WO2017104355A1 - Composition de réserve, film de réserve, ébauche de masque, procédé de formation de motif, et procédé de fabrication de dispositif électronique - Google Patents

Composition de réserve, film de réserve, ébauche de masque, procédé de formation de motif, et procédé de fabrication de dispositif électronique Download PDF

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Publication number
WO2017104355A1
WO2017104355A1 PCT/JP2016/084490 JP2016084490W WO2017104355A1 WO 2017104355 A1 WO2017104355 A1 WO 2017104355A1 JP 2016084490 W JP2016084490 W JP 2016084490W WO 2017104355 A1 WO2017104355 A1 WO 2017104355A1
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Prior art keywords
group
repeating unit
general formula
resist composition
hydrogen atom
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PCT/JP2016/084490
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English (en)
Japanese (ja)
Inventor
暁 ▲高▼田
土村　智孝
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2017556436A priority Critical patent/JPWO2017104355A1/ja
Publication of WO2017104355A1 publication Critical patent/WO2017104355A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • 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

Definitions

  • the present invention relates to a resist composition, a resist film, a mask blank, a pattern formation method, and an electronic device manufacturing method. More specifically, the present invention relates to a resist that can be used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications.
  • the present invention relates to a composition, a resist film, a mask blank, a pattern forming method, and an electronic device manufacturing method.
  • Patent Document 1 has both a group that generates an acid upon irradiation with actinic rays or radiation and a proton acceptor group.
  • a resist composition containing a resin having a repeating unit is disclosed.
  • Patent Document 2 discloses a resist composition containing a resin having a repeating unit having an amine structure and a resin having a repeating unit having a sulfonium salt structure of sulfonic acid.
  • An object of the present invention is to provide a resist film, a mask blank, a pattern forming method, and an electronic device manufacturing method using the resist composition.
  • Amplified resist compositions usually contain a basic compound (quencher).
  • quencher basic compound
  • the basic compound is unevenly distributed in the plane of the resist film or is eluted in an immersion liquid or the like in immersion exposure, the acid capturing function in the unexposed area is lost. This lowers the dissolution contrast in the developing solution between the exposed and unexposed areas, and the pattern boundary part is partially dissolved in the developing solution, resulting in lower EL, lower LWR performance, and resolution. There has been a problem of lowering.
  • Low molecular weight compounds having an inner salt structure have been known to be excellent in LWR performance and EL improvement, but there are limitations on introduction into a resist composition from the viewpoint of aggregation and solubility.
  • the problem of aggregation and solubility has been overcome by introducing an internal salt structure into the repeating unit of the resin.
  • the quencher is uniformly distributed in the surface of the resist film, and the diffusion of the acid can be prevented.
  • the reaction in which the polar group is generated by the action of the acid hardly proceeds in the resin in the unexposed area.
  • the exposed portion or the unexposed portion is surely removed by a developer containing an alkali developer or an organic solvent, so that it is considered that the resolution is excellent. Thereby, it is thought that the pattern which is excellent in high resolution and LWR performance can be obtained.
  • the present inventors have found that the above problems can be solved by the following means.
  • a resist composition containing a resin (P) having a repeating unit (a) having an inner salt structure ⁇ 2> The resist composition according to ⁇ 1>, wherein the inner salt structure is any one of structures represented by the following general formula (U-1), (U-2), or (U-3).
  • E 1 and E 2 each represent a structure having a cation
  • G 1 and G 2 each represent a structure having an anion
  • L 0 is Represents a single bond or a linking group. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • Y 1 , Y 2 , R 101 , R 102 , R 103 and R 104 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group.
  • L 1 to L 4 , Z 1 and Z 2 each independently represents a single bond or a divalent linking group.
  • E 1 and E 2 represent a structure having a cation, and G 1 and G 2 represent a structure having an anion.
  • Y 1 , Y 2 , R 101 , R 102 , R 103 and R 104 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group.
  • L 1 to L 4 , Z 1 and Z 2 each independently represents a single bond or a divalent linking group.
  • E 1 represents a structure having a cation
  • G 1 represents a structure having an anion.
  • R 41 to R 43 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 41 and R 42 may be linked to each other to form a ring structure.
  • R 50 represents a substituent, and k represents an integer of 0 to 4. When k represents an integer of 2 or more, R 50 may be the same or different from each other.
  • E 1 is a group represented by the following (e1-1) or (e1-2), and G 1 is a group represented by any of the following (g1-1) to (g1-5)
  • R 31 to R 33 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 31 and R 32 represent They may be connected to each other to form a ring structure.
  • * Represents a linking site to the L 4.
  • Z may have a hydroxyl group as a substituent.
  • m represents an integer of 1 to 5.
  • the resin (P) has a repeating unit (c) having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid.
  • the resist composition as described.
  • the repeating unit (c) is a repeating unit represented by the following general formula (AI) or (AII).
  • Xa 1 represents a hydrogen atom or an alkyl group.
  • T represents a single bond or a divalent linking group.
  • Y represents a group capable of leaving by the action of an acid, and represents a group represented by —C (R 36 ) (R 37 ) (OR 38 ).
  • R 36 to R 38 each independently represents a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be bonded to each other to form a ring.
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
  • X 6 represents a single bond, —COO—, or —CONR 64 —.
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 6 represents a single bond or an alkylene group.
  • Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
  • Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2.
  • At least one of Y 2 represents a group capable of leaving by the action of an acid, and represents a group represented by —C (R 36 ) (R 37 ) (OR 38 ).
  • R 36 to R 38 each independently represents a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be bonded to each other to form a ring.
  • n represents an integer of 1 to 4.
  • the repeating unit (c) is a repeating unit represented by the general formula (AII), and a group that is eliminated by the action of an acid as at least one of Y 2 in the general formula (AII) is:
  • the resist composition according to ⁇ 8> which has a structure represented by the general formula (Y3-1).
  • L 10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group
  • L 20 represents a tertiary alkyl group
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
  • the repeating unit (c) is a repeating unit represented by the general formula (AII), and a group that is eliminated by the action of an acid as at least one of Y 2 in the general formula (AII) is
  • the resist composition according to ⁇ 8> which has a structure represented by the formula (Y3-2).
  • L 10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group
  • L 21 represents a secondary alkyl group
  • M represents a single bond or a divalent linking group
  • Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
  • the repeating unit (c) is a repeating unit represented by the following general formula (AI-2).
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may be bonded to each other to form a non-aromatic ring.
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
  • X 6 represents a single bond, —COO—, or —CONR 64 —.
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 6 represents a single bond or an alkylene group.
  • Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
  • n represents an integer of 1 to 4.
  • Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid, and represents a group represented by the following general formula (Y1), (Y2) or (Y4).
  • Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring.
  • the resin (P) is a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, an aryl group having 6 or more carbon atoms,
  • ⁇ 15> ⁇ 1> to ⁇ 14> A resist film formed from the resist composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 17> (A) a step of forming a resist film from the resist composition according to any one of ⁇ 1> to ⁇ 14>; (C) A pattern forming method comprising: exposing the resist film with actinic rays or radiation; and (d) developing the exposed resist film with a developer.
  • ⁇ 19> The pattern forming method according to ⁇ 17> or ⁇ 18>, wherein the developer is a step of developing with a developer containing an organic solvent to form a negative pattern.
  • the developer is a step of developing using an alkali developer to form a positive pattern.
  • ⁇ 21> ⁇ 17> A method for manufacturing an electronic device, comprising the pattern forming method according to any one of ⁇ 20>.
  • a resist composition that can form a pattern excellent in resolution and LWR performance and has a small number of particles, A resist film, a mask blank, a pattern formation method, and a method for manufacturing an electronic device using the resist composition can be provided.
  • the description which is not describing substitution and no substitution includes not only what does not have a substituent but what has 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 light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like.
  • light means actinic rays or radiation.
  • exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
  • (meth) acrylate and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
  • the molecular weight is expressed as a weight average molecular weight when having a distribution.
  • the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method.
  • HLC-8120 manufactured by Tosoh Corporation
  • TSK gel Multipore HXL-M Tosoh Corporation, 7.8 mm ID ⁇ 30.0 cm
  • THF tetrahydrofuran
  • the resist composition of the present invention is a resist composition containing a resin (P) having a repeating unit (a) having an internal salt structure.
  • the resist composition of the present invention is preferably a chemically amplified resist composition.
  • the resist composition of the present invention is preferably a resist composition for organic solvent development using a developer containing an organic solvent and / or alkali development using an alkali developer.
  • the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
  • for alkali development means at least a use provided for a step of developing using an alkali developer.
  • the resist composition of the present invention may be a positive resist composition or a negative resist composition.
  • the resist composition of the present invention is preferably used for electron beam or extreme ultraviolet exposure.
  • Resin (P) having repeating unit (a) having inner salt structure The resin (P) having the repeating unit (a) having an inner salt structure (hereinafter, also simply referred to as “resin (P)”) will be described.
  • the resin (P) has a repeating unit (a) having an inner salt structure (hereinafter, also simply referred to as “repeating unit (a)”).
  • inner salt structure hereinafter, also simply referred to as “repeating unit (a)”.
  • intramolecular salt structure refers to a structure in which at least one cation and at least one anion are linked by a covalent bond within the same molecule.
  • the intramolecular salt structure is preferably any of the structures represented by the following general formulas (U-1), (U-2), or (U-3).
