.
  • Z represents a substituent containing a polar group, and when there are a plurality of substituents, each is independent.
  • p represents 0 or a positive integer.
  • the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and a cycloalkyl group, with preference given to Is an alkyl group having a hydroxyl group.
  • An isopropyl group is particularly preferred as the branched alkyl group.
  • the resin (A1) preferably contains the repeating unit represented by the general formula (3).
  • R 31 represents a hydrogen atom or an alkyl group.
  • R 32 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group.
  • R 33 represents an atomic group necessary to form a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R 32 is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
  • the alkyl group of R 31 may have a substituent, and examples of the substituent include a fluorine atom, a hydroxyl group and the like.
  • R 31 preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • R 32 is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a methyl group or an ethyl group.
  • the monocyclic alicyclic hydrocarbon structure formed by R 33 together with a carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.
  • examples of the hetero atom which can constitute a ring include an oxygen atom, a sulfur atom and the like, and a group having a hetero atom is a carbonyl group and the like. It can be mentioned.
  • the group having a hetero atom is preferably not an ester group (ester bond).
  • the monocyclic alicyclic hydrocarbon structure formed by R 33 together with a carbon atom is preferably formed of only a carbon atom and a hydrogen atom.
  • the content of the repeating unit having a structure represented by the general formula (3) is preferably 20 to 80% by mole, more preferably 25 to 75% by mole, relative to all the repeating units in the resin (A1). 70 mol% is more preferred.
  • the resin (A1) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonic acid ester) structure.
  • any lactone structure or sultone structure can be used, but a lactone structure or sultone structure of a 5- to 7-membered ring is preferable, and a 5- to 7-membered lactone is preferable.
  • Those in which other ring structures are fused in a form that forms a bicyclo structure or a spiro structure in the structure or sultone structure are preferable. It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17), (SL1-1) and (SL1-2).
  • the lactone structure or sultone structure may be directly bonded to the main chain.
  • Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5) and (LC1-8), and more preferably (LC1-4).
  • LWR line width roughness
  • development defects become better.
  • the lactone structure moiety or the sultone structure moiety may or may not have a substituent (Rb 2 ).
  • Preferred examples of the substituent (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group And a halogen atom, a hydroxyl group, a cyano group, and an acid-degradable group. More preferably, it is an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group.
  • n 2 represents an integer of 0 to 4; When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different, and a plurality of substituents (Rb 2 ) may be combined to form a ring.
  • the resin (A1) preferably contains a repeating unit having a lactone structure or a sultone structure 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-).
  • R 0 s each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
  • Z's when there are a plurality of Z's, are each independently a single bond, an ether bond, an ester bond, an amide bond, a urethane bond
  • each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
  • R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
  • n is the number of repetitions of the structure represented by -R 0 -Z- and represents an integer of 0 to 2.
  • R 7 represents a hydrogen atom, a halogen atom or an alkyl group.
  • the alkylene group and cycloalkylene group of R 0 may have a substituent.
  • Z is preferably an ether bond or an ester bond, particularly preferably an ester bond.
  • the alkyl group of R 7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
  • the alkylene group of R 0 , the cycloalkylene group, and the alkyl group in R 7 may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, and a hydroxy And alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acetoxy groups such as acetyloxy group and propionyloxy group.
  • R 7 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • the preferred chained alkylene group in R 0 is preferably a chained 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.
  • the preferable cycloalkylene group is a cycloalkylene group having a carbon number of 3 to 20, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. Among them, a linear alkylene group is more preferable, and a methylene group is particularly preferable.
  • the monovalent organic group having a lactone structure or a sultone structure represented by R 8 is not limited as long as it has a lactone structure or a sultone structure, and the general formula (LC1-1) described above as a specific example And lactone structures or sultone structures represented by (LC1-17), (SL1-1) and (SL1-2), and among these, the structure represented by (LC1-4) is particularly preferable.
  • N 2 in (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) is more preferably 2 or less.
  • R 8 is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or a sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, and cyano
  • a monovalent organic group having a lactone structure (cyano lactone) or a sultone structure (cyanosultone) having a group as a substituent is more preferable.
  • n is preferably 1 or 2.
  • repeating unit having a group having a lactone structure or a sultone structure represented by General Formula (III) will be shown below, but the present invention is not limited thereto.
  • R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.
  • Me represents a methyl group.
  • the content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol, based on all repeating units in the resin (A1), in the case of containing plural kinds. %, More preferably 30 to 50 mol%.
  • Resin (A1) may contain the repeating unit which has the lactone structure or sultone structure mentioned above besides the unit represented by General formula (III).
  • repeating unit having a lactone structure or a sultone structure in addition to the specific examples listed above, the following may be mentioned, but the present invention is not limited thereto.
  • particularly preferable repeating units include the following repeating units.
  • the repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • one type of optical isomer is mainly used, one having an optical purity (ee) of 90% or more is preferable, and more preferably 95% or more.
  • the content of the repeating unit having a lactone structure or a sultone structure other than the repeating unit represented by the general formula (III) is 15 to 60% by mole based on all repeating units in the resin in the case of containing plural kinds. It is preferably 20 to 50 mol%, more preferably 30 to 50 mol%.
  • the resin (A1) has substantially no aromatic group from the viewpoint of transparency to ArF light Is preferred. More specifically, it is preferable that the repeating unit which has an aromatic group is 5 mol% or less of the whole in all the repetition of resin (A1), and it is more preferable that it is 3 mol% or less.
  • the resin (A1) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • the resin (A1) has, for example, an alicyclic hydrocarbon structure not having a polar group (eg, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) as a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure. And non-acid-degradable repeating units. As such a repeating unit, the repeating unit represented by general formula (IV) is mentioned.
  • a polar group eg, an alkali-soluble group, a hydroxyl group, a cyano group, etc.
  • R 5 has at least one cyclic structure and represents a hydrocarbon group having no polar group.
  • Ra represents a hydrogen atom, an alkyl group or a -CH 2 -O-Ra 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
  • the cyclic structure possessed by R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
  • a monocyclic hydrocarbon group for example, a cycloalkyl group having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group or cyclooctyl group, or a cycloalkyl group having 3 to 12 carbon atoms such as cyclohexenyl group And cycloalkenyl groups.
  • the preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.
  • the polycyclic hydrocarbon group includes a ring-aggregated hydrocarbon group or a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group or a perhydronaphthalenyl group.
  • bridged cyclic hydrocarbon ring for example, pinane, bornane, norpinane, norbornane, or bicyclooctane ring (such as bicyclo [2.2.2] octane ring or bicyclo [3.2.1] octane ring) 2
  • Tricyclic hydrocarbon ring such as cyclic hydrocarbon ring, homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, or tricyclo [4.3.1.1 2,5 ] undecane ring Or tetracyclo [4.4.0.1 2,5 . 1 7,10] dodecane, or the like 4 ring and perhydro-1,4-methano-5,8 ring.
  • bridged cyclic hydrocarbon ring examples include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene or perhydro Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as phenalene rings are fused.
  • a preferable bridged cyclic hydrocarbon ring a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo [5, 2, 1, 0 2, 6 ] decanyl group and the like can be mentioned.
  • a more preferable bridged cyclic hydrocarbon ring norbornyl group or adamantyl group can be mentioned.
  • These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, or an amino group substituted with a hydrogen atom, etc.
  • the halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom.
  • the alkyl group is preferably a methyl group, an ethyl group, a butyl group or a t-butyl group.
  • the above alkyl group may further have a substituent, and as the substituent which may further have, a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, or a hydrogen atom is substituted Amino groups.
  • a group by which the said hydrogen atom was substituted an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, or the aralkyloxycarbonyl group is mentioned, for example.
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms
  • the substituted methyl group is preferably methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl or 2-methoxyethoxymethyl group
  • a substituted ethyl group Is preferably 1-ethoxyethyl or 1-methyl-1-methoxyethyl
  • the acyl group is an aliphatic having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl or pivaloyl group
  • An acyl group is preferred, and an alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms.
  • the content of this repeating unit is the same as all repeating units in the resin (A1).
  • the amount is preferably 1 to 40 mol%, more preferably 2 to 20 mol%.
  • Specific examples of the non-acid-degradable repeating unit having an alicyclic hydrocarbon structure not having a polar group include the repeating units disclosed in paragraph 0354 of US Published Patent Application 2012/0135348. The present invention is not limited to these.
  • the resin (A1) has an aromatic hydrocarbon group. It is preferable to include a repeating unit, and it is more preferable to include a repeating unit having a phenolic hydroxyl group. As a repeating unit which has phenolic hydroxyl group, the repeating unit shown below is especially preferable.
  • resin which has a repeating unit represented by the following general formula (A) is mentioned.
  • each of R 01 , R 02 and R 03 independently represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • Ar 1 represents, for example, an aromatic ring group.
  • R 03 and Ar 1 may be an alkylene group, and the two may combine with each other to form a 5- or 6-membered ring with the —C—C— chain.
  • n Y's independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
  • n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.
  • the alkyl group as R 01 to R 03 is, for example, an alkyl group having a carbon number of 20 or less, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. These alkyl groups may have a substituent.
  • the alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R 01 to R 03 above.
  • the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
  • monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group can be mentioned.
  • These cycloalkyl groups may have a substituent.
  • a fluorine atom As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are mentioned, and a fluorine atom is more preferable.
  • R 03 represents an alkylene group
  • the alkylene group preferably includes an alkylene group having a carbon number of 1 to 8, such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
  • the aromatic ring group as Ar 1 is preferably an aromatic ring group having a carbon number of 6 to 14, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. These aromatic ring groups may have a substituent.
  • each of R 36 to R 39 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 structure.
  • Each of R 01 and R 02 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • Ar represents an aryl group.
