WO2017056832A1 - Active-light-sensitive or radiation-sensitive composition, resist film in which same is used, pattern formation method, and method for manufacturing electronic device - Google Patents

Active-light-sensitive or radiation-sensitive composition, resist film in which same is used, pattern formation method, and method for manufacturing electronic device Download PDF

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Publication number
WO2017056832A1
WO2017056832A1 PCT/JP2016/075434 JP2016075434W WO2017056832A1 WO 2017056832 A1 WO2017056832 A1 WO 2017056832A1 JP 2016075434 W JP2016075434 W JP 2016075434W WO 2017056832 A1 WO2017056832 A1 WO 2017056832A1
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group
compound
sensitive
radiation
acid
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PCT/JP2016/075434
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French (fr)
Japanese (ja)
Inventor
直也 下重
英宏 望月
修史 平野
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富士フイルム株式会社
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Priority to JP2017543042A priority Critical patent/JP6582053B2/en
Publication of WO2017056832A1 publication Critical patent/WO2017056832A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/26—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/48—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/08—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26—Sulfur atoms
    • 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 an actinic ray-sensitive or radiation-sensitive composition, and a resist film, a pattern forming method and an electronic device manufacturing method using the same. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive material used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and a photolithographic lithography process. The present invention relates to a composition, and a resist film, a pattern forming method, and an electronic device manufacturing method using the composition.
  • the present invention can form a pattern excellent in all of sensitivity, resolution, roughness performance, and pattern cross-sectional shape particularly in the formation of an ultrafine pattern (for example, a line width of 50 nm or less).
  • An object is to provide an actinic ray or radiation sensitive composition, and a resist film, a pattern forming method, and an electronic device manufacturing method using the same.
  • an actinic ray-sensitive or radiation-sensitive composition containing a specific compound As a result of intensive studies, the present inventors have found that the above object can be achieved by an actinic ray-sensitive or radiation-sensitive composition containing a specific compound.
  • the present invention is as follows.
  • X represents an oxygen atom or a sulfur atom
  • R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  • [14] The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [13], further comprising a hydrophobic resin (D).
  • [15] [1] A resist film formed of the actinic ray-sensitive or radiation-sensitive composition according to any one of [14].
  • [16] [15] A pattern forming method comprising irradiating the resist film according to [15] with actinic rays or radiation and developing the film irradiated with the actinic rays or radiation.
  • the pattern forming method according to [16] wherein the film irradiated with the actinic ray or radiation is developed with a developer containing an organic solvent to form a negative pattern.
  • an actinic ray or radiation sensitive composition and a resist film, a pattern forming method and an electronic device manufacturing method using the same.
  • the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do.
  • light means actinic rays or radiation.
  • “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified.
  • the exposure with the particle beam is also included in the exposure.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin are measured by GPC (solvent) using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation).
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention comprises (A) a compound having two or more structures represented by the following general formula (1) and having no acid crosslinkable group, and actinic rays or Contains compounds that generate acid by radiation.
  • X represents an oxygen atom or a sulfur atom
  • R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  • the compound (A) has two or more such highly polar structures. Therefore, in the formed pattern, the compound (A) provides a plurality of very high polar fields, and as a result, the resins interact with each other through such high polar fields. It is considered that a pseudo-crosslinked structure composed of the compound (A) and the resin (B) that can be contained in the actinic ray-sensitive or radiation-sensitive composition of the present invention is formed.
  • the above-described pseudo cross-linking structure improves the cohesiveness of the components constituting the pattern, so that even in an ultrafine pattern (for example, a line width of 50 nm or less), pattern destruction or the like hardly occurs, and resolution is achieved. It is presumed that the cross-sectional shape is improved and the pattern cross-sectional shape is more excellent.
  • the cohesiveness of the resin (B) in the pattern the acid generated in the exposed portion of the chemically amplified resist film was suppressed from diffusing too much into the unexposed portion, resulting in excellent roughness performance. Inferred.
  • the compound (A) exhibits a very high polarity.
  • the compound (A) and the substrate are more firmly adhered to each other, the adhesion between the pattern and the substrate is improved, and the resolution of the pattern is less likely to occur. Possible reason.
  • the pseudo-crosslinking is partially broken, and the additive becomes a plasticizer for the resin.
  • the compound (A) does not have an acid crosslinkable group.
  • the Tg reduction due to the depopulation of the resin (B) does not occur and the effect of the pseudo-crosslinking is more exhibited.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably for ArF excimer laser, electron beam or extreme ultraviolet exposure.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition, or an alkali development. Or a resist composition for organic solvent development.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention is typically a chemically amplified resist composition.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention is (A) a compound having two or more structures represented by the following general formula (1) and having no acid crosslinkable group ( Hereinafter, the compound (A) is also contained.
  • X represents an oxygen atom or a sulfur atom
  • R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  • the compound (A) does not have an acid crosslinkable group. That is, the compound (A) is not a crosslinking agent and does not correspond to a crosslinking agent (C) described later.
  • an acid crosslinkable group a well-known thing is mentioned, A hydroxymethyl group and an alkoxymethyl group are mentioned typically. Therefore, when the actinic ray-sensitive or radiation-sensitive composition of the present invention contains the resin (B), the compound (A) is not crosslinked with the resin (B) by the action of an acid.
  • At least one of the plurality of Rs in the general formula (1) is a hydrogen atom.
  • the high polarity of the structure represented by the general formula (1) is not easily lost, and the effects of the present invention can be sufficiently exhibited.
  • the monovalent organic group as R preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like. C8 or less is preferable.
  • the monovalent organic group as R is preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
  • Compound (A) preferably has no group capable of generating a base by the action of an acid.
  • the compound (A) is preferably a compound having a structure represented by the following general formula (2) as a structure represented by the general formula (1).
  • X and R are synonymous with X and R in the said General formula (1), respectively.
  • A represents —NR′— or an oxygen atom.
  • R ' represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  • Compound (A) has a structure represented by general formula (1) or (2) as an amide group (X represents an oxygen atom in general formula (1)), urea group (X in general formula (2) It preferably represents an oxygen atom, A represents —NR′—, or a urethane group (in the general formula (2), X represents an oxygen atom and A represents an —oxygen atom).
  • the pKa of the conjugate acid of the compound (A) is preferably 1 or less. As a result, the acid generated from the photoacid generator in the exposed area is less likely to be neutralized by the compound (A), and the desired reaction based on the action of the acid proceeds sufficiently, so that the sensitivity is unlikely to decrease. is there.
  • the compound (A) also preferably has an aromatic group, whereby the cohesiveness of the components constituting the pattern is further increased, and the resolution and roughness performance tend to be improved.
  • the compound (A) may have an aromatic group in the structure represented by the general formula (1) or (2), and is represented by the general formula (1) or (2). It may have an aromatic group outside the structure. In the former case, the aromatic group is included in at least one of R in the general formula (1) and R and R ′ in the general formula (2).
  • At least one of R in the general formula (1) and R and R ′ in the general formula (2) is a monovalent organic group having an electron withdrawing group. It is also preferable.
  • the bond between —NR— and —CX— in the structure represented by the general formula (1) or (2) is cleaved by the acid generated from the photoacid generator, and the resist film is removed. This is because aggregation of constituent components tends to be released and the exposed portion is easily developed.
  • the electron withdrawing group is preferably a group having a Hammett's rule ⁇ p value of 0 or more.
  • substituent having a positive ⁇ p value include halogen atoms such as fluorine (0.06), chlorine (0.30), bromine (0.27) and iodine (0.30), —CHO (0.22), —COCH 3 (0.50), —COC 6 H 5 (0.46), —CONH 2 (0.36), —COO— (0.30), —COOH (0.41), —COOCH 3 ( 0.39), a group having a carbonyl such as —COOC 2 H 5 (0.45), —SOCH 3 (0.49), —SO 2 CH 3 (0.72), —SO 2 C 6 H 5 ( 0.68), —SO 2 CF 3 (0.93), —SO 2 NH 2 (0.57), —SO 2 OC 6 H 5 (0.23), —SO 3 — (0.09), —SO 3 H (0.50) sulfony
  • the numerical value in parentheses is the ⁇ p value.
  • Hammett's ⁇ p value is, for example, C.I. Harsch et al. Med. Chem. 16, 1207 (1973), 20, 304 (1977), Chem. Rev. 91, 165 (1991).
  • the compound (A) may or may not have a structure (acid-decomposable group) protected with a leaving group that is decomposed and eliminated by the action of an acid.
  • the compound (A) preferably has no acid-decomposable group.
  • the compound (A) preferably has three or more structures represented by the general formula (1).