  • E 1 and E 2 each represent a structure having a cation
  • G 1 and G 2 each represent a structure having an anion
  • L 0 is Represents a single bond or a linking group. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • E 1 and E 2 each represent a structure having a cation, and preferably a structure having a cation such as ammonium, phosphonium, iodonium, or sulfonium.
  • Examples of E 1 include, but are not limited to, the following groups.
  • R 31 to R 33 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 31 and R 32 are linked to each other to form a ring structure May be. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • Examples of E 2 include the following groups, but are not limited thereto.
  • R 41 to R 43 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 41 and R 42 are connected to each other to form a ring structure. May be. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • G 1 and G 2 represent a structure having an anion, and preferably represent a structure having an anion such as carboxylate, sulfonate, phosphonate, or phosphinate.
  • G 1 examples include, but are not limited to, the following groups. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • G 2 examples include the following groups, but are not limited thereto. * Represents the connecting site to the polymer main chain or side chain of the resin (P).
  • L 0 represents a single bond or a linking group, and in the case of representing a linking group, L 0 is preferably —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • a linking group selected from the group consisting of Examples of the divalent aliphatic group include an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms).
  • Examples of the divalent aromatic group include arylene groups such as a phenylene group and a xylylene group. And groups (preferably having 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms).
  • L 0 include, but are not limited to, the following linking groups.
  • linking groups may further have a substituent.
  • substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups.
  • the number of carbon atoms is preferably 30 or less (when it has a substituent, it is 30 or less including the carbon number of the substituent).
  • the resin (P) preferably has an inner salt structure at the side chain site of the polymer in the repeating unit (a) having an inner salt structure.
  • the repeating unit (a) is preferably represented by the following general formula (i) or (ii).
  • Y 1 , Y 2 , R 101 , R 102 , R 103 and R 104 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group.
  • L 1 to L 4 , Z 1 and Z 2 each independently represents a single bond or a divalent linking group.
  • E 1 and E 2 represent a structure having a cation
  • G 1 and G 2 represent a structure having an anion.
  • Y 1 and Y 2 represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and a hydrogen atom or a methyl group
  • R 101 , R 102 , R 103 and R 104 represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. More preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom.
  • the divalent aliphatic group has preferably 1 to 20, more preferably 1 to 15, and more preferably 1 to 12 carbon atoms (including the carbon number of the substituent when it has a substituent). More preferably, it is more preferably 1 to 10, and most preferably 1 to 8.
  • the divalent aliphatic group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, and an aryl group.
  • divalent aromatic group an aryl group is preferable, and a phenylene group and a naphthylene group are more preferable.
  • the divalent aromatic group may have a substituent, and examples of the substituent include an alkyl group in addition to the examples of the substituent of the divalent aliphatic group.
  • L 1 and L 3 are a single bond, or —CO—, —O—, —COO—, —NH—, —CONH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • the linking group is preferably selected from the group consisting of: a single bond, —O—, —COO—, or —CONH—.
  • Z 1 and Z 2 each represents a single bond or a divalent linking group, and the divalent linking group is the same as L 1 and L 3 described above.
  • Z 1 and Z 2 are a single bond, or —CO—, —O—, —COO—, —NH—, —CONH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. It is preferably a linking group selected from the group consisting of: a single bond, a divalent aliphatic group, or a divalent aromatic group.
  • E 1 , E 2 , G 1 and G 2 are the same as those described in the general formulas (U-1), (U-2) and (U-3).
  • L 2 and L 4 are the same as those described for L 0 in the general formulas (U-1), (U-2), and (U-3) described above.
  • the repeating unit (a) is preferably represented by the following general formula (i-1), (i-2), (i-3) or (ii-1).
  • Y 1 , Y 2 , R 101 , R 102 , R 103 and R 104 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or an organic group.
  • L 1 to L 4 , Z 1 and Z 2 each independently represents a single bond or a divalent linking group.
  • E 1 represents a structure having a cation
  • G 1 represents a structure having an anion.
  • R 41 to R 43 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 41 and R 42 may be linked to each other to form a ring structure.
  • R 50 represents a substituent, and k represents an integer of 0 to 4. When k represents an integer of 2 or more, R 50 may be the same or different from each other.
  • Y 1 , Y 2 , R 101 , R 102 , R 103 , R 104 , L 1 to L 4 , Z 1 , Z 2 , E 1 and G 1 are the same as those in general formulas (i) and (ii), respectively.
  • R 41 to R 43 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R 41 And R 42 may be connected to each other to form a ring structure.
  • the ring structure may have a hetero atom such as an oxygen atom, and is preferably a 5- to 10-membered ring, more preferably a 5- or 6-membered ring.
  • R 41 to R 43 have preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms (including carbon atoms of substituents when having a substituent). Most preferred are those having 1 to 8 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • alkenyl group examples include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group.
  • alkynyl group examples include ethynyl group, propargyl group, and trimethylsilylethynyl group.
  • Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • examples of the heterocyclic group include a furanyl group, a thiophenyl group, and a pyridinyl group.
  • substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups.
  • R 41 to R 43 from the viewpoint of effects and availability include a hydrogen atom, a methyl group, or an ethyl group.
  • R 50 in the general formula (i-2) represents a substituent.
  • substituents include a halogen atom, an alkyl group, a cycloalkyl group (including a bicycloalkyl group), an alkenyl group, a cycloalkenyl group (a bicycloalkenyl group).
  • K represents an integer of 0 to 4, preferably represents an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • the proportion of the repeating unit (a) having an inner salt structure in the resin (P) is 0.5 to 99 with respect to all repeating units constituting the resin (P) from the viewpoint of resolution and LWR performance. It is preferably in the range of mol%, more preferably in the range of 0.5 to 70 mol%, particularly preferably in the range of 1 to 50 mol%, and in the range of 1 to 30 mol%. Is most preferred.
  • repeating unit (a) containing an inner salt structure Specific examples of the repeating unit (a) containing an inner salt structure are shown below, but the present invention is not limited thereto.
  • Ph represents a phenyl group.
  • the resin (P) can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • the solvent examples include ether solvents such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And solvents for dissolving a resist composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, polymerization is performed using the same solvent as the solvent used in the resist composition. Thereby, generation
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • an inert gas atmosphere such as nitrogen or argon.
  • the polymerization initiator it is preferable to start the polymerization using a commercially available radical initiator (azo initiator, peroxide, etc.).
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
  • an initiator can be added or added in portions, and after completion of the reaction, the desired polymer can be recovered by a method such as powder or solid recovery after being charged into a solvent.
  • the concentration of the reaction is preferably 5 to 50% by mass, and more preferably 10 to 45% by mass.
  • the reaction temperature is usually preferably from 10 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C, still more preferably from 60 ° C to 100 ° C.
  • Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
  • the weight average molecular weight of the resin (P) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a polystyrene converted value by GPC method. 000.
  • the degree of dispersion is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.
  • the resin (P) may contain a repeating unit (b) having an aromatic ring group.
  • the repeating unit (b) having an aromatic ring group is preferably a repeating unit represented by the following general formula (A).
  • R 11 , R 12 and R 13 each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 12 may be bonded to L to form a ring, in which case R 12 represents a single bond or an alkylene group.
  • X represents a single bond, —COO—, or —CONR 30 —, and R 30 represents a hydrogen atom or an alkyl group.
  • L represents a single bond or an alkylene group.
  • Z represents a hydrogen atom or a (m + 1) -valent aromatic ring group, and represents a (m + 2) -valent aromatic ring group when bonded to R 12 to form a ring.
  • Z may have a hydroxyl group as a substituent.
  • m represents an integer of 1 to 5.
  • R 11 , R 12 , R 13 , X, L, and Z in the general formula (A) are R 41 , R 42 , R 43 , X 4 , L 4 , Ar in the general formula (I) described later, respectively. The same as 4 .
  • a repeating unit having a phenolic hydroxyl group can be preferably exemplified.
  • 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 of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
  • repeating unit having a phenolic hydroxyl group examples include a repeating unit represented by the following general formula (I) or (I-1).
  • R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 42 may form a ring with Ar 4, R 42 in this case represents a single bond or an alkylene group.
  • X 4 represents a single bond, —COO—, or —CONR 64 —, and R 64 represents a hydrogen atom or an alkyl group.
  • L 4 each independently represents a single bond or a divalent linking group.
  • Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
  • n represents an integer of 1 to 5.
  • n is an integer of 2 or more, or X 4 is —COO— or —CONR 64 —.
  • the alkyl groups represented by R 41 , R 42 , and R 43 are preferably a methyl group, ethyl group, propyl group, isopropyl group, n, which may have a substituent.
  • An alkyl group having 20 or less carbon atoms such as a -butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group or dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably a carbon number
  • Examples of the alkyl group are 3 or less.
  • the cycloalkyl group of R 41 , R 42 and R 43 in the general formulas (I) and (I-1) may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
  • Examples of the halogen atom of R 41, R 42, R 43 in the general formula (I) and (I-1) a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom is particularly preferred.
  • alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 and R 43 in the general formulas (I) and (I-1) the same alkyl groups as those described above for R 41 , R 42 and R 43 are preferable. .
  • Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.
  • Ar 4 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like.
  • Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
  • n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n + 1) -valent aromatic ring group may have include alkyls exemplified as R 41 , R 42 , and R 43 in formula (I). Group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group and other alkoxy groups; phenyl group and other aryl groups; and the like.