  • R 36 ⁇ R 39, R 01 , or an alkyl group as R 02 is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n- butyl group, sec- Examples include butyl, hexyl and octyl.
  • the cycloalkyl group as R 36 to R 39 , R 01 or R 02 may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
  • the monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.
  • the polycyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinanyl group and a tricyclodecanyl group, And tetracyclododecyl and androstanyl groups.
  • a part of carbon atoms in the cycloalkyl group may be substituted by a heteroatom such as oxygen atom.
  • R 36 ⁇ R 39, R 01 , aryl group of R 02, or Ar is preferably an aryl group having 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group or an anthryl group.
  • the aralkyl group as R 36 to R 39 , R 01 or R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group and a naphthylmethyl group are preferable.
  • R 36 ⁇ R 39, R 01 , or an alkenyl group as R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, for example, cyclohexenyl group vinyl group, an allyl group, a butenyl group and cycloalkyl .
  • the ring which may be formed by bonding R 36 and R 37 to each other may be monocyclic or polycyclic.
  • the monocyclic type is preferably a cycloalkane structure having a carbon number of 3 to 8, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure and a cyclooctane structure.
  • a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure and a tetracyclododecane structure.
  • Some of the carbon atoms in the ring structure may be substituted by heteroatoms such as oxygen atoms.
  • Each of the above groups may have a substituent.
  • this substituent include alkyl, cycloalkyl, aryl, amino, amido, ureido, urethane, hydroxy, carboxy, halogen, alkoxy, thioether, acyl and acyloxy And alkoxycarbonyl groups, cyano groups and nitro groups. It is preferable that these substituents have 8 or less carbon atoms.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group, a cyclic aliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. These cyclic aliphatic groups and aromatic ring groups may contain hetero atoms. At least two of Q, M and L 1 may be bonded to each other to form a 5- or 6-membered ring.
  • the alkyl group as L 1 and L 2 is, for example, an alkyl group having a carbon number of 1 to 8, and specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and the like
  • the octyl group is mentioned.
  • the cycloalkyl group as L 1 and L 2 is, for example, a cycloalkyl group having a carbon number of 3 to 15, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
  • the aryl group as L 1 and L 2 is, for example, an aryl group having a carbon number of 6 to 15, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.
  • the aralkyl group as L 1 and L 2 is, for example, an aralkyl group having a carbon number of 6 to 20, and specific examples thereof include a benzyl group and a phenethyl group.
  • the divalent linking group as M is, for example, an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), a cycloalkylene group (eg, cyclopentylene group or cyclohexylene group) ), An alkenylene group (eg, ethylene group, propenylene group or butenylene group), an arylene group (eg, phenylene group, tolylene group or naphthylene group), -S-, -O-, -CO-, -SO 2 -,- N (R 0 ) — or a combination of two or more of them.
  • an alkylene group eg, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group
  • a cycloalkylene group eg, cyclopentylene group or cyclohe
  • R 0 is a hydrogen atom or an alkyl group.
  • the alkyl group as R 0 is, for example, an alkyl group having a carbon number of 1 to 8, and specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and octyl group are preferable. It can be mentioned.
  • the alkyl group and the cycloalkyl group as Q are the same as the respective groups as L 1 and L 2 described above.
  • the cyclic aliphatic group or an aromatic ring group as Q for example, cycloalkyl group and aryl group as L 1 and L 2 as described above.
  • the cycloalkyl group and the aryl group are preferably groups having 3 to 15 carbon atoms.
  • Examples of the cyclic aliphatic group or aromatic ring group containing a hetero atom as Q include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, Groups having heterocyclic structures such as thiazoles and pyrrolidones can be mentioned.
  • the ring is not limited to these as long as it is a ring formed of carbon and a hetero atom or a ring formed of only a hetero atom.
  • Examples of the ring structure which can be formed by bonding at least two of Q, M and L 1 to each other include a 5- or 6-membered ring structure formed by forming a propylene group or a butylene group.
  • the 5- or 6-membered ring structure contains an oxygen atom.
  • Each group represented by L 1 , L 2 , M and Q in the general formula (B) may have a substituent.
  • this substituent for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group And alkoxycarbonyl groups, cyano groups and nitro groups. It is preferable that these substituents have 8 or less carbon atoms.
  • the group represented by-(MQ) is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • resin (A1) which has a hydroxystyrene repeating unit below is shown, this invention is not limited to these.
  • tBu represents a t-butyl group
  • Et represents an ethyl group.
  • the resin (A1) in the present invention can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight of the resin (A1) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3 as a polystyrene conversion value by GPC (Gel Permeation Chromatography) method. And preferably from 3,000 to 11,000.
  • the dispersion degree (molecular weight distribution) of the resin (A1) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, still more preferably 1. 1 to 2.0. The smaller the molecular weight distribution, the better.
  • the content of the resin (A1) is preferably 30 to 99% by mass, and more preferably 50 to 95% by mass, based on the total solid content.
  • the resin (A1) may be used alone or in combination of two or more.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain, as the resin (A), a resin (A2) having a phenolic hydroxyl group.
  • the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group.
  • the aromatic ring is a monocyclic or polycyclic aromatic ring, and includes a benzene ring, a naphthalene ring and the like.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (A2), it is generated from an acid generator by irradiation with actinic rays or radiation in the exposed area formed using this composition
  • the acid generally formula (I) described above
  • the crosslinking reaction between the resin (A2) having a phenolic hydroxyl group and the acid crosslinking agent (C) described later proceeds to form a negative pattern.
  • resin (A2) which has a phenolic hydroxyl group contains the repeating unit which has at least 1 type of phenolic hydroxyl group. It does not specifically limit as a repeating unit which has phenolic hydroxyl group, It is preferable that it is a repeating unit represented by following General formula (1).
  • R 11 represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.
  • B 1 represents a single bond or a divalent linking group.
  • Ar represents an aromatic ring.
  • m1 represents an integer of 1 or more.
  • Examples of the methyl group which may have a substituent in R 11 include trifluoromethyl group and hydroxymethyl group.
  • R 11 is preferably a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of developability.
  • the aromatic ring of Ar is a monocyclic or polycyclic aromatic ring and has a substituent having 6 to 18 carbon atoms such as benzene ring, naphthalene ring, anthracene ring, fluorene ring, and phenanthrene ring.
  • an aromatic hydrocarbon ring or, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzoimidazole ring, triazole ring, thiadiazole ring, and Mention may be made of aromatic heterocycles containing heterocycles such as thiazole rings.
  • a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is more preferable from the viewpoint of sensitivity.
  • m1 is preferably an integer of 1 to 5, and more preferably 1.
  • the substitution position of -OH is either the para or meta position relative to the bonding position of the benzene ring to B 1 (the polymer main chain when B 1 is a single bond) Although it may be ortho position, from the viewpoint of crosslinking reactivity, para position and meta position are preferable, and para position is more preferable.
  • the aromatic ring of Ar may have a substituent in addition to the group represented by -OH, and examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group and a carboxy group.
  • substituents include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group and a carboxy group.
  • the repeating unit having a phenolic hydroxyl group is more preferably a repeating unit represented by the following general formula (2) in view of crosslinking reactivity, developability, and dry etching resistance.
  • R 12 represents a hydrogen atom or a methyl group.
  • Ar represents an aromatic ring.
  • R 12 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of developability.
  • Ar in General formula (2) is synonymous with Ar in General formula (1), and its preferable range is also the same.
  • the repeating unit represented by the general formula (2) is a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R 12 is a hydrogen atom and Ar is a benzene ring in the general formula (2)) Is preferred from the viewpoint of sensitivity.
  • resin (A2) has a repeating unit represented by following General formula (3).
  • R 13 represents a hydrogen atom or a methyl group.
  • X represents a group having a non-acid degradable polycyclic alicyclic hydrocarbon structure.
  • Ar 1 represents an aromatic ring.
  • m2 is an integer of 1 or more.
  • R 13 in the general formula (3) represents a hydrogen atom or a methyl group, with a hydrogen atom being particularly preferred.
  • the aromatic ring of Ar 1 in the general formula (3) may have, for example, a substituent having a carbon number of 6 to 18, such as benzene ring, naphthalene ring, anthracene ring, fluorene ring, and phenanthrene ring.
  • aromatic heterocycles containing such heterocycles Among them, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.
  • the aromatic ring of Ar 1 may have a substituent other than the group represented by -OX, and examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 6) and a cycloalkyl group. (Preferably 3 to 10 carbon atoms), aryl group (preferably 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxy group, alkoxycarbonyl group (preferably carbon number) 2 to 7), and an alkyl group, an alkoxy group or an alkoxycarbonyl group is preferable, and an alkoxy group is more preferable.
  • X represents a group having a non-acid degradable polycyclic alicyclic hydrocarbon structure.
  • preferable non-acid-degradable polycyclic alicyclic hydrocarbon structures include an adamantane structure, a decalin structure, a norbornane structure, a norbornene structure, a sedrol structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, cyclooctyl
  • a structure having a plurality of groups, a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure can be mentioned.
  • an adamantane structure is preferable.
  • m2 is preferably an integer of 1 to 5, and 1 is most preferable.
  • the substitution position of -OX may be para, meta or ortho to the bonding position of the benzene ring to the polymer main chain, but the para or meta position is Preferably, the para position is more preferred.
  • repeating unit represented by the general formula (3) include the following.
  • the content thereof is preferably 1 to 40 mol%, more preferably about all the repeating units of the resin (A2). 2 to 30 mol%.
  • the resin (A2) used in the present invention preferably further has the following repeating unit (hereinafter, also referred to as "other repeating unit”) as a repeating unit other than the above-mentioned repeating unit.