  • the compound (A) is preferably a compound represented by the following general formula (a).
  • L represents a trivalent linking group
  • Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the general formula (1).
  • the monovalent organic group as Y 1 , Y 2 and Y 3 preferably has 1 to 30 carbon atoms.
  • an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryloxy group examples include groups. These groups may further have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like. C8 or less is preferable.
  • the monovalent organic group having a structure represented by the general formula (1) typically has a structure represented by the general formula (1) in the group.
  • an atom (typically a carbon atom) constituting the monovalent organic group is replaced with a structure represented by the general formula (1).
  • trivalent linking group as L examples include groups in which two hydrogen atoms are further removed from the specific examples of the monovalent organic group as Y 1 , Y 2 and Y 3 described above. be able to.
  • the compound (A) may be in the form of a low molecular compound or may be in the form of a polymer (a form incorporated in a polymer (typically part of the polymer)). Moreover, you may use together the form of a low molecular compound, and the form of a polymer.
  • the compound (A) has substantially no molecular weight distribution.
  • the molecular weight is preferably 3000 or less, more preferably 2000 or less, from the viewpoint of suppressing the occurrence of development defects. More preferably, it is 1500 or less, and most preferably 1000 or less.
  • the molecular weight of a compound (A) is 450 or more from a viewpoint that volatilization of a compound (A) is suppressed.
  • carbamate compounds compounds having carbamate bonds
  • urea compounds compounds having urea bonds
  • amide compounds compounds having amide bonds
  • barbituric acid compounds barbituric acid structure
  • a compound having a cyanuric acid structure an imide compound (a compound having an imide bond), and a cyanuric acid compound (a compound having a cyanuric acid structure).
  • compound (A) when the compound (A) is in the form of a polymer, the compound (A) may be incorporated in the resin (B) described later.
  • compound (A) when compound (A) is in the form of a polymer, compound (A) also preferably has a repeating unit represented by the following general formula (I) or (II).
  • Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
  • T represents a single bond or a divalent linking group. Several T may mutually be same or different.
  • A represents a group having a structure represented by the general formula (1).
  • Examples of the optionally substituted alkyl group represented by Xa 1 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, —COO—Rt— group, —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.
  • the plurality of X 6 may be the same as or different from each other.
  • 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.
  • A represents a group having a structure represented by the general formula (1).
  • n represents an integer of 1 to 4. When n is an integer greater than or equal to 2, several A may mutually be same or different.
  • 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.
  • Compound (A) may be incorporated in the main chain of the polymer or in the side chain of the polymer, but when compound (A) is incorporated in the side chain of the polymer, “Especially, in the formation of an ultrafine pattern (for example, a line width of 50 nm or less), a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.” Since it tends to be expressed more reliably, it is preferable.
  • an ultrafine pattern for example, a line width of 50 nm or less
  • the content of the repeating unit having the structure represented by the general formula (1) is 1 to It is preferably 30 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%.
  • the content of the compound (A) is preferably 1 to 30% by mass with respect to the content of the resin (B) described later. It is more preferably 30% by mass, and further preferably 10 to 25% by mass.
  • the content of the compound (A) is 1 to 30% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive composition.
  • it is 3 to 25% by mass, more preferably 5 to 20% by mass.
  • the content of the compound (A) is 50 to 99.9% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive composition. It is preferably 60 to 99.0% by mass.
  • the weight average molecular weight of the compound (A) is preferably 1,000 to 200,000 as a polystyrene conversion value by GPC method, more preferably 3, 000 to 20,000, most preferably 5,000 to 15,000.
  • the degree of dispersion (molecular weight distribution) of the compound (A) is usually from 1 to 5, preferably from 1 to 3, more preferably from 1.2 to 3.0, particularly preferably from 1.1 to 2.0. Things are used.
  • the actinic ray-sensitive or radiation-sensitive composition preferably contains the resin (B), and the resin (B) preferably has an aromatic group.
  • the resin (B) can have various repeating units described later.
  • the resin (B) has a repeating unit (a) having an aromatic ring group.
  • 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.
  • the actinic ray or radiation sensitive composition when the actinic ray or radiation sensitive composition is for electron beam or extreme ultraviolet exposure, or contains a crosslinking agent described later (for example, the actinic ray or radiation sensitive composition is used for alkali development.
  • the resin (B) preferably has a repeating unit having a phenolic hydroxyl group.
  • 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 contained in the resin (B) is preferably a repeating unit represented by the following general formula (p1).
  • R in the general formula (p1) 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.
  • Resin (B) may have one or more repeating units (a) having a phenolic hydroxyl group, or two or more.
  • the content of the repeating unit (a) having a phenolic hydroxyl group is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, based on all repeating units of the resin (B). More preferably, it is 30 to 85 mol%.
  • the repeating unit (a) having an aromatic ring group may be a repeating unit represented by the following general formula (X).
  • 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 63 may be bonded to Ar to form a ring, in which case R 62 represents a single bond or an alkylene group.
  • Ar represents an (n + 1) -valent aromatic ring group, and when bonded to R 62 to form a ring, represents an (n + 2) -valent aromatic ring group.
  • 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.
  • the following 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.
  • Resin (B) may have one type of repeating unit (a) represented by general formula (X) or two or more types.
  • the content of the repeating unit represented by the general formula (X) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on all the repeating units of the resin (B). More preferably, it is 5 to 30 mol%.
  • the repeating unit (a) having an aromatic ring group has an aromatic ring group in the repeating unit (c) having a structure in which a polar group described later is protected by a leaving group that decomposes and leaves by the action of an acid. It may be a thing.
  • Resin (B) may have one type of repeating unit (a) having an aromatic ring group or two or more types.
  • the content of the repeating unit (a) having an aromatic ring group is preferably 5 to 100 mol%, more preferably 7 to 98 mol%, based on all repeating units of the resin (B), More preferably, it is 8 to 96 mol%.
  • the resin (B) has a repeating unit (b) 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 (b) 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 (B) having a repeating unit having an acid-decomposable group can be suitably used in the formation of a positive pattern using an alkali developer or the formation of a negative pattern using an organic developer.
  • Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
  • Formula (Y1) —C (Rx 1 ) (Rx 2 ) (Rx 3 )
  • Formula (Y2) —C ( ⁇ O) OC (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. Repeat More preferably, independently is Rx 1 ⁇ Rx 3 each a repeating unit represents a linear or branched alkyl group, more preferably, that each independently is Rx 1 ⁇ Rx 3, represents 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.
  • Resin (B) has a repeating unit represented by the following general formula (AI) or (AII) as the repeating unit having a group that decomposes by the action of an acid to generate a polar group.
  • Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
  • T represents a single bond or a divalent linking group.
  • Y represents a group capable of leaving with an acid.
  • Y is preferably a formula (Y1) to (Y4).
  • Examples of the optionally substituted alkyl group represented by Xa 1 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, —COO—Rt— group, —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 represented by 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 represented by 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.
  • the above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.
  • the content of the repeating unit having an acid-decomposable group in the resin (B) (when there are a plurality of types) is 5 mol% to 80 mol% with respect to all the repeating units in the resin (B). It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.
  • the repeating unit having an acid-decomposable group and an aromatic ring group corresponds to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.
  • the resin (B) also preferably contains a repeating unit having a lactone group or a sultone (cyclic sulfonate ester) group.
  • a 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 part or sultone structure part 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 (AI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb 0 may have include a hydroxyl group and a halogen atom. Examples of 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.
  • Preferred 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 preferably 1 to 30 mol%, more preferably 5 to 25 mol%, still more preferably 5 to 20 mol%, based on all repeating units in the resin (B). %.
  • the resin (B) can further have, as other repeating units, 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. 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 (B). It is ⁇ 25 mol%, more preferably 5 to 20 mol%.
  • resin (B) 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 a compound 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 (B). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
  • the resin (B) may have a repeating unit having a silicon atom in the side chain.
  • the repeating unit having a silicon atom in the side chain include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom.
  • 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 in the side chain is preferably a repeating unit having a silsesquioxane structure.
  • 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. preferable.
  • 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 organic group.
  • a plurality of R may be the same or different.
  • the organic group is not particularly limited, and specific examples include a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, a blocked mercapto group (for example, a mercapto group blocked (protected) with an acyl group) ), An acyl group, an imide group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group optionally having a hetero atom, a (meth) acryl group-containing group, and an epoxy group-containing group.
  • hetero atom of the hydrocarbon group that may have a hetero atom examples 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 examples include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the 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, having 2 to 30 carbon atoms).