  • R 64 represents a hydrogen atom, an alkyl group
  • the alkyl group for R 64 in, preferably an optionally substituted methyl group, an ethyl group, a propyl group , An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, and the like, and an alkyl group having a carbon number of 8 or less is more preferable.
  • X 4 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
  • the divalent linking group as L 4 is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group. And those having 1 to 8 carbon atoms such as an octylene group.
  • Ar 4 an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
  • the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.
  • the repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (p1).
  • R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.
  • Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring.
  • a hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc.
  • aromatic ring heterocycles is especially, a benzene ring is most preferable.
  • M in the general formula (p1) represents an integer of 1 to 5, preferably 1.
  • a 1 or 2.
  • specific examples of the repeating unit having a phenolic hydroxyl group specific examples described in JP-A-2014-232309, [0177] to [0178] can be used, and the contents thereof are incorporated in the present specification.
  • the resin (P) may have one or more repeating units having a phenolic hydroxyl group.
  • the content of the repeating unit having a phenolic hydroxyl group is preferably 10 to 95 mol% with respect to all the repeating units of the resin (P). 20 to 90 mol% is more preferable, and 30 to 85 mol% is still more preferable.
  • the repeating unit (b) having an aromatic ring group may be a repeating unit represented by the following general formula (X).
  • R 7 each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (—OCOR or —COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. n represents an integer of 0 or more.
  • General formula (X) is also preferably a repeating unit represented by the following general formula (V) or the following general formula (VI).
  • n 3 represents an integer of 0 to 4.
  • n 4 represents an integer of 0 to 6.
  • X 4 is a methylene group, an oxygen atom or a sulfur atom.
  • R 7 has the same meaning as R 7 in the general formula (X).
  • repeating unit represented by the general formula (X) are shown below, but are not limited thereto.
  • the resin (P) may have one or more repeating units represented by the general formula (X).
  • the content of the repeating unit represented by the general formula (X) is 5 to 5 with respect to all the repeating units of the resin (P).
  • the amount is preferably 50 mol%, more preferably 5 to 40 mol%, still more preferably 5 to 30 mol%.
  • the resin (P) may have one or more repeating units (b) having an aromatic ring group.
  • the content of the repeating unit (b) having an aromatic ring group is 5 to 100 mol relative to all the repeating units of the resin (P). %, More preferably 7 to 98 mol%, still more preferably 8 to 96 mol%.
  • the resin (P) has a repeating unit (c) having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid.
  • the polar group in the repeating unit (c) having a structure (acid-decomposable group) protected by a leaving group that decomposes and leaves by the action of an acid includes a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, And a sulfonic acid group etc. are mentioned.
  • the polar group is preferably a carboxyl group, an alcoholic hydroxyl group, or a phenolic hydroxyl group, and more preferably a carboxyl group or a phenolic hydroxyl group.
  • the resin (P) has a repeating unit having an acid-decomposable group, the solubility in an alkali developer increases due to the action of an acid, and the solubility in an organic solvent decreases.
  • Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by the following general formulas (Y1) to (Y4).
  • Formula (Y1) —C (Rx 1 ) (Rx 2 ) (Rx 3 )
  • Formula (Y2) —C ( ⁇ O) O (Rx 1 ) (Rx 2 ) (Rx 3 )
  • Formula (Y3) —C (R 36 ) (R 37 ) (OR 38 )
  • Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. More preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear or branched alkyl group, and more preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear alkyl group. Unit. Two of Rx 1 to Rx 3 may combine to form a monocycle or polycycle.
  • the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
  • Examples of the cycloalkyl group formed by combining two 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
  • a monocyclic cycloalkyl group such as a group is preferred.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
  • Repeating unit represented by formula (Y1), (Y2) is, for example, Rx 1 is a methyl group or an ethyl group, by bonding and Rx 2 and Rx 3 form a cycloalkyl radical as defined above Embodiments are preferred.
  • R 36 to R 38 each independently represents a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be bonded to each other to form a ring.
  • the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
  • R 36 is preferably a hydrogen atom.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
  • At least one of L 1 and L 2 is a hydrogen atom, and at least one is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
  • L 2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
  • Examples of the secondary alkyl group include isopropyl group, cyclohexyl group, norbornyl group, and examples of the tertiary alkyl group include tert-butyl group and adamantane.
  • Tg and activation energy become high, in addition to ensuring the film strength, fogging can be suppressed.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may be bonded to each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • Xa 1 represents a hydrogen atom or an alkyl group.
  • T represents a single bond or a divalent linking group.
  • Y represents a group capable of leaving by the action of an acid.
  • Y is preferably any one of the aforementioned general formulas (Y1) to (Y4).
  • the alkyl group represented by Xa 1 may be an alkyl group having a substituent, and examples thereof include a methyl group or a group represented by —CH 2 —R 11 .
  • R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group.
  • Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
  • Examples of the divalent linking group for T include an alkylene group, an arylene group, a —COO—Rt— group, a —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
  • X 6 represents a single bond, —COO—, or —CONR 64 —.
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 6 represents a single bond or an alkylene group.
  • Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
  • Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
  • the group capable of leaving by the action of an acid as Y 2 is preferably any one of the aforementioned general formulas (Y1) to (Y4).
  • n represents an integer of 1 to 4.
  • Each of the above groups may have a substituent.
  • substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group.
  • substituents include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
  • the repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit).
  • the repeating unit represented by the general formula (AII) is preferably a repeating unit represented by the following general formula (AIII).
  • Ar 3 represents an aromatic ring group.
  • Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
  • the group capable of leaving by the action of an acid as Y 2 is preferably any one of the aforementioned general formulas (Y1) to (Y4).
  • n represents an integer of 1 to 4.
  • the aromatic ring group represented by Ar 6 and Ar 3 is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
  • Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Rxa and Rxb each 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 them, each is independent.
  • p represents 0 or a positive integer.
  • Examples of 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. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable. Further, as specific examples of the repeating unit (c), [0227] to [0233], [0270] to [0272] of JP2014-232309A, [0123] to [0131] of JP2012-208447A. Can be incorporated by reference, the contents of which are incorporated herein.
  • the repeating unit (c) having an acid-decomposable group may be one type, or two or more types may be used in combination. Good.
  • the content of the repeating unit (c) having an acid-decomposable group in the resin (P) (when plural types are contained, the sum thereof) is , Preferably from 5 mol% to 80 mol%, more preferably from 5 mol% to 75 mol%, more preferably from 10 mol% to 65 mol%, based on all repeating units in the resin (P). More preferably.
  • the repeating unit having an acid-decomposable group and an aromatic ring group applies to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.
  • the resin (P) may contain a repeating unit having a lactone group or a sultone (cyclic sulfonate ester) group.
  • the lactone group or sultone group any group can be used as long as it contains a lactone structure or sultone structure, but a group containing a 5- to 7-membered lactone structure or sultone structure is preferable.
  • Those in which other ring structures are condensed in a form forming a bicyclo structure or a spiro structure in a 7-membered lactone structure or a sultone structure are preferred.
  • Preferred lactone structures or sultone structures include groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14) It is.
  • the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like.
  • n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to form a ring.
  • repeating unit Having a lactone structure represented by any one of general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any one of general formulas (SL1-1) to (SL1-3)
  • Examples of the repeating unit include a repeating unit represented by the following general formula (BI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  • substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
  • the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express. Preferably, it is a single bond or a linking group represented by —Ab 1 —CO 2 —.
  • Ab 1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
  • V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3).
  • 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.
  • the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
  • repeating unit having a lactone group or a sultone group are given below, but the present invention is not limited thereto.
  • the content of the repeating unit having a lactone group or a sultone group is 1 to 30 mol% with respect to all the repeating units in the resin (P). More preferably, it is 5 to 25 mol%, still more preferably 5 to 20 mol%.
  • the resin (P) may have a repeating unit having a silicon atom in the side chain.
  • the repeating unit having a silicon atom in the side chain is not particularly limited as long as it has a silicon atom in the side chain. Examples thereof include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom. It is done.
  • the repeating unit having a silicon atom is preferably a repeating unit having no structure (acid-decomposable group) protected by a leaving group that is decomposed and eliminated by the action of an acid.
  • the repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain.
  • Examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, and triphenyl.
  • Silyl group tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, or cyclic or Examples include linear polysiloxanes, cage-type, ladder-type or random-type silsesquioxane structures.
  • R and R 1 each independently represents a monovalent substituent. * Represents a bond.
  • repeating unit having the above group for example, a repeating unit derived from an acrylate or methacrylate compound having the above group or a repeating unit derived from a compound having the above group and a vinyl group can be preferably exemplified.
  • the repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, whereby it is ultrafine (for example, a line width of 50 nm or less), and the cross-sectional shape has a high aspect ratio (for example, In the formation of a pattern having a film thickness / line width of 2 or more, a very excellent collapse performance can be exhibited.
  • the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), a random-type silsesquioxane structure, and the like.
  • a cage-type silsesquioxane structure is preferable.
  • the cage silsesquioxane structure is a silsesquioxane structure having a cage structure.
  • the cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure.
  • the ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.
  • the random silsesquioxane structure is a silsesquioxane structure having a random skeleton.
  • the cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).
  • R represents a monovalent substituent.
  • a plurality of R may be the same or different.
  • the monovalent substituent is not particularly limited, and specific examples thereof include a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, blocked with an acyl group ( Protected) mercapto group), acyl group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, hydrocarbon group optionally having hetero atoms, (meth) acryl group-containing group and epoxy group-containing Group and the like.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.
  • hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
  • hydrocarbon group of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which these are combined.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • aliphatic hydrocarbon group examples include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly 2 to 30 carbon atoms).
  • aromatic hydrocarbon group examples include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • the repeating unit having a silicon atom is preferably represented by the following formula (I).
  • L represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • L is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
  • X represents a hydrogen atom or an organic group.
  • the alkyl group which may have substituents such as a fluorine atom and a hydroxyl group
  • a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group are preferable.
  • A represents a silicon atom-containing group. Of these, a group represented by the following formula (a) or (b) is preferable.
  • R represents a monovalent substituent.
  • a plurality of R may be the same or different. Specific examples and preferred embodiments of R are the same as those in the above formula (S).
  • a in the formula (I) is a group represented by the formula (a)
  • the formula (I) is represented by the following formula (Ia).
  • R b represents a hydrocarbon group which may have a hetero atom.
  • Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as R in the above-described formula (S).
  • the resin (P) may have one or more repeating units having a silicon atom.
  • the content of the repeating unit having a silicon atom is preferably 1 to 30 mol% with respect to all the repeating units of the resin (P). It is more preferably ⁇ 20 mol%, further preferably 1-10 mol%.
  • the repeating unit having a silicon atom and a structure (acid-decomposable group) protected by a leaving group in which a polar group is decomposed and eliminated by the action of an acid is a repeating unit having a silicon atom.
  • the resin (P) may have other repeating units other than those described above.
  • a repeating unit containing an organic group having a polar group particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group may be further included. This improves the substrate adhesion and developer compatibility.
  • the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
  • the polar group is preferably a hydroxyl group or a cyano group. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.
  • the content thereof is preferably 1 to 30 mol%, more preferably 5%, based on all repeating units in the resin (P). It is ⁇ 25 mol%, more preferably 5 to 20 mol%.
  • resin (P) can also contain the repeating unit which has the group (photo-acid generating group) which generate
  • the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
  • Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
  • R 41 represents a hydrogen atom or a methyl group.
  • L 41 represents a single bond or a divalent linking group.
  • L 42 represents a divalent linking group.
  • W represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
  • examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs [0094] to [0105] of JP-A No. 2014-041327.
  • the content of the repeating unit having a photoacid generating group is preferably 1 to 40 mol% with respect to all the repeating units in the resin (P). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
  • Resin (P) is a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, an aryl group having 6 or more carbon atoms, and And a repeating unit having one or more groups selected from the group consisting of aralkyl groups having 7 or more carbon atoms.
  • the resin (P) has the above repeating unit, it can be used as a hydrophobic resin described later in the resist composition.
  • the resin (P) As a hydrophobic resin, the resin (P) having a function as a quencher is unevenly distributed on the resist film surface, so that the film loss (top loss) is improved in the positive pattern forming method.
  • the head tension (T-top shape) can be improved.
  • the resin (P) may be used as a resin (main polymer) contained in an amount of 50% by mass or more based on the total solid content of the resist composition, or for uses other than the main polymer (for example, described later). Hydrophobic resin or basic compound).
  • the resin (P) may be used alone or in combination.
  • the content of the resin (P) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the resist composition.
  • the resist composition preferably contains a compound (also referred to as “compound (B)”, “photoacid generator”, or “PAG (Photo Acid Generator)”) that generates an acid by actinic rays or radiation.
  • the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
  • the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the photoacid generator When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (P) contained in the resist composition, or in a resin different from the resin (P). May be.
  • the number of fluorine atoms contained in the acid generator is appropriately adjusted. By adjusting the fluorine atoms, it is possible to control the surface uneven distribution of the acid generator in the resist film. The more fluorine atoms the acid generator has, the more uneven it is on the surface.
  • the photoacid generator is preferably in the form of a low molecular compound.
  • the photoacid generator is not particularly limited, but an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or tris (alkylsulfonyl) methide by irradiation with active light or radiation, preferably electron beam or extreme ultraviolet light.
  • More preferable examples of the photoacid generator include compounds represented by the following general formula (ZI), (ZII), or (ZIII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z ⁇ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
  • Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
  • the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
  • the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
  • an alkylthio group preferably having 1 to 15 carbon atoms
  • an alkylsulfonyl group preferably having 1 to 15 carbon atoms
  • an alkyliminosulfonyl group preferably having 1 to 15 carbon atoms
  • an aryloxysulfonyl group preferably having carbon atoms Number 6 to 20
  • alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
  • cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
  • examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
  • aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
  • the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), fluorinated antimony (eg, SbF 6 ⁇ ), and the like. .
  • non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
  • the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
  • an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 may be mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
  • the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
  • R 1 and R 2 are preferably a fluorine atom or CF 3 .
  • x is preferably from 1 to 10, and more preferably from 1 to 5.
  • y is preferably 0 to 4, more preferably 0.
  • z is preferably 0 to 5, and more preferably 0 to 3.
  • the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
  • —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
  • the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
  • a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
  • an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step.
  • the diffusion property can be suppressed, which is preferable from the viewpoint of improving MEEF (Mask Error Enhancement Factor).
  • Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
  • Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
  • examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the general formulas (LC1-1) to (LC1-17).
  • the cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
  • the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
  • Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
  • aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
  • Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a straight-chain or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • These groups may further have a substituent.
  • substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
  • anion represented by the general formula (AN1) include the following.
  • A represents a cyclic organic group. SO 3 —CF 2 —CH 2 —OCO-A, SO 3 —CF 2 —CHF—CH 2 —OCO—A, SO 3 —CF 2 —COO—A, SO 3 —CF 2 —CF 2 —CH 2 — A, SO 3 —CF 2 —CH (CF 3 ) —OCO-A
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the compound (ZI).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the compound (ZI) may have.
  • Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
  • the photoacid generator has a volume of 130 to 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. It is preferably a compound that generates an acid having a size (more preferably sulfonic acid), more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid), and a volume of 270%.
  • the size of the acid (more preferably sulfonic acid) is a compound which generates an, especially the (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an preferable.
  • the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
  • the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
  • a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the photoacid generator in the resist composition is preferably from 0.1 to 50% by mass, more preferably from 5 to 50% by mass, and still more preferably from 8 to 40%, based on the total solid content of the resist composition. % By mass.
  • the content of the photoacid generator is more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass in order to achieve both high sensitivity and high resolution upon exposure to electron beams and extreme ultraviolet rays. It is.
  • a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the resist composition preferably contains a solvent (also referred to as “resist solvent”).
  • the solvent may contain isomers (compounds having the same number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.
  • the solvent is a group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one of at least one selected from more is included.
  • the solvent may further contain components other than the components (M1) and (M2).
  • Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate is particularly preferable.
  • the component (M2) the following are preferable.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
  • lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
  • acetate ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.
  • butyl butyrate is also preferred.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl.
  • Ketones acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
  • cyclic ketone methylcyclohexanone, isophorone, or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone is preferable.
  • alkylene carbonate propylene carbonate is preferable.
  • Component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone or propylene carbonate.
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
  • ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and isoamyl acetate is particularly preferable.
  • component (M2) one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used.
  • component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
  • flash point means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.
  • the solvent preferably contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).
  • the mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.
  • mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.
  • the solvent may further contain components other than the components (M1) and (M2).
  • the content of components other than components (M1) and (M2) is preferably in the range of 5 to 30% by mass with respect to the total amount of the solvent.
  • the content of the solvent in the resist composition is preferably determined so that the solid content concentration of all components is 1 to 40% by mass, more preferably 1 to 30% by mass. More preferably, it is determined to be mass%. If it carries out like this, the applicability
  • the solid content concentration of the resist composition can be adjusted as appropriate for the purpose of adjusting the thickness of the resist film to be prepared.
  • the resist composition may contain a crosslinking agent.
  • the crosslinking agent typically refers to a compound that reacts with a resin by the action of an acid to form a crosslinked structure.
  • a crosslinking agent a compound having two or more crosslinkable groups in the molecule is preferable, and a methylol-based crosslinking agent (a crosslinking agent having at least one of a methylol group (hydroxymethyl group) and an alkoxymethyl group), an epoxy-based crosslinking agent.
  • Crosslinking agent having an epoxy group oxetane-based crosslinking agent (crosslinking agent having an oxetanyl group), isocyanate-based crosslinking agent (crosslinking agent having an isocyanate group) and the like, and a methylol-based crosslinking agent and an epoxy-based crosslinking agent are preferable. More preferred is a methylol-based crosslinking agent, a crosslinking agent having two or more methylol groups, a crosslinking agent having two or more alkoxymethyl groups, or a crosslinking having one or more methylol groups and one or more alkoxymethyl groups. More preferably, it is an agent.
  • the crosslinking agent may be a low molecular compound or a polymer compound (for example, a compound in which a crosslinking group is supported on the polymer compound, a compound having a repeating unit having a crosslinking group, etc.).
  • the crosslinking agent is a low molecule, the molecular weight is preferably from 100 to 1,000, more preferably from 200 to 900, most preferably from 300 to 800.
  • Preferred examples of the crosslinking agent include hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine compounds, alkoxymethyl glycoluril compounds, and alkoxymethylated urea compounds.
  • Particularly preferred crosslinking agents include phenol derivatives and alkoxymethylglycoluril derivatives containing 3 to 5 benzene rings in the molecule and having two or more hydroxymethyl groups or alkoxymethyl groups, and having a molecular weight of 1200 or less. Can be mentioned.