  • polymerizable monomers for forming these other repeating units include styrene, alkyl substituted styrene, alkoxy substituted styrene, halogen substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene, maleic anhydride Acid, acrylic acid derivative (acrylic acid, acrylic ester etc.), methacrylic acid derivative (methacrylic acid, methacrylic ester etc.), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinyl naphthalene, vinyl anthracene, and substituents Inden etc. which may have can be mentioned.
  • the resin (A2) may or may not contain these other repeating units, but when it is contained, the content of these other repeating units in the resin (A2) is the entire content of the resin (A2).
  • the amount is generally 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%, based on the repeating unit.
  • the resin (A2) can be synthesized by a known radical polymerization method, anion polymerization method or living radical polymerization method (iniferter method etc.).
  • the weight average molecular weight of the resin (A2) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 2,000 to 15,000.
  • the degree of dispersion (molecular weight distribution) (Mw / Mn) of the resin (A2) is preferably 2.0 or less, and more preferably 1.0 to 1.80, from the viewpoint of further improving the sensitivity and resolution. 0 to 1.60 is more preferable, and 1.0 to 1.20 is particularly preferable.
  • living polymerization such as living anionic polymerization, the degree of dispersion (molecular weight distribution) of the obtained polymer compound becomes uniform, which is preferable.
  • the weight average molecular weight and dispersion degree of resin (A2) are defined as polystyrene conversion value by GPC measurement.
  • the resin (A2) When the resin (A2) is contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, its content is preferably 30 to 95% by mass, and 40 to 90% by mass with respect to the total solid content. Is more preferable, and 50 to 85% by mass is more preferable.
  • the resin (A2) may be used alone or in combination of two or more.
  • ⁇ Crosslinking agent (C)> When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used to form a negative pattern, and a resin (A2) having a phenolic hydroxyl group is used as the resin (A), a crosslinking agent It is preferable to use
  • the crosslinking agent preferably contains a compound having two or more methylol groups in the molecule (hereinafter referred to as “compound (C)" or "crosslinking agent”).
  • hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine compounds, alkoxymethyl glycoluril compounds and alkoxymethylated urea compounds are preferable, and these may have any substituent.
  • Particularly preferable compound (C) as a crosslinking agent is a phenol derivative having 3 to 5 benzene rings in the molecule, 2 or more in total of hydroxymethyl group or alkoxymethyl group, and having a molecular weight of 1200 or less, or And alkoxymethyl glycoluril derivatives.
  • the alkoxymethyl group is preferably a methoxymethyl group or an ethoxymethyl group.
  • phenol derivatives having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst.
  • a phenol derivative having an alkoxymethyl group can be obtained by reacting an alcohol with a corresponding phenol derivative having a hydroxymethyl group under an acid catalyst.
  • a compound further having an N-hydroxymethyl group such as an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound and an alkoxymethylated urea compound or an N-alkoxymethyl groupcan be mentioned.
  • Examples of such compounds include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea and bismethoxymethylurea. , 133, 216 A, West German Patent Nos. 3,634,671 and 3,711,264, and EP 0,212,482A. Among these crosslinking agents, particularly preferred ones are listed below.
  • each of L 1 to L 8 independently represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having 1 to 6 carbon atoms.
  • the content of the crosslinking agent is preferably 3 to 65% by mass with respect to the total solid content in the composition, -50% by mass is more preferable.
  • a crosslinking agent (C) may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the composition of the present invention may contain a compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter also referred to as "compound (D)").
  • the group leaving by the action of an acid is not particularly limited, and 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 a carbamate group or a hemiamide
  • the nal ether group is more preferred.
  • the molecular weight of the compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
  • an amine derivative having a group capable of leaving by the action of an acid on a nitrogen atom is preferable.
  • the compound (D) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protective group constituting the carbamate group can be represented by the following general formula (d-1).
  • Each R b independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), an aryl group (preferably having a carbon number of 3 to 30), and an aralkyl group (Preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
  • R b may be linked to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R b are substituted with a functional group such as hydroxy group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group and halogen atom It may be done. The same applies to the alkoxyalkyl group represented by R b .
  • alkyl group, cycloalkyl group, aryl group and aralkyl group of these R b (these alkyl group, cycloalkyl group, aryl group and aralkyl group are substituted by the above functional group, alkoxy group and halogen atom Examples of the group) include groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, and these alkanes.
  • Groups derived from aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, and t-butyl group And the like, a group substituted with one or more or one or more linear or branched alkyl groups, pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, Groups derived from heterocyclic compounds such as quinoline, quinoline, perhydroquinoline, indazole, and benzimidazole, and groups derived from these heterocyclic compounds derived from linear or branched alkyl groups or aromatic compounds Groups substituted with one or more or one or more groups, Groups derived from linear or branched alkanes, Groups derived from cycloalkanes, and aromatic compounds such as phenyl groups, naphthyl
  • a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferable. More preferably, it is a linear or branched alkyl group or a cycloalkyl group.
  • the compound (D) has a structure represented by the following general formula (6).
  • R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • l represents 2
  • two R a s may be the same or different, and two R a s may be mutually linked to form a heterocyclic ring with the nitrogen atom in the formula.
  • the hetero ring may contain a hetero atom other than the nitrogen atom in the formula.
  • R b has the same meaning as R b in formula (d-1), and preferred examples are also the same.
  • l represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • l + m 3 is satisfied.
  • the alkyl group as R a, a cycloalkyl group, an aryl group and, the aralkyl group, the alkyl group represented by R b, cycloalkyl, aryl, and aralkyl groups are substituted It may be substituted by the same group as the group described above as a preferable group.
  • Specific examples of the alkyl group of R a , a cycloalkyl group, an aryl group and an aralkyl group are as follows: And the same groups as the specific examples described above for R b .
  • the heterocyclic ring formed by bonding the R a to each other preferably has a carbon number of 20 or less, and examples thereof include pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,3, 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7- Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2,3,4 -Groups derived from heterocyclic compounds such as -
  • the compound (D) include, but are not limited to, the compounds disclosed in US 2012/0135348 A1 paragraph 0475.
  • the compound represented by the general formula (6) can be synthesized based on JP-A-2007-298569, JP-A-2009-199021, and the like.
  • the low molecular weight compound (D) having a group capable of leaving on the nitrogen atom by the action of an acid can be used alone or in combination of two or more.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the compound (D), its content is preferably 0.001 to 20% by mass, based on the total solid content of the composition, and more preferably Is 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound (E) in order to reduce the change in performance over time from exposure to heating.
  • a basic compound (E) preferably, compounds having the structures represented by the following formulas (A) to (E) can be mentioned.
  • R 200 , R 201 and R 202 may be the same or different, and a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably carbon) And an aryl group (preferably having a carbon number of 6 to 20), wherein R 201 and R 202 may combine with each other to form a ring.
  • alkyl group having a substituent As the alkyl group having a substituent, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
  • R 203 , R 204 , R 205 and R 206 which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group in these general formulas (A) and (E) is more preferably unsubstituted.
  • Examples of preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkyl morpholine, and piperidine.
  • Further preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium. Examples thereof include compounds having a carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
  • As compounds having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4, 0] Undeca-7-ene and the like.
  • examples thereof include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
  • the compound having an onium carboxylate structure is a compound in which the anion part of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate and the like.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
  • alkylamine derivatives having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like.
  • alkylamine derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
  • the amine compound which has a phenoxy group and the ammonium salt compound which has a phenoxy group can be mentioned further.
  • amine compound primary, secondary and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound may be a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (in addition to an alkyl group) as long as at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to a nitrogen atom.
  • 6 to 12 carbon atoms may be bonded to the nitrogen atom.
  • the amine compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group.
  • the number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferable, and more preferably an oxy alkylene group It is an ethylene group.
  • ammonium salt compounds primary, secondary, tertiary and quaternary ammonium salt compounds can be used, and ammonium salt compounds in which at least one alkyl group is bonded to a nitrogen atom are preferable.
  • the ammonium salt compound may be a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group, in addition to an alkyl group, provided that at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to a nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
  • the ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group.
  • the number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferable, and more preferably an oxy alkylene group It is an ethylene group.
  • the anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a borate, or a phosphate. Among them, a halogen atom or a sulfonate is preferred.
  • the halogen atom is preferably chloride, bromide or iodide
  • the sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms.
  • the organic sulfonate include alkyl sulfonate having 1 to 20 carbon atoms and aryl sulfonate.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group.
  • alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
  • aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring.
  • the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
  • a linear or branched alkyl group or cycloalkyl group specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group And cyclohexyl group and the like.
  • the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.
  • the amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the end opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound.
  • the phenoxy group may have a substituent.
  • a substituent of phenoxy group for example, alkyl group, alkoxy group, halogen atom, cyano group, nitro group, carboxy group, carboxylic acid ester group, sulfonic acid ester group, aryl group, aralkyl group, acyloxy group, and aryl An oxy group etc. are mentioned.
  • the substitution position of the substituent may be any one of 2 to 6 positions.
  • the number of substituents may be in the range of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6.
  • Oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3) CH 2 O- or CH 2 CH 2 CH 2 O-) are preferred among the oxyalkylene groups, more preferably polyoxyethylene It is a group.
  • the amine compound having a phenoxy group is reacted by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
  • an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium It can also be obtained by extraction with an organic solvent such as ethyl acetate or chloroform after the addition of
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with an actinic ray or radiation to reduce the proton acceptor property.
  • the compound may further contain a compound [hereinafter, also referred to as compound (PA)] which generates a compound which has disappeared or has changed from proton acceptor property to acidity.
  • the proton acceptor functional group is a functional group having an electrostatic interaction with a proton or a functional group having an electron, and for example, a functional group having a macrocyclic structure such as cyclic polyether or ⁇ conjugated
  • the nitrogen atom having a noncovalent electron pair not contributing to the ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
  • Examples of preferable partial structures of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
  • the compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is reduced, eliminated, or changed from the proton acceptor property to the acidity.