  • the 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 resin (B) can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent capable of dissolving an actinic ray-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition. Thereby, generation
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
  • an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
  • the concentration of the reaction is 5 to 50% by mass, preferably 10 to 45% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 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 (B) 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 the GPC method. 000.
  • the weight average molecular weight 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 the GPC method. 000.
  • Another particularly preferable form of the weight average molecular weight of the resin (B) is 3,000 to 9,500 in terms of polystyrene by GPC method.
  • the degree of dispersion (molecular weight distribution) 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 content of the resin (B) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.
  • the resin (B) may be used alone or in combination.
  • the actinic ray-sensitive or radiation-sensitive composition contains a compound that generates an acid by actinic rays or radiation (also referred to as “photoacid generator ⁇ PAG: Photo Acid Generator”).
  • 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 (B) or in a resin different from the resin (B). In the present invention, the photoacid generator is preferably in the form of a low molecular compound.
  • the photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred. More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (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. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
  • 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 also include a lactone structure, and specific examples include lactone structures represented by the above-described 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 may be 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.
  • 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 aforementioned compound (ZI).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned 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).
  • Portions other than A anions represented by the general formula (AN1) i.e., - O 3 S- ⁇ C ( Xf) (Xf) ⁇ x - ⁇ (R 1) (R 2) ⁇ y- (L) z - preferred examples of the group represented by the, - O 3 S-CF 2 -CH 2 -OCO-, - O 3 S-CF 2 -CHF-CH 2 -OCO-, - O 3 S-CF 2 - COO-, - O 3 S-CF 2 -CF 2 -CH 2 -, and, - O 3 S-CF 2 -CH (CF 3) -OCO- , and the like.
  • AN1 i.e., - O 3 S- ⁇ C ( Xf) (Xf) ⁇ x - ⁇ (R 1) (R 2) ⁇ y- (L) z - preferred examples of the group represented by the, - O 3 S-CF 2 -CH 2 -OCO-, -
  • 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.
  • the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid).
  • more preferably 270 ⁇ 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Particularly preferred.
  • 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.
  • One foot is 1 ⁇ 10 ⁇ 10 m.
  • 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 actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition.
  • the content is preferably 8 to 40% by mass.
  • the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention may further contain a crosslinking agent (hereinafter also referred to as “compound (C)”).
  • the compound (C) is a component different from the compound (A).
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention is usually a negative actinic ray-sensitive or radiation-sensitive composition.
  • the cross-linking agent is typically a compound that cross-links with the resin (B) by the action of an acid, a compound having an acid cross-linkable group, and a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. It is.
  • the crosslinking agent preferably contains a methylol group.
  • the compound (C) may be in the form of a low molecular compound or may be in a form 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 molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the compound (C ′) is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound.
  • Particularly preferred compounds (C ′) include phenol derivatives and alkoxymethyl glycols having 3 to 5 benzene rings in the molecule, and further having two or more hydroxymethyl groups or alkoxymethyl groups, and a molecular weight of 1200 or less. Examples include uril derivatives.
  • the 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 having no 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 compound (C ′) further have an N-hydroxymethyl group or an N-alkoxymethyl group such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds.
  • a compound can be mentioned.
  • 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.
  • the compound (C ′) those particularly preferred are listed below.
  • L 1 to L 8 each independently represents a hydroxymethyl group or an alkoxymethyl group.
  • the compound (C ′) is preferably a compound represented by the following general formula (I).
  • 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 (I) are preferably bonded to form a polycyclic fused ring containing a benzene ring, and more preferably a fluorene structure is formed. preferable.
  • R 3 and R 4 in the general formula (I) are preferably 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 compound (C ′) 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 (I).
  • the compound (C ′) is preferably a compound having a total of two or more aromatic rings and two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.
  • the manufacturing method of compound (C ') represented by general formula (I) is demonstrated.
  • the bisphenol compound serving as the mother nucleus of the compound (C ′) represented by the general formula (I) is generally a dehydration condensation reaction between two corresponding molecules of a phenol compound and one corresponding molecule of a ketone in the presence of an acid catalyst. To be 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 (I).
  • 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 synthesis method via a hydroxymethyl compound under a basic condition for example, JP 2008-273844 A.
  • Specific examples of the compound (C ′) represented by the general formula (I) are shown below.
  • the compound (C ′) 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 compound (C) when in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (B) or in a resin different from the resin (B).
  • the actinic ray-sensitive or radiation-sensitive composition according to the present invention may or may not contain the compound (C), but when it is contained, the content of the compound (C)
  • the total solid content of the radiation composition is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass.
  • the actinic ray-sensitive or radiation-sensitive composition used in the present invention preferably contains a solvent (also referred to as “resist solvent”).
  • This solvent comprises (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 the group is included.
  • this solvent may further contain components other than component (M1) and (M2).
  • the present inventors have found that when such a solvent and the above-described resin are used in combination, the coating property of the composition is improved and a pattern with a small number of development defects can be formed. The reason for this is not necessarily clear, but the present inventors have found that these solvents have a good balance of solubility, boiling point, and viscosity of the resin described above. It is thought that it originates in being able to suppress generation
  • 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, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, 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, and further 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, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.
  • 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.
  • the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.
  • the solvent may further contain components other than the components (M1) and (M2).
  • the content of components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.
  • the content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined such that the solid content concentration of all components is preferably 0.5 to 30% by mass, and is determined to be 1 to 20% by mass. It is more preferable. If it carries out like this, the applicability
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains (E) a basic compound in order to reduce changes in performance over time from exposure to heating.
  • a basic compound in order to reduce changes in performance over time from exposure to heating.
  • Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably a carbon atom). 3 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 (A) and (E) 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 oxy 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 oxy 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 oxy 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.
  • a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc.
  • an organic solvent such as chloroform.
  • composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).
  • PA acidic property
  • 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 amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.
  • the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment.
  • the photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
  • the composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”).
  • the hydrophobic resin (D) is preferably different from the resin (B).
  • the hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface.
  • unlike the surfactant it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to Examples of the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.
  • the hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
  • the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.
  • the hydrophobic resin (D) contains a fluorine atom
  • it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
  • a cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.
  • alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
  • the invention is not limited to this.
  • R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched).
  • R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
  • R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
  • the hydrophobic resin (D) may contain a silicon atom.
  • the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
  • Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
  • the hydrophobic resin (D) it is also preferred to include CH 3 partial structure side chain moiety.
  • CH 3 partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH 3 partial structure")
  • The, CH 3 partial structure an ethyl group, and a propyl group having Is included.
  • a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an ⁇ -methyl group of a repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH 3 partial structure in the present invention.
  • the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M).
  • R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
  • CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
  • R 11 is an ethyl group (CH 2 CH 3 )
  • R 11 to R 14 each independently represents a side chain portion.
  • R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
  • the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
  • Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).
  • X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
  • R 2 has one or more CH 3 partial structure represents a stable organic radical to acid.
  • the organic group that is stable to an acid is more specifically an organic group that does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferred.
  • the alkyl group of Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
  • X b1 is preferably a hydrogen atom or a methyl group.
  • R 2 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH 3 partial structures.
  • R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
  • Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.
  • the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
  • the repeating unit represented by formula (III) will be described in detail.
  • X b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom
  • R 3 represents an acid-stable organic group having one or more CH 3 partial structures
  • n represents an integer of 1 to 5.
  • the alkyl group of Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
  • X b2 is preferably a hydrogen atom. Since R 3 is an organic group that is stable against acid, more specifically, R 3 is preferably an organic group having no acid-decomposable group.
  • R 3 includes an alkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has 1 or more and 10 or less CH 3 partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
  • n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • the repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
  • the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
  • the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
  • the content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin (D).
  • the hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ),
  • the surface free energy of the hydrophobic resin (D) increases.
  • the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.
  • the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH 3 partial structure is included in the side chain portion. ) May have at least one group selected from the group of (X) an acid group, (Y) a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter also referred to as a polar conversion group); (Z) a group decomposable by the action of an acid
  • Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
  • Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and
  • the repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable.
  • the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.
  • Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto.
  • Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • the group (y) that decomposes by the action of an alkali developer and increases the solubility in the alkali developer is preferably a group having a lactone structure, an acid anhydride group, or an acid imide group, and particularly preferably a group having a lactone structure.
  • the repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group.
  • this repeating unit may be introduce
  • the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin P.
  • the content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is preferably 3 to 98 mol%, more preferably 5 to 95 mol%.
  • examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin P.
  • the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
  • the hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
  • the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
  • hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion
  • a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable.
  • hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
  • the standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
  • the hydrophobic resin (D) may be used alone or in combination.
  • the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.
  • the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
  • hydrophobic resin (D) various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
  • the actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a surfactant (F).