  • alkoxymethyl group a methoxymethyl group and an ethoxymethyl group are preferable.
  • a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound not having a hydroxymethyl group with formaldehyde under a base catalyst.
  • a phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.
  • Examples of another preferable crosslinking agent further include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group, such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds. be able to.
  • Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like.
  • 133, 216A West German Patent 3,634,671, 3,711,264, EP 0,212,482A.
  • crosslinking agent those particularly preferred are listed below.
  • L 1 to L 8 each 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 crosslinking agent is preferably a compound represented by the following general formula (CI).
  • R 1 and R 6 each independently represents a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.
  • R 2 and R 5 each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.
  • R 3 and R 4 each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R 3 and R 4 may combine with each other to form a ring.
  • R 1 and R 6 are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, and particularly preferably a methyl group, an ethyl group, Examples include a propyl group and an isopropyl group.
  • R 2 and R 5 for example, an alkyl group having 1 to 6 carbon atoms is preferable, and as a cycloalkyl group, for example, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and as an aryl group, For example, an aryl group having 6 to 12 carbon atoms is preferred, and an acyl group having, for example, an alkyl moiety having 1 to 6 carbon atoms is preferred.
  • R 2 and R 5 are preferably alkyl groups, more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.
  • Examples of the organic group having 2 or more carbon atoms represented by R 3 and R 4 include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, and an aryl group, and R 3 and R 4 are bonded to each other. It is preferable to form the ring described in detail below.
  • Examples of the ring formed by combining R 3 and R 4 with each other include, for example, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a combination of two or more of these rings
  • the polycyclic fused ring formed can be mentioned.
  • These rings may have a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, and an alkoxycarbonyl group. , A nitro group, a halogen, or a hydroxy group.
  • R 3 and R 4 in the general formula (CI) are bonded to form a polycyclic condensed ring including a benzene ring, and more preferably that a fluorene structure is formed.
  • the cross-linking agent preferably has, for example, R 3 and R 4 in the general formula (CI) bonded to form a fluorene structure represented by the following general formula (Ia).
  • R 7 and R 8 each independently represents a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen, and a hydroxy group.
  • n1 and n2 each independently represents an integer of 0 to 4, preferably 0 or 1. * Represents a linking site with a phenol nucleus.
  • the crosslinking agent is preferably represented by the following general formula (Ib).
  • R 1b and R 6b each independently represents an alkyl group having 5 or less carbon atoms.
  • R 2b and R 5b each independently represents an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.
  • Z represents an atomic group necessary for forming a ring together with the carbon atom in the formula. The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring formed by combining R 3 and R 4 with each other in the description of the general formula (CI).
  • the crosslinking agent is preferably a compound having a total of two or more aromatic rings and two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.
  • a bisphenol compound serving as a mother core of a crosslinking agent represented by the general formula (CI) is obtained by subjecting two corresponding phenol compounds and one corresponding ketone to a dehydration condensation reaction in the presence of an acid catalyst. Synthesized.
  • the obtained bisphenol compound is treated with paraformaldehyde and dimethylamine and aminomethylated to obtain an intermediate represented by the following general formula (IC). Subsequently, the target acid crosslinking agent is obtained through acetylation, deacetylation, and alkylation.
  • R ⁇ 1 >, R ⁇ 3 >, R ⁇ 4 > and R ⁇ 6 > are synonymous with each group in general formula (CI).
  • This synthesis method has an effect of inhibiting particle formation because it is difficult to produce an oligomer as compared with a synthesis method via a hydroxymethyl compound under a basic condition (for example, JP 2008-273844 A).
  • a basic condition for example, JP 2008-273844 A.
  • Specific examples of the crosslinking agent are shown below.
  • the crosslinking agent may be used alone or in combination of two or more. From the viewpoint of a good pattern shape, it is preferable to use a combination of two or more.
  • the content of the crosslinking agent is preferably 0.1 to 40% by mass, and preferably 1 to 35% by mass with respect to the total solid content of the resist composition. More preferred is 5 to 30% by mass.
  • the resist composition preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
  • Preferred examples of the basic compound include compounds having structures represented by the following general formulas (E-1) to (E-5).
  • the above-mentioned resin (P) can also be used as a basic compound.
  • R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 carbon atoms). To 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R 201 and R 202 may be bonded to each other to form a ring.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (E-1) and (E-5) are more preferably unsubstituted.
  • Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
  • Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. And undeca-7-ene.
  • Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium.
  • Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
  • the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
  • 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 derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
  • aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
  • Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
  • amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
  • 6 to 12 carbon atoms may be bonded to the nitrogen atom.
  • the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • 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 oxyalkylene group Ethylene group.
  • ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
  • the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, 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 oxyalkylene group Ethylene group.
  • the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
  • the halogen atom is particularly preferably chloride, bromide or iodide
  • the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
  • the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
  • 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.
  • the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like.
  • the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
  • An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
  • the phenoxy group may have a substituent.
  • the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
  • the substitution position of the substituent may be any of the 2-6 positions.
  • the number of substituents may be any in the range of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups is one or more in the molecule, 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 oxyalkylene group Ethylene group.
  • the amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, 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 is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.
  • the actinic ray-sensitive or radiation-sensitive resin composition has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or It may further contain a compound that generates a compound that has been changed from proton acceptor property to acidity (hereinafter also referred to as compound (PA)).
  • the proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron.
  • a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
  • Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
  • the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
  • the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
  • a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
  • Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.
  • the content of the basic compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the solid content of the resist composition.
  • the photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
  • the resist composition may contain a hydrophobic resin.
  • the hydrophobic resin may contain a hydrophobic resin different from the resin (P), or the resin (P) may be used as the hydrophobic resin.
  • a resin similar to the resin preferably contained in the upper layer forming composition can also be used.
  • the hydrophobic resin is preferably designed to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film.
  • the hydrophobic resin does not necessarily have a hydrophilic group in the molecule and is polar / non-polar. It is not necessary to contribute to mixing the polar substance uniformly. Examples of the effect of adding the hydrophobic resin include control of static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film surface with respect to water, suppression of outgassing, and the like.
  • the hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types.
  • the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the hydrophobic resin or may be substituted on the side chain.
  • the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.
  • the hydrophobic resin when it contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
  • the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
  • the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
  • Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.
  • the hydrophobic resin preferably includes a CH 3 partial structure in the side chain portion.
  • the CH 3 partial structure contained in the side chain portion of the hydrophobic resin is intended to encompass CH 3 partial structure an ethyl group, and a propyl group having.
  • methyl groups directly bonded to the main chain of the hydrophobic resin (for example, ⁇ -methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH 3 partial structure in the present invention.
  • hydrophobic resin those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
  • hydrophobic resin a resin having the following structure can also be used.
  • the content of the hydrophobic resin is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass with respect to the total solid content of the resist composition. More preferably.
  • the resist composition may further contain a surfactant.
  • a surfactant By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
  • the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
  • F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or
  • the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and still more preferably 0.0005 to 1% by mass, based on the total solid content of the resist composition. .
  • the resist composition contains a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or a carboxy group). It may further contain an alicyclic or aliphatic compound).
  • the resist composition may further contain a dissolution inhibiting compound.
  • the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.
  • the resist composition may contain (G) a carboxylic acid onium salt.
  • the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt.
  • the (G) carboxylic acid onium salt is preferably an iodonium salt or a sulfonium salt.
  • the carboxylate residue of the (G) carboxylic acid onium salt does not contain an aromatic group or a carbon-carbon double bond.
  • a particularly preferred anion moiety is a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable.
  • the alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.
  • Fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , Anions of 2-bistrifluoromethylpropionic acid, and the like.
  • (G) carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.
  • the content of (G) carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably based on the total solid content of the resist composition. 1 to 7% by mass.
  • the present invention also relates to a resist film formed from the resist composition of the present invention.
  • a resist film formed from the resist composition of the present invention.
  • 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, and still more preferably 0.03 ⁇ m or less.
  • the resist composition is applied on a substrate (eg, silicon, silicon dioxide coating) used in the manufacture of precision integrated circuit elements.
  • a substrate eg, silicon, silicon dioxide coating
  • the resist composition on the substrate it is applied on the substrate by an appropriate application method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., but spin coating is preferable,
  • the rotation speed is preferably 1000 to 3000 rpm.
  • various base films inorganic films, organic films, antireflection films
  • a method of drying by heating is generally used. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
  • the heating temperature is not particularly limited, but is preferably 60 to 150 ° C. for 1 to 20 minutes, more preferably 80 to 120 ° C. for 1 to 15 minutes.
  • the thickness of the resist film is preferably 0.02 to 0.5 ⁇ m, more preferably 0.02 to 0.3 ⁇ m, even more preferably 0.02 to 0.2 ⁇ m.
  • the thickness of the resist film is a resist such as dry etching resistance. It can adjust suitably for the purpose of adjusting various performances. For the purpose of improving the dry etching resistance, a higher film thickness is preferable, and 0.05 to 0.3 ⁇ m is also preferable.
  • the pattern forming method of the present invention comprises: (A) a step of forming a resist film from the resist composition; Preferably, the pattern forming method includes: (c) a step of exposing the resist film with actinic rays or radiation; and (d) a step of developing the exposed resist film with a developer.