  • the reduction in proton acceptor property, disappearance, or change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of a proton to the proton acceptor functional group, Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
  • a compound As a specific example of a compound (PA), the following compounds can be mentioned, for example. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP-A 2014-41328 and paragraphs 0108 to 0116 of JP-A 2014-134686 can be used. , The contents of which are incorporated herein. In the following formula, Bu represents a butyl group.
  • the amount of the basic compound to be used is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content in the composition.
  • the acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
  • the basic compound for example, compounds (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) described in paragraphs 0140 to 0144 of JP-A-2013-11833 can be used.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant (F), and a fluorine-based and / or silicon-based surfactant (a fluorine-based surfactant, a silicon-based surfactant, It may contain one or more of a surfactant, a surfactant having both a fluorine atom and a silicon atom).
  • a surfactant F
  • a fluorine-based and / or silicon-based surfactant a fluorine-based surfactant, a silicon-based surfactant, It may contain one or more of a surfactant, a surfactant having both a fluorine atom and a silicon atom.
  • fluorine type and / or silicon type surfactant for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862, US Patent No. 5405720 specification, No. 5360692 specification, No. 5529881 specification, No. 5296330 specification, No. 5436098 specification, No. 5576143 specification, No. 5294511 specification, No. 5824451 specification A surfactant can be mentioned, and the following commercially available surfactant can also be used as it is.
  • F-top EF301, EF303 (manufactured by Shin Akita Kasei Co., Ltd.), Florard FC 430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F 171, F 173, F 176, F 189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surfron S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (trade name) Troy Chemical Co., Ltd.
  • GF-300, GF-150 made by Toa Synthetic Chemical Co., Ltd.
  • Surflon S-393 made by Seimi Chemical Co., Ltd.
  • EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos) And fluorine-containing surfactants, or silicon-containing surfactants.
  • Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
  • the surfactant in addition to the known ones as described above, it is derived from fluoroaliphatic compounds produced by telomerization method (also referred to as telomer method) or oligomerization method (also referred to as oligomer method)
  • telomerization method also referred to as telomer method
  • oligomerization method also referred to as oligomer method
  • a surfactant using a polymer having a fluoroaliphatic group can be used.
  • the fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
  • polymer having a fluoroaliphatic group a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and it is randomly distributed Or may be block copolymerized.
  • poly (oxyalkylene) group examples include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group and the like, and poly (blocked product of oxyethylene, oxypropylene and oxyethylene) Or, it may be a unit having different chain lengths of alkylene within the same chain length, such as poly (block linkage of oxyethylene and oxypropylene).
  • copolymers of monomers having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) are not only binary copolymers, but monomers having two or more different fluoroaliphatic groups, Alternatively, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates) and the like.
  • surfactants other than fluorine-based and / or silicon-based surfactants can also be used.
  • polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether Etc., polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate
  • Fatty acid esters such as polyoxyethylene sorbitan, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate
  • surfactants may be used alone or in some combinations.
  • the content of the surfactant in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total amount of the composition (excluding the solvent).
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (hereinafter, also referred to as "hydrophobic resin (H)” or simply “resin (H)”).
  • the hydrophobic resin (H) is preferably different from the resin (A).
  • the hydrophobic resin (H) is preferably designed to be localized at the interface, but unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar / nonpolar substance is uniformly mixed. It does not have to contribute to As the effect of adding a hydrophobic resin, control of static / dynamic contact angle of the resist film surface with water, improvement of immersion liquid followability, suppression of outgassing, etc. can be mentioned.
  • the hydrophobic resin (H) is any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of localization to the film surface layer. It is preferable to have the above, and it is more preferable to have 2 or more types.
  • the hydrophobic resin (H) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or the silicon atom in the hydrophobic resin (H) may be contained in the main chain of the resin And may be contained in the side chain.
  • the hydrophobic resin (H) contains a fluorine atom
  • it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom Is preferred.
  • the alkyl group having a fluorine atom (preferably having a carbon number of 1 to 10, more preferably having a carbon number of 1 to 4) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. You may have substituents other than.
  • the cycloalkyl group having a fluorine atom and the aryl group having a fluorine atom are respectively a cycloalkyl group having one hydrogen atom substituted by a fluorine atom and an aryl group having a fluorine atom, and further a substituent other than a fluorine atom You may have.
  • alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
  • the invention is not limited to this.
  • Each of R 57 to R 68 independently represents a hydrogen atom, a fluorine atom or an alkyl group (linear or branched).
  • at least one of R 57 to R 61 , at least one of R 62 to R 64 and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom
  • R 62 , R 63 and R 68 are preferably an alkyl group (preferably having a carbon number of 1 to 4) in which at least one hydrogen atom is substituted with a fluorine atom, and is a perfluoroalkyl group having a carbon number of 1 to 4 More preferable.
  • R 62 and R 63 may be linked to each other to form a ring.
  • the hydrophobic resin (H) may contain a silicon atom.
  • a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure is preferable.
  • the repeating unit which has a fluorine atom or a silicon atom what was illustrated by US2012 / 0251948A1 [0519] can be mentioned.
  • the hydrophobic resin (H) also preferably contains a CH 3 partial structure in the side chain portion.
  • the CH 3 partial structure possessed by the side chain portion in the hydrophobic resin (H) (hereinafter, also simply referred to as “side chain CH 3 partial structure”) is a CH 3 partial structure possessed by an ethyl group, a propyl group, etc. Is included.
  • the methyl group directly bonded to the main chain of the hydrophobic resin (H) (for example, ⁇ -methyl group of the repeating unit having a methacrylic acid structure) is the surface of the hydrophobic resin (H) due to the influence of the main chain Because the contribution to the localization is small, it is not included in the CH 3 partial structure in the present invention.
  • the hydrophobic resin (H) is, for example, a repeating unit derived from a monomer having a polymerizable site 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 "it 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 )
  • Each of R 11 to R 14 independently represents a side chain moiety.
  • R 11 to R 14 in the side chain moiety include a hydrogen atom and a monovalent organic group.
  • the monovalent organic group for R 11 to R 14 is an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group A group, and an arylamino carbonyl group etc. are mentioned, These groups may have a substituent further.
  • the hydrophobic resin (H) is preferably a resin having a repeating unit having a CH 3 partial structure in a side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and Among repeating units represented by the following general formula (III), it is more preferable to have at least one repeating unit (x).
  • X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
  • R 2 represents an acid-stable organic group having one or more CH 3 partial structures.
  • the acid-stable organic group is more preferably an organic group having no acid-degradable group.
  • the alkyl group of X b1 is preferably an alkyl group having a carbon number of 1 to 4, 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 preferable.
  • X b1 is preferably a hydrogen atom or a methyl group.
  • R 2 includes an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group having one or more CH 3 partial structures.
  • R 2 is preferably an alkyl group or an alkyl substituted cycloalkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
  • Preferred specific examples of the repeating unit represented by formula (II) are listed below. The present invention is not limited to this.
  • the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-degradable) repeating unit, and specifically, a group which is decomposed by the action of an acid to form a polar group. It is preferable that it is a repeating unit which does not have.
  • X b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R 3 represents an acid-stable organic group having one or more CH 3 partial structures, n represents an integer of 1 to 5;
  • the alkyl group of X b2 is preferably one 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 hydrogen atom is preferable.
  • X b2 is preferably a hydrogen atom. More preferably, R 3 is an organic group having no acid-degradable group, because R 3 is an organic group stable to an acid.
  • R 3 includes an alkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has one or more and ten or less CH 3 partial structures, and more preferably one or more and eight or less. It is more preferable to have one or more and four or less.
  • n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • the repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-degradable) repeating unit, and specifically, a group which is decomposed by the action of an acid to form a polar group. It is preferable that it is a repeating unit which does not have.
  • the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and further, particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II),
  • the content of at least one repeating unit (x) in the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (H), It is more preferable that it is 95 mol% or more.
  • the content is usually 100 mol% or less based on all repeating units of the hydrophobic resin (H).
  • the hydrophobic resin (H) comprises at least one repeating unit (x) of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III)
  • the surface free energy of the hydrophobic resin (H) is increased by containing at 90 mol% or more with respect to all the repeating units of (a).
  • the hydrophobic resin (H) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film to water can be surely improved to improve the immersion liquid followability. it can.
  • the hydrophobic resin (H) has the following (x) to (z) in the cases (i) including a fluorine atom and / or a silicon atom and (ii) including a CH 3 partial structure in the side chain portion: It may have at least one group selected from the group.
  • Examples of the acid group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkyl (Carbonyl) imide group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl) And sulfonyl) methylene group and the like.
  • Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, or bis (alkylcarbonyl)
  • a repeating unit having an acid group (x) a repeating unit in which an acid group is directly bonded to the main chain of a resin such as a repeating unit of acrylic acid or methacrylic acid, or a resin of the resin via a linking group
  • bonded with the principal chain are mentioned, Furthermore, the polymerization initiator or chain transfer agent which has an acidic radical can be used at the time of superposition
  • the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having an acid group (x) is preferably 1 to 50% by mole, more preferably 3 to 35% by mole, still more preferably 5 to 50% by mole based on all repeating units in the hydrophobic resin (H). It is 20 mol%.
  • Rx represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH.
  • a group having a lactone structure an acid anhydride group or an acid imide group (y), a group having a lactone structure is particularly preferable.
  • the repeating unit containing these groups is, for example, a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester.
  • this repeating unit may be a repeating unit in which this group is linked to the main chain of the resin via a linking group.
  • this repeating unit may be introduced at the end of the resin using a polymerization initiator or chain transfer agent having this group at the time of polymerization.
  • a repeating unit which has a group which has lactone structure the thing similar to the repeating unit which has the lactone structure previously demonstrated by the term of resin (A) is mentioned, for example.