  • 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 thereof is preferably 0 to 2% by mass, more preferably based on the total solid content of the composition.
  • the content is 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.
  • the actinic ray- or radiation-sensitive composition used in the present invention is a compound (for example, molecular weight) that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer. 1000 or less phenol compounds, or alicyclic or aliphatic compounds containing a carboxy group) may further be included.
  • the actinic ray-sensitive or radiation-sensitive composition used in the present invention 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 actinic ray-sensitive or radiation-sensitive composition used in the present invention preferably contains an organic acid.
  • the amount of the organic acid is preferably larger from the viewpoint of stability over time, and the content of the organic acid in the actinic ray-sensitive or radiation-sensitive composition of the present invention is 5% by mass with respect to the total solid content. It is preferable to add so that it may become super.
  • the organic acid content in the composition of the present invention is more preferably more than 5% by weight and less than 15% by weight based on the total solid content in the composition, more than 5% by weight. More preferably, it is less than 10 mass%.
  • the organic acid preferably has a pKa in the range of 0 to 10, more preferably in the range of 2 to 8, and still more preferably in the range of 3 to 7, from the viewpoint of stability over time.
  • pKa represents pKa in an aqueous solution.
  • Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • a lower value indicates a higher acid strength.
  • pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation.
  • the values of pKa in this specification all indicate values obtained by calculation using this software package.
  • Software package 1 Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).
  • the pKa of the organic acid is preferably lower than the pKa of the resin, and preferably higher than the pKa of the acid generated from the acid generator. .
  • the pKa of the organic acid is preferably 3 or more and more preferably 5 or more lower than the pKa of the resin (B).
  • the pKa of the organic acid is preferably 2 or more, and more preferably 3 or more, higher than the pKa of the acid generated from the photoacid generator.
  • organic acid examples include organic carboxylic acids and organic sulfonic acids, among which organic carboxylic acids are preferable.
  • organic carboxylic acid examples include aromatic organic carboxylic acids, aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, and alkoxycarboxylic acids.
  • the organic acid is preferably an organic carboxylic acid, more preferably an aromatic organic carboxylic acid, benzoic acid, salicylic acid, 2-hydroxy-3-naphthoic acid, 2-naphthoic acid. Are more preferable, and salicylic acid is most preferable.
  • the pKa of the organic carboxylic acid is preferably 3.3 or more.
  • the organic carboxylic acid preferably has no acid group other than the carboxyl group.
  • the actinic ray or radiation sensitive composition contains an organic carboxylic acid
  • the organic carboxylic acid neutralizes the basic compound in the actinic ray or radiation sensitive composition, whereby the resin (B), The time-dependent degradation of the hydrophobic resin (D) and the compound (A) in a form incorporated in the polymer is prevented, and the stability over time of the actinic ray-sensitive or radiation-sensitive composition tends to be improved.
  • the present invention also relates to a resist film formed with the actinic ray-sensitive or radiation-sensitive composition of the present invention.
  • the composition of the present invention is coated on a support such as a substrate. Is formed.
  • the thickness of this film is preferably 0.02 to 0.1 ⁇ m.
  • spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. are applied on the substrate, but spin coating is preferred, and the number of rotations is 1000 to 3000 rpm is preferred.
  • the coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes to form a thin film.
  • a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer.
  • the material that becomes the outermost layer include Si, SiO 2 , SiN, SiON, TiN, Examples thereof include WSi, BPSG, SOG, and an organic antireflection film.
  • an antireflection film may be coated on the substrate in advance.
  • the antireflection film any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used.
  • the organic antireflection film commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.
  • a top coat may be formed on the upper layer of the resist film. 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 top coat is not particularly limited, and the same hydrophobic resin that can be contained in the actinic ray-sensitive or radiation-sensitive composition can be used. (D) can be mentioned suitably.
  • 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 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, are increased. High sensitivity and high resolution can be expected when forming a repeating unit having an aromatic ring.
  • 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 the 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, a crosslinking agent, and the compound (A). 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 behind 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 (topcoat-forming composition) 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 applied uniformly 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 that of the developer (organic developer) containing an organic solvent, which will be described in detail later.
  • 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 present invention relates to a pattern forming method including irradiating (exposing) actinic light or radiation to the resist film and developing the film irradiated with the actinic light or radiation.
  • the exposure is preferably performed using an ArF excimer laser, an electron beam or extreme ultraviolet rays.
  • the exposure (pattern formation process) on the resist film is performed by first irradiating the resist film of the present invention with ArF excimer laser, electron beam or extreme ultraviolet (EUV). preferable.
  • Exposure in the case of ArF excimer laser 1 ⁇ 100mJ / cm 2, preferably about 20 ⁇ 60mJ / cm 2 or so, when the electron beam, 0.1 ⁇ 20 ⁇ C / cm 2, preferably about 3 ⁇ 10 [mu] C / cm about 2, in the case of extreme ultraviolet, 0.1 ⁇ 20 mJ / cm 2, preferably about exposed so that the 3 ⁇ 15 mJ / cm 2 or so.
  • post-exposure heating on a hot plate preferably at 60 to 150 ° C. for 5 seconds to 20 minutes, more preferably at 80 to 120 ° C. for 15 seconds to 10 minutes, and even more preferably at 80 to 120 ° C. for 1 to 10 minutes.
  • post exposure baking is performed, and then a pattern is formed by developing, rinsing and drying.
  • the post-exposure heating is appropriately adjusted depending on the acid decomposability of the repeating unit (b) having an acid decomposable group in the resin (B).
  • the post-exposure heating temperature is preferably 110 ° C. or higher and the heating time is preferably 45 seconds or longer.
  • the post-exposure heating temperature is 110 ° C. or higher, and the heating time is 45 seconds or longer. It is also preferable.
  • the developer is appropriately selected, but it is preferable to use an alkali developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer).
  • the developer When the developer is an alkaline aqueous solution, it is 0.1 to 5% by mass, preferably 2 to 3% by mass alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH),
  • TMAH tetramethylammonium hydroxide
  • TBAH tetrabutylammonium hydroxide
  • the development is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a paddle method, or a spray method.
  • An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.
  • the pattern forming method of the present invention it is preferable to form a negative pattern by developing a film irradiated with actinic rays or radiation with a developer containing an organic solvent.
  • the pattern forming method of the present invention includes a step of developing using an alkali developer
  • examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
  • Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, and triethanol Alcohol amines such as amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyl Tetraalkylammonium hydroxide such as ammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammoni
  • 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.
  • an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
  • 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.
  • a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
  • the developer in the step includes a ketone solvent and an ester solvent.
  • Polar solvents such as solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
  • the ester solvent is a solvent having an ester group in the molecule
  • the ketone solvent is a solvent having a ketone group in the molecule
  • the alcohol solvent is alcoholic in the molecule.
  • It is a solvent having a hydroxyl group
  • 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.
  • a developer containing at least one kind of solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.
  • the developer has 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10), and 2 or less heteroatoms from the viewpoint that the swelling of the resist film can be suppressed. It is preferable to use the ester solvent.
  • 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 include heptyl propionate, butyl butanoate, isobutyl isobutanoate and the like, and it is particularly preferable to use isoamyl acetate or isobutyl isobutanoate.
  • the developer is a mixed solvent of the following ester solvent and the following hydrocarbon solvent, or the following ketone solvent and the following carbonized solvent.
  • a mixed solvent of hydrogen 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.
  • 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.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, Examples include isophorone and propylene carbonate, and diisobutyl ketone and 2,5-dimethyl-4-hexanone are particularly preferable.
  • ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl.
  • Examples include butyl and methyl 2-hydroxyisobutyrate.
  • alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
  • ether solvent examples include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
  • the aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures.
  • 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane which are compounds having the same carbon number and different structures
  • isooctane which are compounds having the same carbon number and different structures
  • 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 the above solvents may be mixed, or may be used by mixing with a solvent other than those described above 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. That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
  • the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
  • the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • vapor pressure of 5 kPa or less examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl a
  • vapor pressure of 2 kPa or less examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio , Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl
  • Glycol solvents ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents, N- Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents, aromatic hydrocarbon solvents such as xylene, octane, decane, include aliphatic hydrocarbon solvents undecane.
  • the organic developer may contain a basic compound.
  • Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the aforementioned actinic ray-sensitive or radiation-sensitive composition.
  • the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
  • fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos.
  • the surfactant is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer.
  • 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.
  • dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
  • paddle 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
  • spray method a method of spraying the developer on the substrate surface
  • the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less.
  • There is no particular lower limit on the flow rate but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
  • the details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer may be reduced, and the resist film / pattern may be cut or collapsed carelessly. This is considered to be suppressed.