  • the resist composition of the present invention described above is used as the resist composition. Also, between steps (a) and (c), (B) a step of forming an upper layer film on the resist film with the composition for forming an upper layer film, You may have.
  • Step (a) of the pattern forming method of the present invention is a step of forming a resist film with a resist composition, and preferably a step of forming a resist film by applying the resist composition on a substrate.
  • Step (b) of the pattern forming method of the present invention is a step of forming an upper layer film on the resist film with the upper layer film forming composition.
  • a composition for forming an upper layer film also referred to as a “topcoat composition” is applied on the resist film formed in the step (a), and then heated (pre-baking (PB; It is preferable to form an upper layer film (also referred to as “top coat”) by performing Prebake)).
  • composition for forming upper layer film The composition for forming an upper layer film used in the pattern forming method of the present invention will be described. It is preferable that the top coat is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
  • the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method.
  • the topcoat can be formed based on the description in paragraphs 0072 to 0082 of JP-A No. 2014-059543.
  • the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond.
  • the top coat preferably contains a resin.
  • the resin that can be contained in the topcoat is not particularly limited, and the same resins as the hydrophobic resin that can be included in the resist composition described above can be used.
  • the hydrophobic resin [0017] to [0023] of JP2013-61647A (corresponding [0017] to [0023] of US Patent Publication No. 2013/244438) and JP2014-56194A. [0016] to [0165] can be referred to, the contents of which are incorporated herein.
  • the top coat preferably contains a resin containing a repeating unit having an aromatic ring.
  • the resin By containing a repeating unit having an aromatic ring, the generation efficiency of secondary electrons and the efficiency of acid generation from a compound that generates an acid by actinic rays or radiation, particularly during electron beam or EUV exposure, is increased. High sensitivity and high resolution can be expected during formation.
  • the resin When used in ArF immersion exposure, the resin preferably has substantially no aromatic group from the viewpoint of transparency to ArF light.
  • the weight average molecular weight of the resin is preferably 3000 to 100,000, more preferably 3000 to 30000, and most preferably 5000 to 20000.
  • the amount of the resin in the composition for forming a top coat is preferably 50 to 99.9% by mass, more preferably 70 to 99.7% by mass, and still more preferably 80 to 99.5% by mass in the total solid content. .
  • the top coat contains a plurality of resins
  • the topcoat composition contains at least one resin (XA) having a fluorine atom and / or silicon atom, and a resin (XB) having a fluorine atom and / or silicon atom content smaller than that of the resin (XA). More preferred. Thereby, when the topcoat film is formed, the resin (XA) is unevenly distributed on the surface of the topcoat film, so that performance such as development characteristics and immersion liquid followability can be improved.
  • the content of the resin (XA) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.1 to 8% by mass, based on the total solid content contained in the topcoat composition. % Is more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the content of the resin (XB) is preferably 50.0 to 99.9% by mass, more preferably 60 to 99.9% by mass, based on the total solid content in the topcoat composition, and 70 to 99.99%. 9% by mass is more preferable, and 80 to 99.9% by mass is particularly preferable.
  • the preferred range of fluorine atoms contained in the resin (XA) is preferably 5 to 80% by mass, and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the resin (XA).
  • the preferable range of the silicon atoms contained in the resin (XA) is preferably 2 to 50% by mass, more preferably 2 to 30% by mass with respect to the weight average molecular weight of the resin (XA).
  • the resin (XB) a form that substantially does not contain a fluorine atom and a silicon atom is preferable.
  • the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom is, It is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, ideally with respect to all repeating units in the resin (XB). Is 0 mol%, that is, does not contain fluorine atoms or silicon atoms.
  • the compounding amount of the resin in the entire topcoat composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
  • the top coat may contain an acid generator and a crosslinking agent. Specific examples and preferred examples of these components are as described above.
  • the top coat is typically formed from a composition for forming a top coat. It is preferable that the composition for forming a top coat is dissolved in a solvent and filtered.
  • 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, and still more preferably 0.03 ⁇ m or less. Note that a plurality of types of filters may be connected in series or in parallel.
  • the composition may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.
  • the topcoat-forming composition of the present invention preferably contains no impurities such as metals.
  • the content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably (not more than the detection limit of the measuring device). .
  • the top coat is disposed between the resist film and the immersion liquid, and also functions as a layer that does not directly contact the resist film with the immersion liquid.
  • preferable properties of the topcoat include suitability for application to a resist film, transparency to radiation, particularly 193 nm, and poor solubility in an immersion liquid (preferably water).
  • the top coat is not mixed with the resist film and can be uniformly applied to the surface of the resist film.
  • the topcoat-forming composition preferably contains a solvent that does not dissolve the resist film. .
  • the solvent that does not dissolve the resist film it is more preferable to use a solvent having a component different from the developer containing the organic solvent (organic developer).
  • the application method of the composition for forming a top coat is not particularly limited, and a conventionally known spin coat method, spray method, roller coat method, dipping method, or the like can be used.
  • the thickness of the top coat is not particularly limited, but is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and still more preferably 30 nm to 100 nm from the viewpoint of transparency to the exposure light source. .
  • the substrate is heated (PB) as necessary.
  • the refractive index of the top coat is preferably close to the refractive index of the resist film from the viewpoint of resolution.
  • the top coat is preferably insoluble in the immersion liquid, and more preferably insoluble in water.
  • the receding contact angle of the top coat is preferably 50 to 100 degrees, and preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability. More preferred.
  • the top coat in a dynamic state is necessary because the immersion liquid needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed and form an exposure pattern.
  • an organic developer may be used, or a separate release agent may be used.
  • a solvent having a small penetration into the resist film is preferable.
  • the top coat is preferably peelable by an organic developer.
  • the organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the resist film.
  • the topcoat preferably has a dissolution rate in the organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
  • the dissolution rate of the top coat with respect to the organic developer is a film thickness reduction rate when the top coat is formed and then exposed to the developer.
  • the top coat was immersed in butyl acetate at 23 ° C. Speed.
  • the line edge roughness of the pattern after developing the resist film is likely to be better due to the effect of reducing the exposure unevenness during immersion exposure. effective.
  • the top coat may be removed using another known developer, for example, an alkaline aqueous solution.
  • an alkaline aqueous solution Specific examples of the aqueous alkali solution that can be used include an aqueous solution of tetramethylammonium hydroxide.
  • the pre-wet solvent is not particularly limited as long as it has low solubility in the actinic ray-sensitive or radiation-sensitive film, but it is not limited to alcohol solvents, fluorine solvents, ether solvents, hydrocarbon solvents, ester solvents.
  • a pre-wet solvent for the upper layer film containing one or more compounds selected from can be used.
  • solvents may be used singly or in combination.
  • a solvent other than the above the solubility in the resist film, the solubility of the resin in the composition for forming the upper layer film, the elution characteristics from the resist film, and the like can be appropriately adjusted.
  • Step (c) of the pattern forming method of the present invention is a step of exposing the resist film, and can be performed, for example, by the following method.
  • the resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common. Although it does not specifically limit as actinic light or radiation, For example, it is KrF excimer laser, ArF excimer laser, extreme ultraviolet light (EUV light, Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc., especially extreme ultraviolet rays or an electron beam preferable.
  • the exposure may be immersion exposure.
  • baking is preferably performed after exposure and before development.
  • the reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
  • the heating temperature is not particularly limited as long as a good pattern is obtained, and is usually 40 ° C. to 160 ° C.
  • the number of times PEB is performed may be one time or a plurality of times.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
  • Step (d) of the pattern forming method of the present invention is a step of developing the exposed resist film with a developer containing an organic solvent.
  • the developer used in the developing step (d) is preferably an alkali developer or a developer containing an organic solvent.
  • a developer containing an organic solvent can also be referred to as an organic developer.
  • alkali developer examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such
  • an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
  • the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • the pH of the alkali developer is usually from 10.0 to 15.0.
  • a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is particularly desirable.
  • the vapor pressure of the organic solvent (the vapor pressure as a whole in the case of a mixed solvent) is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • the vapor pressure of the organic solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • An ester solvent is a solvent having an ester bond in the molecule
  • a ketone solvent is a solvent having a ketone group in the molecule
  • an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule.
  • An amide solvent is a solvent having an amide group in the molecule
  • an ether solvent is a solvent having an ether bond in the molecule.
  • diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification.
  • the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
  • an organic developer containing at least one solvent selected from an ester solvent, a ketone solvent, an ether solvent, and a hydrocarbon solvent is preferable, and an organic developer containing an ester solvent is preferable. More preferably, it is a liquid.
  • ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, butyl butyrate, methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2- Acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether a
  • butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl butanoate are preferably used, and isoamyl acetate is particularly preferable. Preferably used.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, ⁇ -butyrolactone, etc. Heptanone is preferred.
  • alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl- -Pentanol, 4-methyl-3-pentanol,
  • ether solvents include hydroxyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether in addition to glycol ether solvents that contain hydroxyl groups.
  • Glycol ether solvents aromatic ether solvents such as anisole and phenetole, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.