  • the content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100% by mole, based on all repeating units in the hydrophobic resin (H), and 3 to 98 The mole percent is more preferable, and 5 to 95 mole percent is more preferable.
  • the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin (H) is, for example, a repeating unit having a group which is decomposed by the action of the acid mentioned in the resin (A) to form a carboxy group Similar examples include, but are not limited to.
  • the repeating unit having a group (z) capable of decomposing by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin (H) is preferably 1 to 80 mol%, more preferably about all the repeating units in the resin (H). It is 10 to 80 mol%, more preferably 20 to 60 mol%.
  • the hydrophobic resin (H) may further have another repeating unit other than the above-described repeating unit.
  • the repeating unit containing a fluorine atom is preferably 10 to 100% by mole, and more preferably 30 to 100% by mole, in all repeating units contained in the hydrophobic resin (H).
  • the repeating unit containing a silicon atom is preferably 10 to 100% by mole, and more preferably 20 to 100% by mole, in all repeating units contained in the hydrophobic resin (H).
  • the hydrophobic resin (H) does not substantially contain a fluorine atom and a silicon atom, particularly when the hydrophobic resin (H) contains a CH 3 partial structure in the side chain portion.
  • the hydrophobic resin (H) is preferably substantially constituted only by a repeating unit constituted only by an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.
  • the weight average molecular weight of the hydrophobic resin (H) in terms of standard polystyrene is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.
  • the hydrophobic resin (H) may be used alone or in combination of two or more.
  • the content of the hydrophobic resin (H) in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass, relative to the total solid content in the composition.
  • the amount of residual monomers and oligomer components in the hydrophobic resin (H) is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass.
  • the molecular weight distribution (Mw / Mn, also referred to as the degree of dispersion) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.
  • hydrophobic resin (H) Various commercially available products can be used as the hydrophobic resin (H), and the hydrophobic resin (H) can be synthesized according to a conventional method (for example, radical polymerization).
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention usually further contains a solvent.
  • a solvent for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxy propionate, cyclic lactone (preferably having a carbon number of 4 to 10), and monoketone which may contain a ring
  • Organic solvents such as compounds (preferably having a carbon number of 4 to 10), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates and the like can be mentioned.
  • alkylene glycol monoalkyl ether carboxylate for example, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate Propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferably mentioned.
  • PMEA propylene glycol monomethyl ether acetate
  • propylene glycol monopropyl ether acetate propylene glycol monopropyl ether acetate
  • propylene glycol monobutyl ether acetate Propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl
  • alkylene glycol monoalkyl ether for example, propylene glycol monomethyl ether (PGME, aka 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and And ethylene glycol monoethyl ether are preferably mentioned.
  • PGME propylene glycol monomethyl ether
  • PGME 1-methoxy-2-propanol
  • propylene glycol monoethyl ether propylene glycol monopropyl ether
  • propylene glycol monobutyl ether propylene glycol monobutyl ether
  • ethylene glycol monomethyl ether propylene glycol monobutyl ether
  • ethylene glycol monoethyl ether ethylene glycol monoethyl ether
  • alkyl lactate ester examples include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
  • alkyl alkoxy propionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.
  • cyclic lactones include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ -octano.
  • Preferred examples include ic lactone and ⁇ -hydroxy- ⁇ -butyrolactone.
  • Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, and the like.
  • alkylene carbonate a propylene carbonate, vinylene carbonate, ethylene carbonate, and a butylene carbonate are mentioned preferably, for example.
  • alkyl alkoxy acetates examples include: 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and Methoxy-2-propyl is preferably mentioned.
  • alkyl pyruvate examples include methyl pyruvate, ethyl pyruvate and propyl pyruvate.
  • a solvent having a boiling point of 130 ° C. or higher at normal temperature and normal pressure is mentioned.
  • the above solvents may be used alone or in combination of two or more.
  • a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used as the organic solvent.
  • the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether, Ethyl lactate is more preferred.
  • alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether acetate, Ethyl ethoxy propionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone are still more preferable.
  • the mixing ratio (mass ratio) of the hydroxyl group-containing solvent to the hydroxyl group-free solvent is, for example, 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60. / 40.
  • a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferred in view of coating uniformity.
  • the solvent is preferably a mixture of two or more of propylene glycol monomethyl ether acetate.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention can appropriately contain a carboxylic acid onium salt, a dye, a plasticizer, a photosensitizer, a light absorber, and the like in addition to the components described above.
  • 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 described later (for example, resist solvent, developer, rinse liquid, composition for forming antireflective film)
  • the composition for forming a top coat etc. preferably does not contain impurities such as metals.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less.
  • metal impurities Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, And Zn and the like.
  • 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.
  • the filter may be a composite material in which these materials and ion exchange media are combined.
  • the filter may be one previously washed with an organic solvent.
  • plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination.
  • the 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 step of filtering a plurality of times may be a circulating filtration step.
  • the pressure difference between the filters is preferably as small as possible, generally 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less.
  • the pressure difference between the filter and the filling nozzle is also preferably as small as possible, generally 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less.
  • the inside of the manufacturing apparatus of actinic-ray-sensitive or radiation-sensitive resin composition performs gas substitution by inert gas, such as nitrogen. Thereby, it can suppress that active gas, such as oxygen, melt
  • the actinic ray-sensitive or radiation-sensitive resin composition is filtered by a filter and then filled in a clean container.
  • the composition filled in the container is preferably stored refrigerated. As a result, performance degradation due to aging is suppressed.
  • the time to start refrigerated storage is preferably as short as possible, generally within 24 hours, preferably within 16 hours, and more preferably within 12 hours. Less than time is more preferred.
  • the storage temperature is preferably 0 to 15 ° C., more preferably 0 to 10 ° C., and still more preferably 0 to 5 ° C.
  • a raw material having a small metal content is selected as a raw material constituting the various materials, filter filtration is performed on the raw materials constituting the various materials,
  • the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under conditions that minimize contamination as much as possible.
  • Teflon registered trademark
  • distillation may be performed under conditions that minimize contamination as much as possible.
  • the preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the conditions mentioned above.
  • adsorbent Besides filter filtration, removal of impurities by adsorbent may be performed, and filter filtration and adsorbent may be used in combination.
  • adsorbent known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • inorganic adsorbents such as silica gel and zeolite
  • Organic processing solutions such as developers and rinse solutions are used to prevent the breakdown of chemical solution piping and various parts (filters, O-rings, tubes, etc.) caused by electrostatic charge and subsequent electrostatic discharge. You may add.
  • the conductive compound is not particularly limited, and examples thereof include methanol. Although the addition amount is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics and rinse characteristics.
  • SUS stainless steel
  • polyethylene, polypropylene or fluorine resin polytetrafluoroethylene, perfluoroalkoxy resin, etc.
  • antistatic-treated polyethylene, polypropylene, or fluorocarbon resin such as polytetrafluoroethylene and perfluoroalkoxy resin
  • the inner wall surface of the container for storing the various materials described above is preferably treated so as to prevent elution of impurities such as metals.
  • the inner wall surface of the container is more preferably a surface made of electrolytically polished stainless steel, a surface lined with glass, or a surface coated with a fluorine-containing resin.
  • a method of improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention.
  • a method of improving the surface roughness of the pattern for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in WO 2014/002808 may be mentioned.
  • a known method may be applied as described in 8328 83280 N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”.
  • the pattern formation method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Page 4815-4823).
  • DSA Directed Self-Assembly
  • the resist pattern formed by the above method can be used, for example, as a core material (core) of the spacer process disclosed in JP-A-3-270227 and JP-A-2013-164509.
  • the present invention also relates to a resist film formed of the actinic ray-sensitive or radiation-sensitive resin composition described above.
  • a resist film is formed, for example, by applying the above-described actinic ray-sensitive or radiation-sensitive resin composition on a substrate at a solid content concentration as described later.
  • the actinic ray-sensitive or radiation-sensitive resin composition described above is coated on a substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., at 60 to 150 ° C.
  • the resist film is formed by prebaking for 1 to 20 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes.
  • the thickness of the formed resist film is preferably 10 to 200 nm, more preferably 10 to 150 nm, and still more preferably 20 to 150 nm.
  • the substrate examples include a silicon substrate, a metal vapor deposited film, or a substrate provided with a film containing a metal, and a vapor deposited film of Cr, MoSi or TaSi, or an oxide or nitride thereof is provided on the surface.
  • a substrate is preferred.
  • 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 the present invention comprises a resist film formation step of forming a resist film using the above-described actinic ray-sensitive or radiation-sensitive resin composition, an exposure step of exposing the resist film, and the exposed resist Developing the film with a developer.
  • the pattern formation method of the present invention may further include a rinse step of rinsing using a rinse solution, if necessary.
  • the total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition is generally 1.0 to 10% by mass, preferably 1.0 to 8.0% by mass, more preferably 1.0 to It is 6.0 mass%.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used by dissolving the above components in a solvent, filtering it, and then applying it to a support.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, still more preferably 0.03 ⁇ m or less.
  • a plurality of types of filters may be connected in series or in parallel.
  • the composition may be filtered multiple times.
  • the composition may be subjected to a degassing treatment and the like before and after the filter filtration.
  • composition is applied on a substrate (eg, a silicon / silicon dioxide coating) as used in the manufacture of integrated circuit devices by a suitable coating method such as a spinner. Thereafter, it is dried to form an actinic ray-sensitive or radiation-sensitive resin film (resist film).
  • a substrate eg, a silicon / silicon dioxide coating
  • a suitable coating method such as a spinner.
  • resist film an actinic ray-sensitive or radiation-sensitive resin film
  • the resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained.
  • a predetermined mask preferably baked (heated), developed and rinsed.
  • drawing direct drawing not through a mask is common.