  • the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
  • Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
  • a step of stopping development may be performed while substituting with another solvent.
  • a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to include the step of using and washing.
  • the rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
  • a rinse liquid a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
  • hydrocarbon solvent the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent
  • the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent can include the same as those described in the developer containing an organic solvent, Particularly preferred are butyl acetate and methyl isobutyl carbinol.
  • a rinse solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is used. It is preferable to perform a cleaning step using a rinsing liquid containing an alcohol solvent or a hydrocarbon solvent.
  • the organic solvent contained in the rinsing liquid it is also preferable to use a hydrocarbon solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent.
  • 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
  • a plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
  • the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
  • the vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic 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 at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable.
  • An appropriate amount of a surfactant can be added to the rinse solution.
  • the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent.
  • the cleaning method 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), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied.
  • a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
  • a heating process (PostBake) after the rinsing process.
  • the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
  • the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
  • JP-A-2015-216403 In the case where there is no washing step using a rinsing solution, for example, the development processing methods described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be employed.
  • the pattern forming method of the present invention may have a developing step using an organic developer and a developing step using an alkali developer. A portion with low exposure intensity is removed by development using an organic developer, and a portion with high exposure intensity is also removed by development using an alkali developer.
  • a pattern can be formed without dissolving only an intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A). [Mechanism similar to [0077]).
  • Actinic ray-sensitive or radiation-sensitive composition in the present invention and various materials used in the pattern forming method of the present invention (for example, resist solvent, developer, rinse solution, antireflection film-forming composition, topcoat formation) It is preferable that the composition or the like does not contain impurities such as a metal, a metal salt containing a halogen, an acid, an alkali, a component containing a sulfur atom or a phosphorus atom.
  • impurity containing a metal atom include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. it can.
  • 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 the method for removing impurities such as metals from various materials include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • 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.
  • a raw material having a low metal content is selected as a raw material constituting various materials, and a filter is provided for the raw materials constituting various materials.
  • a filter is provided for the raw materials constituting various materials. Examples thereof include a method of performing filtration and distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
  • Teflon registered trademark
  • 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 by an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • the adsorbent known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • An organic solvent (also referred to as “organic processing solution”) that can be used for the developer and the rinsing solution is a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified resist film having a storing portion. It is preferable to use a stored one.
  • the inner wall of the container that comes into contact with the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention / metal elution prevention treatment is performed. It is preferably a container for an organic processing liquid for patterning a resist film, which is formed from applied metal.
  • An organic solvent to be used as an organic processing liquid for patterning a resist film is accommodated in the accommodating portion of the accommodating container, and the one discharged from the accommodating portion at the time of patterning the resist film can be used. .
  • the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.
  • the seal part means a member capable of shutting off the accommodating part and the outside air, and can preferably include a packing, an O-ring and the like.
  • the resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and 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 preferable 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.
  • film technology as rust prevention and metal elution prevention treatment.
  • metal coating variable plating
  • inorganic coating variable chemical conversion treatment, glass, concrete, ceramics, etc.
  • organic coating rust prevention oil, paint, rubber, plastics.
  • Preferred film technology includes surface treatment with a rust inhibitor oil, a rust inhibitor, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
  • 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 includes 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 solution of the present invention can be added with a conductive compound to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
  • a conductive compound for example, methanol is mentioned.
  • the good addition 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 developer and the rinse liquid are stored in a waste liquid tank through a pipe after use.
  • a hydrocarbon-based solvent is used as the rinsing solution
  • the resist dissolved in the developer is deposited, and in order to prevent the resist from adhering to the back surface of the wafer or the side of the pipe, the solvent in which the resist dissolves is added to the pipe again.
  • As a method of passing through the piping after cleaning with a rinsing liquid, 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 is mentioned.
  • the solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA propylene glycol monoethyl ether acetate
  • propylene glycol monopropyl propylene glycol monopropyl.
  • Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, or the like can be used.
  • PGMEA, PGME, and cyclohexanone can be preferably used.
  • a pattern obtained by the pattern forming method of the present invention as a mask a semiconductor fine circuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation.
  • the pattern formed by the above method can also be used for guide pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano Vol. 4 No. 8 Page 4815-4823). Further, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
  • DSA Directed Self-Assembly
  • core core material of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
  • Japanese Patent No. 4109085 Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application Deployment” -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".
  • the photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.
  • 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 of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) / media-related device, optical device, communication device, etc.). is there.
  • a mixed solution of ethyl acetate / methanol / hexane 50 mL / 50 mL / 200 mL was added and stirred for 15 minutes.
  • the compound (A) includes compounds C-1 to C-36, U-1 to U-16, A-1 to A-22, BA-1 to BA-14, I-1 to I-14 and CA-1 to CA-10 were appropriately selected and used.
  • the compound (A) in a form incorporated in the polymer the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) shown in the table below. A compound having was used.
  • PGMEA Propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-acetoxypropane)
  • PGME Propylene glycol monomethyl ether (also known as 1-methoxy-2-propanol)
  • EL ethyl lactate CyHx: cyclohexanone
  • Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-5 (electron beam (EB) exposure; positive pattern formation)]
  • Coating composition preparation and coating of resist composition The components shown in Tables 1 to 3 below are dissolved in the solvents shown in Tables 1 to 3 to prepare a solution having a solid content concentration of 4.0% by mass. Filtration through a polyethylene filter having a pore size of 0.02 ⁇ m gave resist composition solutions of Examples 1-1 to 1-30 and Comparative Examples 1-1 to 1-5.
  • the numerical values for the solvents in Tables 1 to 3 below indicate the content of the solvent with respect to the total amount in terms of mass%.
  • the 1: 1 line and space pattern having a line width of 68 nm was resolved, and in the comparative examples 1-3 to 1-5, the 1: 1 line and space pattern having a line width of 66 nm was resolved.
  • the exposure amount (electron beam irradiation amount) at the time of performing was defined as sensitivity (Eop).
  • the resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount (electron beam irradiation amount) showing the above sensitivity.
  • the 1: 1 line and space pattern with a line width of 68 nm in Comparative Example 1-2, the 1: 1 line and space pattern with a line width of 68 nm, and in Comparative Examples 1-3 to 1-5, the 1: 1 line and space pattern with a line width of 66 nm, respectively.
  • the pattern cross-sectional shape is preferably “rectangular”.
  • Compound H-4 corresponds to a compound having an acid crosslinkable group (crosslinking agent).
  • Examples 1-1 to 1-30 using a resist composition containing a compound compatible with the compound (A) are Comparative Examples 1-1 to 1 using a resist composition not containing the compound. Compared to -5, it was found that in the formation of an ultrafine pattern, a pattern excellent in all of sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
  • Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-3 (electron beam (EB) exposure; negative pattern formation)
  • the components shown in Table 5 below were dissolved in the solvent shown in Table 5 below to prepare a solution having a solid content concentration of 2.7% by mass, and this was filtered through a polyethylene filter having a pore size of 0.02 ⁇ m.
  • Resist composition solutions of -1 to 2-13 and Comparative Examples 2-1 to 2-3 were obtained.
  • the numerical value in the solvent of the following Table 5 shows content with respect to the whole quantity of a solvent with the mass%. Except for using these resist compositions, coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1. The results are shown in Table 6 below.
  • Examples 2-1 to 2-13 using a resist composition containing a compound compatible with compound (A) are comparative examples 2-1 to 2-2 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
  • the same effect can be obtained by forming a negative pattern by changing the developing solution and the rinsing solution to the organic solvent described above.
  • Examples 3-1 to 3-8, Comparative Examples 3-1 to 3-3 (ArF excimer laser exposure; negative pattern formation)]
  • Coating composition preparation and coating of resist composition The components shown in Table 7 below are dissolved in the solvent shown in Table 7 below to prepare a solution having a solid content concentration of 3.5% by mass. Filtration through a polyethylene filter having a pore size gave resist composition solutions of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-3.
  • the numerical value in the solvent of the following Table 7 shows content with respect to the whole quantity of a solvent with the mass%.
  • resist composition solutions were 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 100 ° C. for 60 seconds. A resist film having a thickness of 120 nm was obtained.
  • HMDS hexamethyldisilazane
  • the resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount showing the above sensitivity.
  • Examples 3-1 to 3-8 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 3-1 to 3-3 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
  • Examples 4-1 to 4-13, Comparative Examples 4-1 to 4-3 (EUV exposure; negative pattern formation)]
  • Coating composition preparation and coating of resist composition The components shown in Table 9 below are dissolved in the solvent shown in Table 9 below to prepare a solution having a solid content concentration of 1.3% by mass. Filtration through a polyethylene filter having a pore size gave resist composition solutions of Examples 4-1 to 4-13 and Comparative Examples 4-1 to 4-3.