  • cycloaliphatic ether solvents having a branched alkyl group such as cyclopentyl isopropyl ether, cyclopentyl sec-butyl ether, cyclopentyl tert-butyl ether, cyclohexyl isopropyl ether, cyclohexyl sec-butyl ether, cyclohexyl tert-butyl ether, and di-n-propyl
  • Acyclic aliphatic ether solvents having a linear alkyl group such as ether, di-n-butyl ether, di-n-pentyl ether, di-n-hexyl ether, diisohexyl ether, methyl isopentyl ether, ethyl Isopentyl ether, propyl isopentyl ether, diisopentyl ether, methyl isobutyl ether, ethyl isobutyl group
  • an acyclic aliphatic ether solvent having 8 to 12 carbon atoms is preferable from the viewpoint of in-plane uniformity of the wafer, and more preferably, an acyclic fatty acid having a branched alkyl group having 8 to 12 carbon atoms.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
  • hydrocarbon solvent examples include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane.
  • Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc.
  • aromatic hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
  • the unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain.
  • a cis or trans body having a double bond may be mixed.
  • the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures.
  • decane when used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
  • the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
  • the organic solvent contained in the organic developer has 7 or more carbon atoms (preferably 7 to 14 and preferably 7 to 14) from the viewpoint that the swelling of the resist film can be suppressed when EUV light and EB are used in the exposure step. 12 is more preferable, and 7 to 10 is more preferable), and it is preferable to use an ester solvent having 2 or less heteroatoms.
  • the hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the number of heteroatoms is preferably 2 or less.
  • ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples thereof include butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
  • the organic solvent contained in the organic developer is replaced with the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, and the ester solvent and A mixed solvent of the hydrocarbon solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
  • isoamyl acetate is preferably used as the ester solvent.
  • the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
  • a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
  • 2-heptanone is preferably used as the ketone solvent.
  • the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
  • the content of the hydrocarbon solvent is not particularly limited because it depends on the solvent solubility of the resist film, and the necessary amount may be determined by appropriately preparing.
  • a plurality of the above organic solvents may be mixed, or may be used by mixing with other solvents or water.
  • the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
  • the concentration of the organic solvent (total in the case of a plurality of mixtures) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, and even more preferably 90 to 100% by mass. %, Particularly preferably 95 to 100% by mass. Most preferably, it consists essentially of an organic solvent.
  • the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.
  • the developer preferably contains an antioxidant.
  • an antioxidant thereby, generation
  • the antioxidant known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.
  • the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0% with respect to the total mass of the developer. More preferred is 0.01 mass%. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, development residue tends to be suppressed.
  • the developer may contain a basic compound, and specifically, the same one as the basic compound that may be contained in the resist resin composition may be mentioned.
  • the developer may contain a surfactant.
  • the surfactant the same surfactants that can be contained in the resist composition can be used.
  • the surfactant content is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the developer. %, More preferably 0.01 to 0.5% by mass.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
  • the development time is not particularly limited, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
  • the temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • both development using a developer containing an organic solvent and development with an alkali developer may be performed (so-called double development may be performed).
  • the pattern forming method of the present invention preferably includes a step (e) of rinsing (cleaning) the developed resist film with a rinsing liquid after the step (d).
  • rinse solution As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added. In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
  • a rinsing liquid in the rinsing treatment performed after the organic solvent development it is preferable to use a rinsing liquid containing an organic solvent (organic rinsing liquid).
  • the vapor pressure of the rinsing liquid (the vapor pressure as a whole in the case of a mixed solvent) is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more at 20 ° C. Most preferably, it is 3 kPa or less.
  • Organic solvent As the organic solvent contained in the organic rinsing liquid, various organic solvents are used. From the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferable to use at least one organic solvent selected. In particular, it is preferable that the rinse liquid contains a hydrocarbon-based solvent. Specific examples of these organic solvents are the same as those described for the developer.
  • the organic solvent contained in the organic rinsing liquid when EUV light or EB is used in the exposure step, it is preferable to use a hydrocarbon solvent among the above organic solvents, and use an aliphatic hydrocarbon solvent. Is more preferable.
  • an aliphatic hydrocarbon solvent having 5 or more carbon atoms for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.
  • aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred
  • aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
  • the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
  • decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.
  • a hydrocarbon solvent especially an aliphatic hydrocarbon solvent
  • hydrocarbon solvent examples include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
  • unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain. Cis and trans isomers having a double bond may be mixed.
  • the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures.
  • decane when used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
  • the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
  • a plurality of organic solvents may be mixed, or may be used by mixing with an organic solvent other than the above.
  • the solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there.
  • a favorable rinse characteristic can be acquired by making a moisture content into 60 mass% or less.
  • the rinse liquid contains a surfactant.
  • a surfactant the same surfactants as those used in the resist composition can be used.
  • the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total mass of the rinse liquid. .
  • the rinse liquid preferably contains an antioxidant. Thereby, generation
  • Specific examples and contents of the antioxidant are as described in the above developer.
  • the developed wafer is cleaned using the above rinsing liquid.
  • the method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) in which a rinse liquid is sprayed onto the substrate surface. Among these, it is preferable to remove the rinse liquid from the substrate by performing a cleaning process by a spin coating method and then rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm.
  • the developer and the rinsing liquid are stored in a waste liquid tank through a pipe after use.
  • a hydrocarbon solvent is used as the rinsing liquid
  • the resist dissolves again in order to prevent the dissolved resist from being deposited in the developer and adhering to the back surface of the wafer or the side of the pipe.
  • As a method of passing through the piping after washing with a rinsing solution, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing in is mentioned.
  • the resist composition in the present invention and various materials used in the pattern forming method of the present invention for example, a resist solvent, a developer, a rinse solution, an antireflection film forming composition, an upper layer film forming composition, etc.
  • impurities such as metal, metal salt containing halogen, acid, alkali (excluding alkali in alkali developer) are not contained.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
  • Examples of methods for removing impurities such as metals from various materials include filtration using a filter and purification steps by distillation (particularly, thin film distillation, molecular distillation, etc.).
  • the purification process by distillation is, for example, “ ⁇ Factory Operation Series> Augmentation / Distillation, issued July 31, 1992, Chemical Industry Co., Ltd.” or “Chemical Engineering Handbook, Issued September 30, 2004, Asakura Shoten, pages 95-102” Page ".
  • 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 obtained by combining these materials and ion exchange media.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different hole diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • an apparatus that selects a raw material having a low metal content as a raw material constituting each material, and performs filter filtration on the raw material constituting each material.
  • Examples thereof include a method of performing distillation under a condition in which the inside is lined with Teflon (registered trademark) and contamination is suppressed as much as possible.
  • the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
  • impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the organic solvent (organic processing solution) that can be used for the developing solution and the rinsing solution contains an organic processing solution for patterning of a chemically amplified resist film having a storing portion. It is preferable to use one stored in a container.
  • the inner wall of the container that comes into contact with the organic treatment liquid is subjected to a resin different from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust prevention and metal elution prevention treatment.
  • the container is a container for an organic processing solution for patterning a chemically amplified resist film formed from the formed metal.
  • An organic solvent to be used as an organic processing liquid for patterning a chemically amplified resist film is stored in the container of the container and discharged from the container when patterning the chemically amplified resist film. Can be used.
  • the seal part is also a resin different from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or It is preferably formed from a metal that has been subjected to rust prevention and metal elution prevention treatment.
  • a seal part means the member which can interrupt
  • the resin different from the polyethylene resin, the polypropylene resin, and the polyethylene-polypropylene resin is preferably a perfluoro resin.
  • Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride.
  • PTFE tetrafluoroethylene resin
  • PFA perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer resin
  • Ethylene-ethylene copolymer resin Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
  • Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
  • Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.
  • As the rust prevention / metal elution prevention treatment it is preferable to apply a film technology.
  • Preferable film technology includes surface treatment with a rust preventive oil, a rust preventive agent, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
  • a rust preventive oil various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids)
  • chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine trisuccinic acid, diethylene triamine pentic acid, and fluororesin lining.
  • pretreatment is a stage before rust prevention treatment. It is also preferable to adopt.
  • a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.
  • the storage container include the following. ⁇ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining) ⁇ JFE steel drums (wetted inner surface; zinc phosphate coating)
  • Examples of the storage container that can be used in the present invention include the containers described in JP-A-11-021393 [0013] to [0030] and JP-A-10-45961 [0012] to [0024]. be able to.
  • the organic processing liquid in the present invention may be added with a conductive compound in order to prevent chemical piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to electrostatic charging and subsequent electrostatic discharge. good.
  • a conductive compound for example, methanol is mentioned.
  • the addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics.
  • SUS stainless steel
  • various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can.
  • polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.
  • the pattern obtained by the pattern forming method of the present invention is generally suitably used as an etching mask for a semiconductor device or the like, but can also be used for other purposes.
  • Other uses include, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4, No. 8, Page 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).
  • the present invention also relates to a mask blank provided with the resist film of the present invention.
  • the transparent substrate used may be a transparent substrate such as quartz or calcium fluoride. be able to.
  • a light shielding film, an antireflection film, a phase shift film, and additional functional films such as an etching stopper film and an etching mask film are laminated on the substrate.
  • a film containing a transition metal such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium is laminated.
  • silicon or a material containing oxygen and / or nitrogen in silicon as a main constituent material
  • silicon compound material containing a transition metal-containing material as a main constituent material
  • a transition metal in particular, one or more selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or a material further containing one or more elements selected from oxygen, nitrogen, and carbon
  • the transition metal compound material is exemplified.
  • the light shielding film may be a single layer, but more preferably has a multilayer structure in which a plurality of materials are applied.
  • the thickness of the film per layer is not particularly limited, but is preferably 5 to 100 nm, and more preferably 10 to 80 nm.