  • PB preheating step
  • the heating temperature is preferably 70 to 120 ° C. for both PB and PEB, and more preferably 80 to 110 ° C.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
  • the heating can be performed by means provided in a common exposure developing machine, and may be performed using a hot plate or the like.
  • the bake accelerates the reaction in the exposed area and improves the sensitivity and pattern profile.
  • the actinic ray or radiation is not particularly limited, and examples thereof include a KrF excimer laser, an ArF excimer laser, an electron beam, and EUV light. Among them, electron beam or EUV light (extreme ultraviolet light) is preferable from the viewpoint of achieving better resolution and exposure latitude.
  • the developer used in the step of developing a resist film formed using the actinic ray-sensitive or radiation-sensitive composition of the present invention is not particularly limited, and, for example, an alkaline developer or a developer containing an organic solvent ( Hereinafter, the organic developer may be used). Among them, it is preferable to use an organic developer from the viewpoint of achieving better resolution and exposure latitude.
  • alkali developing solution for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, etc., primary amines such as ethylamine and n-propylamine , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxy
  • Aqueous alkaline solutions such as cyclic ammonium and quaternary ammonium salts such as tetraethyl ammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used.
  • an appropriate amount of alcohol and surfactant can be added to the alkaline aqueous solution and used.
  • the alkali concentration of the alkali developer is usually 0.1 to
  • organic developer polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and the like, and hydrocarbon solvents can be used.
  • 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 thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.
  • ester solvents for example, 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 Ether acetate, ethyl 3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate etc Can be mentioned.
  • alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, Alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl Ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and meth Shi glycol ether solvents such as methyl butanol.
  • glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoe
  • ether solvents include, in addition to the above glycol ether solvents, dioxane, tetrahydrofuran and the like.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Etc. can be used.
  • hydrocarbon-based solvent examples include aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as pentane, hexane, octane and decane.
  • a plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water.
  • the content of water contained in the organic developer is preferably less than 10% by mass, and more preferably substantially free of water.
  • the use amount of the organic solvent with respect to the organic developer is preferably 90% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass, with respect to the total amount of the developer.
  • the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
  • the surfactant is not particularly limited, and, for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
  • fluorine and / or silicone surfactants for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No.
  • the surfactants described in the specifications of 5360692, 5529881, 5296330, 5436098, 5576143, 5294511 and 5824451 can be mentioned.
  • they are nonionic surfactants.
  • the nonionic surfactant is not particularly limited, and it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
  • the amount of surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.
  • Pure water may be used as the rinse liquid, and an appropriate amount of surfactant may be added thereto.
  • a developing method for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of developing by standing up the developer on the substrate surface by surface tension and standing for a certain time (paddle Method), spraying the developer on the substrate surface (spraying method), and continuing to discharge the developer while scanning the developer discharging nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method) Etc.
  • dip method a method of immersing the substrate in a bath filled with a developer for a certain time
  • paddle Method a method of developing by standing up the developer on the substrate surface by surface tension and standing for a certain time
  • spraying the developer on the substrate surface spraying the developer on the substrate surface
  • continuing to discharge the developer while scanning the developer discharging nozzle at a constant speed onto the substrate rotating at a constant speed
  • dynamic dispensing method dynamic dispensing method
  • a treatment of removing the developer or rinse solution adhering on the pattern with a supercritical fluid can be performed.
  • an antireflective film may be coated on the substrate in advance.
  • the antireflective film any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and organic film types made of a light absorber and a polymer material can be used.
  • organic antireflective film commercially available organic antireflective films such as DUV30 series and DUV-40 series manufactured by Brewer Science, and AR-2, AR-3 and AR-5 manufactured by Shipley can also be used.
  • Exposure may be performed by filling a liquid (immersion medium) having a refractive index higher than that of air between the film and the lens at the time of irradiation with actinic rays or radiation. This can improve the resolution.
  • a liquid immersion medium
  • Water is preferably used as the immersion medium to be used. Water is also preferred in view of the low temperature coefficient of refractive index, the availability and the ease of handling.
  • a medium having a refractive index of 1.5 or more can also be used in that the refractive index can be improved.
  • the medium may be an aqueous solution or an organic solvent.
  • additives for the purpose of improving the refractive index may be added in a small proportion. Examples of additives are described in detail in Chapter 12 of CMC publication "Process and materials for immersion lithography".
  • distilled water is preferable as water to be used because a substance opaque to 193 nm light and an impurity whose refractive index is largely different from water cause distortion of an optical image projected onto a film.
  • pure water purified with an ion exchange filter or the like may be used.
  • the electric resistance of pure water is preferably 18.3 M ⁇ cm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and degassing is preferably performed.
  • a film which is hardly soluble in the immersion liquid a film (resist film) formed of the actinic ray-sensitive or radiation-sensitive composition and the immersion liquid
  • an “upper layer film” or “top coat” may be provided.
  • the functions required for the top coat include coating suitability on a resist film, transparency to radiation, particularly radiation having a wavelength of 193 nm, and low immersion liquid solubility.
  • composition for forming the top coat (“the composition for forming the upper layer film” or “the top coat composition”) is not mixed with the actinic ray-sensitive or radiation-sensitive composition that constitutes the resist film, and thus the resist It is preferable to use one that can be uniformly applied on the film.
  • polymers containing no aromatic group are preferable as the material contained in the top coat.
  • Such polymers include, for example, hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ethers, silicon containing polymers and fluorine containing polymers.
  • the hydrophobic resin described above is also suitable as a top coat. Since the elution of impurities from the top coat to the immersion liquid contaminates the optical lens, the residual monomer component of the polymer contained in the top coat is preferably as small as possible.
  • the top coat is preferably applied and formed on the resist film using, for example, a top coat composition containing the above-described hydrophobic resin and a solvent.
  • the solvent that can be used is not particularly limited as long as it dissolves the resin described later and does not dissolve the resist film, and, for example, alcohol solvents, ether solvents, ester solvents, fluorine solvents, or hydrocarbon solvents And the like, and it is more preferable to use a non-fluorinated alcohol solvent.
  • the viscosity of the solvent is preferably 5 cP (centipoise) or less, more preferably 3 cP or less, still more preferably 2 cP or less, and particularly preferably 1 cP or less.
  • solvents may be used alone or in combination of two or more.
  • the topcoat composition preferably further contains at least one compound selected from the group consisting of the following (A1) to (A3).
  • A1 Acid diffusion control agent (A2) Compound having bond or group selected from the group consisting of ether bond, thioether bond, hydroxy group, thiol group, carbonyl bond and ester bond (A3) Compound having a radical trap group
  • A1 to (A3) will be respectively described.
  • the top coat composition preferably further contains an acid diffusion control agent.
  • an acid diffusion control agent which can be contained in the topcoat composition, for example, the same one as the basic compound (E) which can be contained in the actinic ray-sensitive or radiation-sensitive resin composition can be used.
  • the content of the acid diffusion control agent in the topcoat composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass based on the solid content of the topcoat composition. % Is more preferred.
  • the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxy group, a thiol group, a carbonyl bond and an ester bond. Since the oxygen atom or sulfur atom contained in these groups or bonds has a noncovalent electron pair, the acid can be trapped by the interaction with the acid diffused from the resist film.
  • the compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and still more preferably four or more.
  • groups or bonds selected from a plurality of ether bonds, thioether bonds, hydroxy groups, thiol groups, carbonyl bonds and ester bonds contained in the compound (A2) may be identical to or different from one another. Good.
  • the molecular weight of the compound (A2) is preferably 3,000 or less, more preferably 2,500 or less, still more preferably 2,000 or less, and particularly preferably 1,500 or less.
  • the number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more.
  • the number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • 200 degreeC or more is preferable, as for the boiling point of a compound (A2), 220 degreeC or more is more preferable, and 240 degreeC or more is still more preferable.
  • the compound (A2) is preferably a compound having an ether bond, preferably having two or more ether bonds, more preferably having three or more, and still more preferably having four or more.
  • the compound (A2) preferably contains a repeating unit containing an oxyalkylene structure represented by the following general formula (1).
  • R 11 represents an alkylene group which may have a substituent
  • n represents an integer of 2 or more
  • * represents a bond.
  • the carbon number of the alkylene group represented by R 11 in the general formula (1) is not particularly limited, and is preferably 1 to 15, more preferably 1 to 5, still more preferably 2 or 3, and particularly preferably 2.
  • the substituent is not particularly limited, and, for example, an alkyl group (preferably having a carbon number of 1 to 10) is preferable.
  • n is preferably an integer of 2 to 20, and more preferably 10 or less because the DOF (depth of field) becomes larger.
  • the average value of n is preferably 20 or less, more preferably 2 to 10, still more preferably 2 to 8, and particularly preferably 4 to 6, because the DOF becomes larger. preferable.
  • the “average value of n” means the value of n determined so that the weight-average molecular weight of the compound (A2) is measured by GPC and the obtained weight-average molecular weight matches the general formula. If n is not an integer, the value is rounded off.
  • Plural R 11 may be the same or different.
  • the compound having a partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) because the DOF becomes larger.
  • R 12 and R 13 each independently represent a hydrogen atom or an alkyl group.
  • the carbon number of the alkyl group is not particularly limited, and is preferably 1 to 15.
  • R 12 and R 13 may combine with each other to form a ring.
  • m represents an integer of 1 or more.
  • m is preferably an integer of 1 to 20, and more preferably 10 or less because the DOF becomes larger.
  • the average value of m is preferably 20 or less, more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable.
  • the “average value of m” is synonymous with the “average value of n” described above.
  • a plurality of R 11 may be the same or different.
  • the compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.
  • the compound (A2) may be a commercially available product, or may be synthesized by a known method.
  • the content of the compound (A2) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and further preferably 2 to 20% by mass, based on the total solid content in the upper layer film (top coat). Preferably, 3 to 18% by mass is particularly preferred.