  • the numerical value in the solvent of the following Table 9 shows content with respect to the whole quantity of a solvent with the mass%.
  • resist composition solutions were 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 100 ° C. for 60 seconds. A resist film having a thickness of 40 nm was obtained.
  • HMDS hexamethyldisilazane
  • the resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount showing the above sensitivity.
  • Examples 4-1 to 4-13 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 4-1 to 4-4 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
  • compositions of the examples in Table 9 are exposed to EUV, the same effect can be obtained by mixing isoamyl acetate with 50:50 parts by mass of diisobutyl ketone and isoamyl acetate.
  • the same effect can be obtained even if the rinsing liquid is a mixture of 40:60 parts by mass of undecane and diisobutyl ketone.
  • Example 5-1 to 5-13 Comparative Examples 5-1 to 5-2 (electron beam (EB) exposure; positive pattern formation)
  • the components shown in Table 11 below were dissolved in the solvent shown in Table 11 below to prepare a solution having a solid content concentration of 4.0% by mass, and this was filtered through a polyethylene filter having a pore size of 0.02 ⁇ m.
  • Example 5 Resist composition solutions of -1 to 5-13 and Comparative Examples 5-1 to 5-2 were obtained.
  • the numerical values for the solvents in Table 11 below indicate the content of the solvent with respect to the total amount in mass%. Except for using these resist compositions, coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1. The results are shown in Table 12 below.
  • Examples 5-1 to 5-13 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 5-1 to 5-5 using a resist composition not containing the compound. Compared to -2, it was found that in the formation of an ultrafine pattern, a pattern excellent in all of sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
  • the same performance is exhibited even when the developer and the rinsing liquid are changed within the above-described preferable range.
  • the same performance is exhibited even when two or more types of developer and two or more types of rinse solutions are mixed and used.
  • the same effect is acquired even if it provides the topcoat demonstrated in the form for inventing on a resist film.
  • an actinic ray or radiation sensitive composition, and a resist film, a pattern formation method, and an electronic device manufacturing method using the same can be provided.

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Abstract

Provided is an active-light-sensitive or radiation-sensitive composition that contains (A) a compound having two or more of the structures represented by general formula (1), the compound not having an acid crosslinking group, and (B) a resin, said composition making it possible to form a pattern having exceptional sensitivity, resolution, roughness performance, and pattern cross-section shape, particularly when ultrafine patterns (e.g., having a line width of 50 nm or less) are formed. Also provided are a resist film in which the active-light-sensitive or radiation-sensitive composition is used, a pattern formation method, and a method for manufacturing an electronic device. In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. ＊represents a bond.

Description

感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法Actinic ray or radiation sensitive composition, and resist film, pattern forming method and electronic device manufacturing method using the same
　本発明は、感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法に関する。
　より詳細には、本発明は、ＩＣ等の半導体製造工程、液晶及びサーマルヘッド等の回路基板の製造、更にはその他のフォトファブリケーションのリソグラフィー工程などに使用される、感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法に関する。 The present invention relates to an actinic ray-sensitive or radiation-sensitive composition, and a resist film, a pattern forming method and an electronic device manufacturing method using the same.
More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive material used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and a photolithographic lithography process. The present invention relates to a composition, and a resist film, a pattern forming method, and an electronic device manufacturing method using the composition.
　従来、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ、集積回路）やＬＳＩ（Ｌａｒｇｅ　Ｓｃａｌｅ　Ｉｎｔｅｇｒａｔｅｄ　ｃｉｒｃｕｉｔ、大規模集積回路）などの半導体デバイスの製造プロセスにおいては、フォトレジスト組成物を用いたリソグラフィーによる微細加工が行われている。
　集積回路の高集積化に伴い、サブミクロン領域やクオーターミクロン領域の超微細パターン形成が要求されるようになってきている。それに伴い、露光波長もｇ線からｉ線に、更にエキシマレーザー光（ＫｒＦ、ＡｒＦ）に、というように短波長化の傾向が見られる。更には、現在では、エキシマレーザー光以外にも、電子線やＸ線、あるいはＥＵＶ光（Ｅｘｔｒｅｍｅ　Ｕｌｔｒａ　Ｖｉｏｌｅｔ、極紫外線）を用いたリソグラフィーも開発が進んでいる。
　このような現状のもと、レジスト組成物として、種々の構成が提案されており、例えば、樹脂及び光酸発生剤に加えて、特定の添加剤を含有するレジスト組成物も知られている（特許文献１参照）。 Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), fine processing by lithography using a photoresist composition has been performed.
With the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Accordingly, there is a tendency for the exposure wavelength to be shortened from g-line to i-line and further to excimer laser light (KrF, ArF). Further, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light (Extreme Ultra Violet, extreme ultraviolet rays) is now under development.
Under such circumstances, various configurations have been proposed as resist compositions. For example, resist compositions containing specific additives in addition to resins and photoacid generators are also known ( Patent Document 1).
日本国特許第５６４４７６４号Japanese Patent No. 5644764
　しかしながら、昨今、各種電子機器についてさらなる高機能化が要求されるなか、より微細な配線の作製が求められており、これに伴って、感度、解像性、ラフネス性能及びパターン断面形状等の諸性能の更なる向上が求められている。
　そこで、本発明は、特に、超微細（例えば、線幅５０ｎｍ以下）のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成することができる、感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法を提供することを目的とする。 However, in recent years, various electronic devices have been required to have higher functions, and therefore, finer wirings have been required. Accordingly, sensitivity, resolution, roughness performance, pattern cross-sectional shape, etc. There is a need for further improvements in performance.
Therefore, the present invention can form a pattern excellent in all of sensitivity, resolution, roughness performance, and pattern cross-sectional shape particularly in the formation of an ultrafine pattern (for example, a line width of 50 nm or less). An object is to provide an actinic ray or radiation sensitive composition, and a resist film, a pattern forming method, and an electronic device manufacturing method using the same.
　本発明者らは、鋭意検討した結果、特定の化合物を含有する感活性光線又は感放射線性組成物により上記目的が達成されることを見出した。 As a result of intensive studies, the present inventors have found that the above object can be achieved by an actinic ray-sensitive or radiation-sensitive composition containing a specific compound.
　即ち、本発明は以下の通りである。 That is, the present invention is as follows.
〔１〕
　（Ａ）下記一般式（１）で表される構造を２個以上有し、酸架橋性基を有さない化合物、及び、活性光線又は放射線により酸を発生する化合物を含有する、感活性光線又は感放射線性組成物。
Figure JPOXMLDOC01-appb-C000004
 
式中、Ｘは、酸素原子又は硫黄原子を表し、Ｒは、水素原子又は１価の有機基を表す。＊は、結合手を表す。
〔２〕
　上記一般式（１）における複数個のＲの内の少なくとも１つが水素原子である、〔１〕に記載の感活性光線又は感放射線性組成物。
〔３〕
　上記化合物（Ａ）が、上記一般式（１）で表される構造として、下記一般式（２）で表される構造を有する、〔１〕又は〔２〕に記載の感活性光線又は感放射線性組成物。
Figure JPOXMLDOC01-appb-C000005
 
式中、Ｘ及びＲは、それぞれ、上記一般式（１）におけるＸ及びＲと同義である。Ａは、－ＮＲ’－又は酸素原子を表す。Ｒ’は、水素原子又は１価の有機基を表す。＊は、結合手を表す。
〔４〕
　上記化合物（Ａ）の分子量が４５０以上である、〔１〕～〔３〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔５〕
　上記化合物（Ａ）が、芳香族基を有する、〔１〕～〔４〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔６〕
　上記化合物（Ａ）の共役酸のｐＫａが１以下である、〔１〕～〔５〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔７〕
　上記化合物（Ａ）が、極性基が酸の作用により分解し脱離する脱離基で保護された構造を有さない、〔１〕～〔６〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔８〕
　上記化合物（Ａ）が、上記一般式（１）で表される構造を３個以上有する、〔１〕～〔７〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔９〕
　上記化合物（Ａ）が、下記一般式（ａ）で表される化合物である、〔８〕に記載の感活性光線又は感放射線性組成物。
Figure JPOXMLDOC01-appb-C000006
 
　Ｌは３価の連結基を表し、Ｙ１、Ｙ２及びＹ３は、それぞれ独立して、上記一般式（１）で表される構造を有する１価の有機基を表す。
〔１０〕
　上記化合物（Ａ）が、重合体である、〔１〕～〔９〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔１１〕
　樹脂（Ｂ）を更に含有し、上記化合物（Ａ）の含有量が、上記樹脂（Ｂ）の含有量に対して１～３０質量％である、〔１〕～〔１０〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔１２〕
　樹脂（Ｂ）を更に含有し、上記樹脂（Ｂ）が、芳香族基を有する、〔１〕～〔１１〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔１３〕
　架橋剤（Ｃ）を更に含有する、〔１〕～〔１２〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔１４〕
　疎水性樹脂（Ｄ）を更に含有する、〔１〕～〔１３〕のいずれか１項に記載の感活性光線又は感放射線性組成物。
〔１５〕
　〔１〕～〔１４〕のいずれか１項に記載の感活性光線又は感放射線性組成物により形成されたレジスト膜。
〔１６〕
　〔１５〕に記載のレジスト膜に活性光線又は放射線を照射することと、上記活性光線又は放射線を照射した膜を現像することとを含むパターン形成方法。
〔１７〕
　上記活性光線又は放射線を照射した膜を、有機溶剤を含有する現像液により現像して、ネガ型パターンを形成する、〔１６〕に記載のパターン形成方法。
〔１８〕
　〔１６〕又は〔１７〕に記載のパターン形成方法を含む、電子デバイスの製造方法。 [1]
(A) An actinic ray containing a compound having two or more structures represented by the following general formula (1), having no acid crosslinkable group, and a compound capable of generating an acid by actinic rays or radiation. Or a radiation sensitive composition.