  • the thickness of the entire light shielding film is not particularly limited, but is preferably 5 to 200 nm, and more preferably 10 to 150 nm.
  • the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention.
  • the electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitably mounted in the manufacture of electrical / electronic equipment (home appliances, OA (Office Appliance) / media-related equipment, optical equipment, communication equipment, etc.). It is.
  • Resins (P-1) to (P-27) were synthesized in the same manner as Resin (P-20).
  • GPC carrier: tetrahydrofuran (THF)
  • the composition ratio (molar ratio) was calculated by 1 H-NMR (Nuclear Magnetic Resonance) measurement.
  • the structure of the synthesized resin is shown below together with the composition ratio (molar ratio) of repeating units, the weight average molecular weight (Mw), and the dispersity (Mw / Mn).
  • resins (PR-1) to (PR-5) were synthesized in the same manner.
  • the structure, composition ratio (molar ratio), weight average molecular weight, and dispersity of each synthesized resin are shown below.
  • the photoacid generator the basic compound, the crosslinking agent, the hydrophobic resin, the surfactant, the solvent, the composition for forming the upper layer film, the developer, and the rinse liquid used in Examples and Comparative Examples are shown.
  • the photoacid generator was appropriately selected from the above-mentioned specific compounds (z1 to z35).
  • W-1 Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon-based)
  • W-2 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
  • W-3 Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
  • W-4 PF6320 (manufactured by OMNOVA; fluorine-based)
  • composition for upper layer film As an upper layer film composition, the components shown in Table 2 below are dissolved in a solvent, and a solution having a solid content concentration of 2.0% by mass is prepared for each, and filtered through a polyethylene filter having a pore size of 0.04 ⁇ m. A forming composition was prepared.
  • G-1 2.38 mass% tetramethylammonium hydroxide aqueous solution
  • G-2 butyl acetate
  • G-3 3-methylbutyl acetate
  • G-4 pure water
  • G-5 undecane
  • G-6 diisobutyl ketone
  • G-7 Isobutyl isobutanoate
  • G-8 Methyl amyl ketone
  • G-9 4-Methyl-2-heptanol
  • G-10 Diisobutyl ether
  • G-11 Diisopentyl ether
  • G-12 Diisohexyl ether
  • G-13 Decane
  • Coating composition preparation and coating of resist composition The coating composition having a solid content concentration of 2.5% by mass having the composition shown in Table 3 below is precisely filtered through a membrane filter having a pore size of 0.1 ⁇ m to obtain a resist. A composition solution was obtained. This resist composition solution was applied onto a 6-inch Si substrate previously subjected to hexamethyldisilazane (HMDS) treatment using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds. A resist film having a thickness of 50 nm was obtained.
  • HMDS hexamethyldisilazane
  • the upper layer film-forming composition shown in Table 3 was further applied on the resist film. Thereafter, baking was performed at 110 ° C. for 90 seconds to form an upper film having a thickness of 50 nm. Here, 1 inch is 0.0254 m.
  • PEB Post Exposure Bake
  • the developer (23 ° C.) shown in Table 3 was fed at a flow rate of 200 mL / min while rotating the wafer at 50 rpm (rpm). The developer was deposited on the wafer by spraying for 5 seconds. Next, the wafer rotation was stopped, and development was performed by leaving the wafer to stand for 60 seconds.
  • a shower type developing device AD3000S manufactured by ACTES Co., Ltd.
  • the LWR performance is the length of the 1: 1 line and space pattern with a line width of 50 nm in the above Eop (however, for Comparative Examples 1-AR to 4-AR, the 1: 1 line and space pattern with a line width of 100 nm).
  • the line width was measured at any 50 points in the direction of 0.5 ⁇ m, the standard deviation was obtained, and 3 ⁇ was calculated. A smaller value indicates better performance.
  • the prepared resist composition solution was allowed to stand at 4 ° C. for 1 week, and then the number of particles having a particle diameter of 0.2 ⁇ m or more present in the solution was counted using a particle counter manufactured by Rion. Smaller values indicate better performance.
  • Examples 1-B to 20-B Comparative Example 1-BR to 4-BR (extreme ultraviolet (EUV) exposure)
  • a coating composition having a solid content concentration of 1.5% by mass having the composition shown in Table 4 below is precisely filtered through a membrane filter having a pore size of 0.1 ⁇ m to obtain a resist.
  • a composition solution was obtained.
  • This resist composition solution was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 120 ° C. for 60 seconds.
  • a resist film having a thickness of 50 nm was obtained.
  • the upper layer film-forming composition shown in Table 4 was further applied on the resist film. Thereafter, baking was performed at 120 ° C. for 60 seconds to form an upper film having a thickness of 50 nm.
  • the rinse treatment (23 ° C.) shown in Table 4 below was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment. Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
  • the LWR performance is as follows.
  • an isolated line pattern with a line width of 50 nm (however, in Comparative Examples 1-BR to 4-BR, an isolated line pattern with a line width of 100 nm) is an arbitrary 50 ⁇ m in the longitudinal direction of 0.5 ⁇ m.
  • the line width was measured, the standard deviation was obtained, and 3 ⁇ was calculated. A smaller value indicates better performance.
  • the prepared resist composition solution was allowed to stand at 4 ° C. for 1 week, and then the number of particles having a particle diameter of 0.2 ⁇ m or more present in the solution was counted using a particle counter manufactured by Rion. Smaller values indicate better performance.
  • the prepared resist composition solution was allowed to stand at 4 ° C. for 1 week, and then the number of particles having a particle diameter of 0.2 ⁇ m or more present in the solution was counted using a particle counter manufactured by Rion. Smaller values indicate better performance.
  • Examples 1-A to 20-A and Examples 1-B to 20- using the resin (P) having the repeating unit (a) having an inner salt structure B and Examples 1-C to 6-C were superior in resolution, LWR performance, and number of particles as compared with the comparative example. This is the effect of introducing the inner salt structure into the polymer, and the quencher is uniformly distributed in the system, preventing the diffusion of acid generated from the photoacid generator and controlling the aggregation derived from the inner salt structure. It is thought that there is. Further, as is clear from Examples 15-A and 5-B, the resin (P) having the repeating unit (a) having an inner salt structure is used as a basic compound (quencher) instead of the main polymer.
  • a resin (P) having a repeating unit (a) having an inner salt structure can be used as a hydrophobic resin by combination with a fluorine component or the like.
  • the base component is unevenly distributed on the resist film surface, and the film loss (top loss) can be improved by the positive pattern forming method.
  • the head pattern (T-top shape) can be applied to the negative pattern forming method. Can improve. Therefore, the pattern shape can be improved by applying the resin (P) having the repeating unit (a) having an inner salt structure to the added polymer.
  • a resist composition that can form a pattern excellent in resolution and LWR performance and has a small number of particles, A resist film, a mask blank, a pattern formation method, and a method for manufacturing an electronic device using the resist composition can be provided.

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

Abstract

La présente invention concerne : une composition de réserve qui contient une résine (P) qui a une unité de répétition (a) ayant une structure de sel interne ; un film de réserve qui est formé à partir de cette composition de réserve ; une ébauche de masque ; un procédé de formation de motif qui utilise cette composition de réserve ; et un procédé de fabrication d'un dispositif électronique, qui comprend ce procédé de formation de motif.
PCT/JP2016/084490 2015-12-18 2016-11-21 Composition de réserve, film de réserve, ébauche de masque, procédé de formation de motif, et procédé de fabrication de dispositif électronique Ceased WO2017104355A1 (fr)

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JPWO2019009001A1 (ja) * 2017-07-04 2020-04-16 富士フイルム株式会社 デバイスの製造方法
CN111596533A (zh) * 2019-02-21 2020-08-28 东友精细化工有限公司 抗蚀剂剥离液组合物
KR20210086483A (ko) * 2019-12-31 2021-07-08 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 중합체 및 포토레지스트 조성물
WO2021177201A1 (fr) * 2020-03-02 2021-09-10 京セラ株式会社 Copolymère, son procédé de production, dispositif de mesure et support de mesure
JPWO2022102304A1 (fr) * 2020-11-10 2022-05-19
KR20250121533A (ko) 2022-12-13 2025-08-12 제이에스알 가부시키가이샤 감방사선성 조성물 및 레지스트 패턴 형성 방법

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CN111596533A (zh) * 2019-02-21 2020-08-28 东友精细化工有限公司 抗蚀剂剥离液组合物
CN111596533B (zh) * 2019-02-21 2023-09-15 东友精细化工有限公司 抗蚀剂剥离液组合物
KR20210086483A (ko) * 2019-12-31 2021-07-08 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 중합체 및 포토레지스트 조성물
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CN113121734B (zh) * 2019-12-31 2024-07-30 罗门哈斯电子材料有限责任公司 聚合物及光致抗蚀剂组合物
WO2021177201A1 (fr) * 2020-03-02 2021-09-10 京セラ株式会社 Copolymère, son procédé de production, dispositif de mesure et support de mesure
JPWO2022102304A1 (fr) * 2020-11-10 2022-05-19
WO2022102304A1 (fr) * 2020-11-10 2022-05-19 Jsr株式会社 Composition pour formation de film de sous-couche, film de sous-couche et procédé de lithographie
KR20250121533A (ko) 2022-12-13 2025-08-12 제이에스알 가부시키가이샤 감방사선성 조성물 및 레지스트 패턴 형성 방법

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