  • the compound having a radical trap group is also referred to as Compound (A3).
  • the radical trap group is a group that traps active radicals and stops radical reactions. Examples of such radical trap groups include groups that react with active radicals to be converted into stable free radicals, and groups having stable free radicals. Examples of such compounds having a radical trap group include hydroquinone, catechol, benzoquinone, nitroxyl radical compound, aromatic nitro compound, N-nitroso compound, benzothiazole, dimethylaniline, phenothiazine, vinyl pyrene, and derivatives thereof. Etc.
  • the radical trap group having no basicity is, for example, at least one selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group.
  • a hindered phenol group for example, at least one selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group.
  • a hindered phenol group for example, at least one selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group.
  • a nitroso group for example, at least one selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group,
  • radical trap groups there is no particular limitation on the number of radical trap groups that the compound (A3) has, and when the compound (A3) is a compound other than a polymer compound, 1 to 10 radical trap groups are preferable in one molecule, and 1 to 5 The number is more preferably 1 to 3.
  • the repeating unit having a radical trap group preferably has 1 to 5 radical trap groups, and has 1 to 3 radical trap groups. Is more preferred.
  • the composition ratio of the repeating unit having a radical trap group in the polymer compound is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and still more preferably 30 to 100 mol%.
  • the compound (A3) having a radical trap group a compound having a nitrogen-oxygen bond is preferable, and a compound represented by any one of the following formulas (1) to (3) is more preferable.
  • the compound represented by the following general formula (1) corresponds to a compound having an N-oxyl free radical group
  • the compound represented by the following general formula (2) corresponds to a compound having a nitroso group
  • the compound represented by Formula (3) corresponds to the compound which has a nitrone group.
  • R 1 to R 6 each independently represent an alkyl group, a cycloalkyl group or an aryl group.
  • R 1 and R 2 may combine to form a ring, and in formula (3), at least two of R 4 to R 6 may combine to form a ring.
  • R 1 ⁇ R 6 represents an alkyl group, a cycloalkyl group, and an aryl group, optionally formed by R 1 and R 2 are bonded rings, as well, and at least two binding of R 4 ⁇ R 6
  • the ring which may be formed may have a substituent.
  • Examples of the alkyl group represented by R 1 to R 6 include linear or branched alkyl groups having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group and an n-propyl group. , I-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc. A methyl group, an ethyl group, an n-butyl group or a t-butyl group is preferred.
  • the cycloalkyl group represented by R 1 to R 6 includes, for example, a cycloalkyl group having a carbon number of 3 to 15, and specific examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl Preferred examples include a group, cyclooctyl group, norbornyl group, and adamantyl group.
  • Examples of the aryl group represented by R 1 to R 6 include an aryl group having a carbon number of 6 to 14, and specific examples thereof preferably include a phenyl group, a tolyl group, and a naphthyl group.
  • the ring which may be formed by R 1 and R 2 and the ring which may be formed by R 4 to R 6 is preferably a 5- to 10-membered ring, more preferably a 5- or 6-membered ring It is.
  • R 1 ⁇ R 6 represents an alkyl group, a cycloalkyl group, and an aryl group, optionally formed by R 1 and R 2 are bonded rings, as well, and at least two binding of R 4 ⁇ R 6
  • the compound represented by any one of the general formulas (1) to (3) may be in the form of a resin, in which case at least one of R 1 to R 6 is bonded to the main chain or side chain of the resin It may be done.
  • the molecular weight is not particularly limited, and the molecular weight is preferably 100 to 5,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. preferable.
  • the compound (A3) having a radical trap group is a polymer compound having a repeating unit, its weight average molecular weight is preferably 5,000 to 20,000, and more preferably 5,000 to 10,000.
  • a commercially available compound may be used as the compound (A3) having a radical trap group, or a compound synthesized by a known method may be used.
  • the compound (A3) is synthesized by the reaction of a low molecular weight compound having a commercially available radical trap group with a polymer compound having a reactive group such as an epoxy group, a halogenated alkyl group, an acid halide group, a carboxy group and an isocyanate group. You may
  • the content of the compound (A3) having a radical trap group is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the topcoat composition.
  • the top coat composition may contain a plurality of one compound selected from the group consisting of (A1) to (A3). For example, two or more kinds of compounds (A1) which are distinguished from each other may be included.
  • the topcoat composition may contain two or more compounds selected from the group consisting of (A1) to (A3). For example, both the compound (A1) and the compound (A2) may be contained.
  • the topcoat composition contains a plurality of compounds selected from the group consisting of (A1) to (A3)
  • the total content of these compounds is usually 0 based on the total solids of the topcoat composition. It is from .001 to 20% by mass, preferably from 0.01 to 10% by mass, and more preferably from 1 to 8% by mass.
  • the compound (A3) which has a radical trap group can be used individually by 1 type or in combination of 2 or more types.
  • a developer may be used, or a separate peeling agent may be used.
  • the release agent a solvent having a small penetration into the actinic ray-sensitive or radiation-sensitive film is preferable. From the viewpoint that the peeling process can be performed simultaneously with the development process of the resist, it is preferable that the peeling can be performed by an alkaline developer.
  • the top coat is preferably acidic from the viewpoint of peeling with an alkaline developer, but may be neutral or alkaline from the viewpoint of non-intermixing with the resist.
  • the resolution can be improved.
  • the exposure light source is an ArF excimer laser (wavelength: 193 nm)
  • the top coat for ArF immersion exposure may be close to the refractive index (1.44) of water. preferable.
  • the top coat is preferably a thin film.
  • the topcoat is preferably not mixed with the actinic or radiation sensitive film, and further not mixed with the immersion liquid.
  • the solvent used for the top coat is poorly soluble in the solvent used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and insoluble in water. It is preferable that it is a medium of sex.
  • the immersion liquid is an organic solvent
  • the top coat may be water soluble or water insoluble. Even in the case of performing exposure by means other than immersion exposure processing, a top coat may be formed on the resin film.
  • the present invention also relates to a method of manufacturing an electronic device including the above-described pattern forming method of the present invention.
  • the electronic device obtained by the above manufacturing method is suitably mounted on an electric and electronic device (home appliance, office automation (OA) / media related device, optical device, communication device, etc.).
  • OA office automation
  • the present invention also relates to a mask blank with a resist film provided with the resist film obtained as described above.
  • the mask blank with a resist film of the present invention comprises the mask blank and the above-described resist film disposed on the mask blank.
  • the mask blank has, for example, a transparent substrate, and further has a light shielding film and the like disposed thereon.
  • the transparent substrate to be used include transparent substrates such as quartz and calcium fluoride.
  • necessary ones of functional films such as a light shielding film, an antireflective film, a phase shift film, and additionally an etching stopper film and an etching mask film are laminated.
  • Examples of the material of the functional film include silicon or transition metals such as chromium, molybdenum, zirconium, tantalum, tungsten, titanium, and niobium.
  • the material used for the outermost layer is a material mainly composed of silicon or a material containing silicon and oxygen and / or nitrogen; a silicon compound material mainly composed of a material further containing a transition metal therein; Mainly a material containing one or more transition metals, particularly one selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, and niobium, or further containing at least one element selected from oxygen, nitrogen, and carbon. Examples include transition metal compound materials as constituent materials.
  • the light shielding film may have a single layer structure, but preferably has a multilayer structure in which a plurality of materials are coated.
  • the thickness of the film per layer is not particularly limited, and is preferably 5 nm to 100 nm, and more preferably 10 nm to 80 nm.
  • the thickness of the entire light shielding film is not particularly limited, and is preferably 5 nm to 200 nm, and more preferably 10 nm to 150 nm.
  • the present invention also relates to a method for forming a pattern of a resist blank with a resist film provided with the resist film obtained as described above.
  • the pattern forming method of the resist blank with a resist film according to the present invention comprises an exposure step of exposing the resist film in the above-described mask blank with a resist film, a developing step of developing the exposed resist film in the mask blank with a resist film, including.
  • the said exposure process is the same as the exposure process demonstrated as the pattern formation method of the above-mentioned actinic-ray-sensitive or radiation-sensitive resin composition, and the suitable aspect is also the same.
  • the developing step is the same as the developing step described as the method for forming a pattern of the actinic ray-sensitive or radiation-sensitive resin composition described above, and the preferred embodiment is also the same. After forming a pattern on a mask blank with a resist film, using this pattern as a mask, etching processing and ion implantation are appropriately performed to form a semiconductor fine circuit, an imprint mold structure, and the like.
  • actinic-ray-sensitive or radiation-sensitive resin composition are shown below.
  • ⁇ Crosslinking agent> The following were used as a crosslinking agent.
  • W-1 Megafac F176 (made by DIC Corporation) (fluorinated)
  • W-2 Megafac R08 (made by DIC Corporation) (fluorinated and silicon based)
  • W-3 PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorinated)
  • W-4 Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)
  • W-5 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon based)
  • each actinic-ray-sensitive or radiation-sensitive resin composition was prepared by filtering the obtained solution using a polytetrafluoroethylene filter having a pore size of 0.05 ⁇ m.
  • the ratio in the case of using a plurality of each component in each table is a "mass ratio”.
  • the content of each component in the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) is as described in the table.
  • the content of the solvent (* 1 in the table) was such that the composition had the above solid content concentration.
  • the performance of the obtained actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the various methods shown below, and the results are shown in each table.
  • Examples 1A to 18A, Comparative Examples 1A to 4A Exposure condition 1: ArF immersion exposure, alkaline development
  • a composition ARC29SR manufactured by Nissan Chemical Industries, Ltd.
  • a composition ARC29SR for forming an organic antireflective film was coated on a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflective film with a film thickness of 98 nm.