Figure JPOXMLDOC01-appb-C000004

In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
[2]
The actinic ray-sensitive or radiation-sensitive composition according to [1], wherein at least one of the plurality of Rs in the general formula (1) is a hydrogen atom.
[3]
The actinic ray-sensitive or radiation-sensitive compound according to [1] or [2], wherein the compound (A) has a structure represented by the following general formula (2) as a structure represented by the general formula (1). Sex composition.
Figure JPOXMLDOC01-appb-C000005

In formula, X and R are synonymous with X and R in the said General formula (1), respectively. A represents —NR′— or an oxygen atom. R ′ represents a hydrogen atom or a monovalent organic group. * Represents a bond.
[4]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [3], wherein the molecular weight of the compound (A) is 450 or more.
[5]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [4], wherein the compound (A) has an aromatic group.
[6]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [5], wherein the pKa of the conjugate acid of the compound (A) is 1 or less.
[7]
The actinic ray according to any one of [1] to [6], wherein the compound (A) does not have a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid Or a radiation sensitive composition.
[8]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [7], wherein the compound (A) has three or more structures represented by the general formula (1).
[9]
The actinic ray-sensitive or radiation-sensitive composition according to [8], wherein the compound (A) is a compound represented by the following general formula (a).
Figure JPOXMLDOC01-appb-C000006

L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the general formula (1).
[10]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [9], wherein the compound (A) is a polymer.
[11]
Any one of [1] to [10], further comprising a resin (B), wherein the content of the compound (A) is 1 to 30% by mass with respect to the content of the resin (B). The actinic ray-sensitive or radiation-sensitive composition described in 1.
[12]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [11], further comprising a resin (B), wherein the resin (B) has an aromatic group.
[13]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [12], further comprising a crosslinking agent (C).
[14]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [13], further comprising a hydrophobic resin (D).
[15]
[1] A resist film formed of the actinic ray-sensitive or radiation-sensitive composition according to any one of [14].
[16]
[15] A pattern forming method comprising irradiating the resist film according to [15] with actinic rays or radiation and developing the film irradiated with the actinic rays or radiation.
[17]
The pattern forming method according to [16], wherein the film irradiated with the actinic ray or radiation is developed with a developer containing an organic solvent to form a negative pattern.
[18]
The manufacturing method of an electronic device containing the pattern formation method as described in [16] or [17].
　本発明によれば、特に、超微細（例えば、線幅５０ｎｍ以下）のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成することができる、感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法を提供する。 According to the present invention, it is possible to form a pattern that is excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape, particularly in the formation of an ultrafine pattern (for example, a line width of 50 nm or less). Provided are an actinic ray or radiation sensitive composition, and a resist film, a pattern forming method and an electronic device manufacturing method using the same.
　以下に、本発明を実施するための形態の一例を説明する。
　本明細書に於ける基（原子団）の表記に於いて、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線（ＥＢ）等を意味する。また、本発明において光とは、活性光線又は放射線を意味する。
　また、本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、極紫外線、Ｘ線、ＥＵＶ光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
　本明細書において、樹脂の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、及び分散度（Ｍｗ／Ｍｎ）は、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）装置（東ソー製ＨＬＣ－８１２０ＧＰＣ）によるＧＰＣ測定（溶媒：テトラヒドロフラン、流量（サンプル注入量）：１０μｌ、カラム：東ソー社製ＴＳＫ　ｇｅｌ　Ｍｕｌｔｉｐｏｒｅ　ＨＸＬ－Ｍ（×４本）、カラム温度：４０℃、流速：１．０ｍＬ／分、検出器：示差屈折率（ＲＩ）検出器）によるポリスチレン換算値として定義される。 Below, an example of the form for implementing this invention is demonstrated.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, 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).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin are measured by GPC (solvent) using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation). : Tetrahydrofuran, flow rate (sample injection amount): 10 μl, column: TSK gel Multipore HXL-M (× 4) manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index ( RI) is defined as the polystyrene equivalent value by the detector).
　本発明の感活性光線又は感放射線性組成物は、（Ａ）下記一般式（１）で表される構造を２個以上有し、酸架橋性基を有さない化合物、及び、活性光線又は放射線により酸を発生する化合物を含有する。 The actinic ray-sensitive or radiation-sensitive composition of the present invention comprises (A) a compound having two or more structures represented by the following general formula (1) and having no acid crosslinkable group, and actinic rays or Contains compounds that generate acid by radiation.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
式中、Ｘは、酸素原子又は硫黄原子を表し、Ｒは、水素原子又は１価の有機基を表す。＊は、結合手を表す。 In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
　これにより、特に、超微細（例えば、線幅５０ｎｍ以下）のパターン形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できる理由は定かではないが、以下を推定している。 Thereby, in particular, in the formation of ultrafine patterns (for example, a line width of 50 nm or less), the reason why an excellent pattern can be formed in all of sensitivity, resolution, roughness performance, and pattern cross-sectional shape is not clear. Estimated.
　先ず、上記一般式（１）におけるＮＣ（＝Ｘ）で表される構造は、窒素原子の存在等の理由により、例えば、エステル結合と比較して極性が高い。また、化合物（Ａ）は、このような高極性の構造を２個以上有するものである。
　よって、形成されたパターンにおいて、化合物（Ａ）は非常に高い極性の場を、複数個で提供することになり、その結果、このような高極性場を介して樹脂同士が相互作用することにより、化合物（Ａ）と本発明の感活性光線又は感放射線性組成物が含み得る樹脂（Ｂ）とからなる疑似的な架橋構造が形成されるものと考えられる。
　そして、上記疑似的な架橋構造によって、パターンを構成する成分の凝集性が向上することにより、超微細（例えば、線幅５０ｎｍ以下）のパターンにおいても、パターンの破壊等が生じ難くなり、解像性が向上し、パターン断面形状がより優れたものと推察される。
　また、パターンにおける、樹脂（Ｂ）の凝集性の向上により、化学増幅型レジスト膜の露光部にて発生した酸が、未露光部に拡散しすぎることが抑制された結果、ラフネス性能が優れたものと推察される。
　また、上記のように、化合物（Ａ）は、非常に高い極性を呈する。その結果、化合物（Ａ）と基板とが、より強固に密着することにより、パターンと基板との密着性が向上し、パターンの倒れがより発生し難くなったことも、解像性が向上した理由として考えられる。
　また、露光部は、上記擬似的な架橋が一部破壊され、添加剤が樹脂の可塑剤となる。その結果、露光部内における酸の拡散速度が上がり、感度が向上したと推察される。
　更に、化合物（Ａ）は、酸架橋性基を有さない。これにより、ポジ型のパターン形成においてもネガ化することがない。また、分解物が生成しにくいため、樹脂（Ｂ）の過疎化によるＴｇ低下が起こらず、上記擬似架橋の効果がより発揮されるものと考えられる。 First, the structure represented by NC (= X) in the general formula (1) has a higher polarity than, for example, an ester bond due to the presence of a nitrogen atom or the like. The compound (A) has two or more such highly polar structures.