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition is applied onto the obtained antireflective film, baked at 130 ° C. for 60 seconds (PB: Prebake), and a resist film having a thickness of 120 nm is obtained. It formed.
  • a solution of 3% by mass in which a resin for top coat is further dissolved in decane / octanol (mass ratio 9/1) is applied onto the resist film obtained above, and Baking was performed for 2 seconds to form a top coat layer having a thickness of 50 nm.
  • An ArF excimer laser immersion scanner (ASML XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) is used, and a 1: 1 line and space with a line width of 48 nm.
  • the pattern was exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid.
  • the exposure dose to reproduce a 1: 1 line-and-space pattern with a line width of 48 nm is taken as the optimum exposure dose, and the exposure dose width is determined to allow pattern size of 48 nm ⁇ 10% when the exposure dose is changed.
  • the This value was divided by the optimum exposure and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.
  • CDU In-Plane Uniformity
  • Examples 1B to 18B and Comparative Examples 1B to 4B Exposure condition 2: ArF immersion exposure, organic solvent development
  • a composition ARC29SR manufactured by Nissan Chemical Industries, Ltd.
  • a composition ARC29SR for forming an organic antireflective film was coated on a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflective film with a film thickness of 95 nm.
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition is applied onto the obtained antireflective film, and baking (PB: Prebake) is performed at 100 ° C. for 60 seconds to give a film thickness of 100 nm.
  • a resist film was formed.
  • the obtained wafer was used as an ArF excimer laser immersion scanner (manufactured by ASML; XT 1700 i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) 1: It exposed through 6% halftone mask of 1 line and space pattern. Ultrapure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by puddling with a negative developing solution (butyl acetate) for 30 seconds, and was developed by rinsing with a rinse solution (methyl isobutyl carbinol (MIBC)) for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 resist pattern with a line width of 48 nm and a 1: 1 line and space.
  • PEB Post Exposure Bake
  • Examples 1C to 18C, Comparative Examples 1C to 4C Exposure condition 3: EB (electron beam) exposure, alkali development, positive pattern
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater. Next, heating and drying were performed at 120 ° C. for 90 seconds on a hot plate to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a film thickness of 60 nm. Electron beam irradiation was performed to the obtained actinic-ray-sensitive or radiation-sensitive film using an electron beam irradiation apparatus (HL750, manufactured by Hitachi, Ltd., acceleration voltage: 50 keV).
  • HL750 electron beam irradiation apparatus
  • the resist film was developed at 23 ° C. for 60 seconds using a 2.38 mass% aqueous tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and spin-dried to form a positive resist pattern.
  • Pattern shape evaluation The cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 50 nm at an exposure dose (electron beam dose) exhibiting the above sensitivity is a scanning electron microscope (S-made by Hitachi, Ltd. It observed using 4300).
  • the ratio represented by [line width at bottom (bottom) of line pattern / line width at middle of line pattern (height position of half of line pattern height)] is 1.05
  • the above-mentioned thing was made into "taper”, and the thing with the said ratio is less than 1.05 was made into "rectangle", and evaluation was performed by two steps. The results of these evaluation methods are shown in Table 6.
  • Examples 1D to 18D and Comparative Examples 1D to 4D Exposure condition 4: EB (electron beam) exposure, alkali development, negative pattern
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater. Next, heating and drying were performed at 120 ° C. for 90 seconds on a hot plate to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a film thickness of 60 nm.
  • Electron beam irradiation was performed to the obtained actinic-ray-sensitive or radiation-sensitive film using an electron beam irradiation apparatus (HL750, manufactured by Hitachi, Ltd., acceleration voltage: 50 keV).
  • the resist film was developed at 23 ° C. for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, rinsed with pure water for 30 seconds, and spin-dried to obtain a negative resist pattern.
  • the sensitivity evaluation, the resolution evaluation, and the exposure latitude evaluation were performed on the obtained negative resist pattern. These evaluation methods are the same as the evaluation methods in Examples 1C to 18C.
  • the pattern shape was evaluated by the following method. The results are shown in Table 7. Evaluation of pattern shape
  • the cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 50 nm at an exposure amount (electron beam irradiation amount) exhibiting the above sensitivity is a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.) It observed using.
  • S-4300 scanning electron microscope
  • Examples 1E to 18E and Comparative Examples 1E to 4E Exposure condition 5: EUV (extreme ultraviolet) exposure, alkali development)
  • Application of resist composition and post-application baking (PB) DUV44 (Brewer) a composition for forming an organic film, on a 12-inch silicon wafer Science) was applied and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm.
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition is applied onto the formed organic film, baked at 120 ° C. for 60 seconds, and an actinic ray-sensitive or radiation-sensitive film (resist having a thickness of 40 nm) Film).
  • Exposure (L / S pattern evaluation)
  • the wafer fabricated above was subjected to EUV exposure with NA (lens numerical aperture, Numerical Aperture) 0.25, dipole illumination (Dipole 60x, outer sigma 0.81, outer sigma 0.43).
  • NA latitude and space
  • Dipole illumination Dipole 60x, outer sigma 0.81, outer sigma 0.43
  • the EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a line and space pattern (L / S pattern) having a pitch of 40 nm and a width of 20 nm on the wafer. .
  • PEB Post Exposure Bake
  • TMAH tetramethyl ammonium hydroxide
  • the sensitivity is the irradiation energy when resolving a line and space pattern (L / S pattern) having a pitch of 40 nm and a width of 20 nm. The smaller this value is, the better the performance is.
  • An exposure dose that reproduces a line and space pattern (L / S pattern) with a pitch of 40 nm and a width of 20 nm is regarded as the optimal exposure dose, and a pattern size of 50 nm ⁇ 20% is acceptable when the exposure dose is changed.
  • the amount range was determined. This value was divided by the optimum exposure and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.
  • the resins V-1 to V-3 and the additive X1 used to obtain the composition for forming the upper layer film are shown below.
  • the other additives are the same as those described above.
  • the compositional ratio, weight average molecular weight and degree of dispersion of the resins V-1 to V-3 are shown in Table 10 below.
  • a resist pattern was formed by the following operation.
  • a 12-inch silicon wafer was coated with DUV44 (made by BrewerScience), which is a composition for forming an organic film, and baked at 200 ° C. for 60 seconds to form an organic film having a film thickness of 60 nm.
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition is applied onto the formed organic film, baked at 120 ° C. for 60 seconds, and an actinic ray-sensitive or radiation-sensitive film (resist having a thickness of 40 nm) Film).
  • Exposure (L / S pattern evaluation)
  • the wafer fabricated above was subjected to EUV exposure with NA (lens numerical aperture, Numerical Aperture) 0.25, dipole illumination (Dipole 60x, outer sigma 0.81, outer sigma 0.43).
  • NA latitude and space
  • Dipole illumination Dipole 60x, outer sigma 0.81, outer sigma 0.43
  • the EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a line and space pattern (L / S pattern) having a pitch of 40 nm and a width of 20 nm on the wafer. .
  • PEB Post Exposure Bake
  • the exposure amount that reproduces a line and space pattern (L / S pattern) with a pitch of 40 nm and a width of 20 nm on the wafer is made the optimum exposure amount
  • the pattern size is 50 nm ⁇ 20% when the exposure amount is changed.
  • the exposure amount width to allow for was determined. This value was divided by the optimum exposure and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

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Abstract

L'invention concerne : une composition de résine sensible aux rayons actiniques ou au rayonnement qui présente une excellente résolution, une excellente latitude d'exposition et des propriétés de forme de motif ; un film de réserve, un procédé de formation de motif, un procédé de fabrication d'un dispositif électronique, une découpe de masque équipée d'un film de réserve, et un procédé de formation de motif destiné à une découpe de masque équipée d'un film de réserve, qui utilisent ladite composition de résine sensible aux rayons actiniques ou au rayonnement. Cette composition de résine sensible aux rayons actiniques ou au rayonnement comporte : un composé qui génère un acide représenté par la formule générale spécifique (I) lorsqu'il est exposé à un rayon actinique ou à un rayonnement ; une résine.
PCT/JP2018/029765 2017-08-24 2018-08-08 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique, découpe de masque équipée d'un film de réserve, procédé de formation de motif destiné à une découpe de masque équipée d'un film de réserve WO2019039290A1 (fr)

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JP2021021773A (ja) * 2019-07-25 2021-02-18 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
WO2023085414A1 (fr) 2021-11-15 2023-05-19 日産化学株式会社 Composition de résine photodurcissable aromatique et polycyclique à base d'hydrocarbure
JP7542343B2 (ja) 2020-07-07 2024-08-30 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法

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WO2023127692A1 (fr) * 2021-12-28 2023-07-06 東京応化工業株式会社 Composition de réserve et procédé de formation de motif de réserve

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WO2013140969A1 (fr) * 2012-03-19 2013-09-26 Jsr株式会社 Composition de résine photosensible, composé et son procédé de production
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JP2017156727A (ja) * 2016-03-04 2017-09-07 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、感放射線性酸発生剤及び化合物

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WO2013140969A1 (fr) * 2012-03-19 2013-09-26 Jsr株式会社 Composition de résine photosensible, composé et son procédé de production
JP2014224984A (ja) * 2013-03-08 2014-12-04 Jsr株式会社 フォトレジスト組成物、レジストパターン形成方法、化合物及び重合体
JP2017156727A (ja) * 2016-03-04 2017-09-07 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、感放射線性酸発生剤及び化合物

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JP2021021773A (ja) * 2019-07-25 2021-02-18 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
JP7376269B2 (ja) 2019-07-25 2023-11-08 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
JP7542343B2 (ja) 2020-07-07 2024-08-30 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
WO2023085414A1 (fr) 2021-11-15 2023-05-19 日産化学株式会社 Composition de résine photodurcissable aromatique et polycyclique à base d'hydrocarbure

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