Therefore, in the formed pattern, the compound (A) provides a plurality of very high polar fields, and as a result, the resins interact with each other through such high polar fields. It is considered that a pseudo-crosslinked structure composed of the compound (A) and the resin (B) that can be contained in the actinic ray-sensitive or radiation-sensitive composition of the present invention is formed.
Further, the above-described pseudo cross-linking structure improves the cohesiveness of the components constituting the pattern, so that even in an ultrafine pattern (for example, a line width of 50 nm or less), pattern destruction or the like hardly occurs, and resolution is achieved. It is presumed that the cross-sectional shape is improved and the pattern cross-sectional shape is more excellent.
In addition, by improving the cohesiveness of the resin (B) in the pattern, the acid generated in the exposed portion of the chemically amplified resist film was suppressed from diffusing too much into the unexposed portion, resulting in excellent roughness performance. Inferred.
Moreover, as described above, the compound (A) exhibits a very high polarity. As a result, since the compound (A) and the substrate are more firmly adhered to each other, the adhesion between the pattern and the substrate is improved, and the resolution of the pattern is less likely to occur. Possible reason.
In the exposed portion, the pseudo-crosslinking is partially broken, and the additive becomes a plasticizer for the resin. As a result, it is presumed that the acid diffusion rate in the exposed area was increased and the sensitivity was improved.
Furthermore, the compound (A) does not have an acid crosslinkable group. Thus, there is no negative even in the formation of a positive type pattern. Moreover, since it is difficult to produce decomposition products, it is considered that the Tg reduction due to the depopulation of the resin (B) does not occur and the effect of the pseudo-crosslinking is more exhibited.
　＜感活性光線又は感放射線性組成物＞
　次に、本発明のパターン形成方法で用いられる感活性光線又は感放射線性組成物について説明する。
　本発明の感活性光線又は感放射線性組成物は、ＡｒＦエキシマレーザー、電子線又は極紫外線露光用であることが好ましい。
　本発明の感活性光線又は感放射線性組成物は、レジスト組成物であることが好ましく、ポジ型のレジスト組成物であっても、ネガ型のレジスト組成物であってもよく、また、アルカリ現像用のレジスト組成物であっても、有機溶剤現像用のレジスト組成物であってもよい。
　また本発明の感活性光線又は感放射線性組成物は、典型的には化学増幅型のレジスト組成物である。 <Actinic ray-sensitive or radiation-sensitive composition>
Next, the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention will be described.
The actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably for ArF excimer laser, electron beam or extreme ultraviolet exposure.
The actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition, or an alkali development. Or a resist composition for organic solvent development.
The actinic ray-sensitive or radiation-sensitive composition of the present invention is typically a chemically amplified resist composition.
　以下、本発明の感活性光線又は感放射線性組成物における各成分について詳細に説明する。 Hereinafter, each component in the actinic ray-sensitive or radiation-sensitive composition of the present invention will be described in detail.
＜（Ａ）一般式（１）で表される構造を２個以上有し、酸架橋性基を有さない化合物＞
　上記したように、本発明の感活性光線又は感放射線性組成物は、（Ａ）下記一般式（１）で表される構造を２個以上有し、酸架橋性基を有さない化合物（以下、化合物（Ａ）とも言う）を含有する。 <(A) Compound having two or more structures represented by formula (1) and having no acid crosslinkable group>
As described above, the actinic ray-sensitive or radiation-sensitive composition of the present invention is (A) a compound having two or more structures represented by the following general formula (1) and having no acid crosslinkable group ( Hereinafter, the compound (A) is also contained.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
式中、Ｘは、酸素原子又は硫黄原子を表し、Ｒは、水素原子又は１価の有機基を表す。＊は、結合手を表す。 In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
　上記の通り、化合物（Ａ）は、酸架橋性基を有さない。すなわち、化合物（Ａ）は、架橋剤ではなく、後述の架橋剤（Ｃ）に相当するものではない。ここで、酸架橋性基としては、公知のものが挙げられ、代表的には、ヒドロキシメチル基及びアルコキシメチル基が挙げられる。
　よって、本発明の感活性光線又は感放射線性組成物が樹脂（Ｂ）を含有する場合、化合物（Ａ）は、酸の作用により樹脂（Ｂ）と架橋するものではない。 As described above, the compound (A) does not have an acid crosslinkable group. That is, the compound (A) is not a crosslinking agent and does not correspond to a crosslinking agent (C) described later. Here, as an acid crosslinkable group, a well-known thing is mentioned, A hydroxymethyl group and an alkoxymethyl group are mentioned typically.
Therefore, when the actinic ray-sensitive or radiation-sensitive composition of the present invention contains the resin (B), the compound (A) is not crosslinked with the resin (B) by the action of an acid.
　また、一般式（１）における複数個のＲの内の少なくとも１つが水素原子であることが好ましい。
　複数個のＲの内の少なくとも１つが水素原子であることにより、一般式（１）で表される構造の高い極性が損なわれにくく、本発明の効果を充分に発現することができる。 Moreover, it is preferable that at least one of the plurality of Rs in the general formula (1) is a hydrogen atom.
When at least one of the plurality of Rs is a hydrogen atom, the high polarity of the structure represented by the general formula (1) is not easily lost, and the effects of the present invention can be sufficiently exhibited.
　Ｒとしての１価の有機基としては、好ましくは炭素数１～３０であり、例えば、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基などを挙げることができる。これらの基は更に置換基を有していてもよい。
　置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、アルコキシカルボニル基（炭素数２～６）などが挙げられ、炭素数８以下が好ましい。 The monovalent organic group as R preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.
Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like. C8 or less is preferable.
　Ｒとしての１価の有機基は、アルキル基であることが好ましく、より好ましくは炭素数１～２０の直鎖及び分岐アルキル基である。アルキル基は、アルキル鎖中に酸素原子、硫黄原子、窒素原子を有していてもよい。 The monovalent organic group as R is preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
　化合物（Ａ）は、酸の作用により塩基を発生する基を有さないことが好ましい。 Compound (A) preferably has no group capable of generating a base by the action of an acid.
　化合物（Ａ）は、一般式（１）で表される構造として、下記一般式（２）で表される構造を有する化合物であることが好ましい。 The compound (A) is preferably a compound having a structure represented by the following general formula (2) as a structure represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
式中、Ｘ及びＲは、それぞれ、上記一般式（１）におけるＸ及びＲと同義である。Ａは、－ＮＲ’－又は酸素原子を表す。Ｒ’は、水素原子又は１価の有機基を表す。＊は、結合手を表す。 In formula, X and R are synonymous with X and R in the said General formula (1), respectively. A represents —NR′— or an oxygen atom. R 'represents a hydrogen atom or a monovalent organic group. * Represents a bond.
　Ｒ’としての１価の有機基の具体例及び好ましい例は、Ｒとしての１価の有機基について上述したものと同様である。 Specific examples and preferred examples of the monovalent organic group as R ′ are the same as those described above for the monovalent organic group as R ′.
　化合物（Ａ）は、一般式（１）又は（２）で表される構造として、アミド基（一般式（１）においてＸが酸素原子を表す）、ウレア基（一般式（２）においてＸが酸素原子を表し、Ａが－ＮＲ’－を表す）又はウレタン基（一般式（２）においてＸが酸素原子を表し、Ａが－酸素原子を表す）を有することが好ましい。 Compound (A) has a structure represented by general formula (1) or (2) as an amide group (X represents an oxygen atom in general formula (1)), urea group (X in general formula (2) It preferably represents an oxygen atom, A represents —NR′—, or a urethane group (in the general formula (2), X represents an oxygen atom and A represents an —oxygen atom).
　化合物（Ａ）の共役酸のｐＫａは１以下であることが好ましい。これにより、露光部において光酸発生剤から発生する酸が、化合物（Ａ）により中和されにくくなり、酸の作用に基づく所望の反応が充分に進行するため、感度が低下し難くなるためである。 The pKa of the conjugate acid of the compound (A) is preferably 1 or less. As a result, the acid generated from the photoacid generator in the exposed area is less likely to be neutralized by the compound (A), and the desired reaction based on the action of the acid proceeds sufficiently, so that the sensitivity is unlikely to decrease. is there.
　化合物（Ａ）は、芳香族基を有することも好ましく、これにより、パターンを構成する成分の凝集性が更に高まり、解像性やラフネス性能がより良化する傾向となる。
　この場合、化合物（Ａ）は、一般式（１）又は（２）で表される構造内に、芳香族基を有していても良く、一般式（１）又は（２）で表される構造外に、芳香族基を有していても良い。前者の場合、芳香族基は、一般式（１）のＲ、及び、一般式（２）のＲ及びＲ’の少なくとも一方に、それぞれ、包含される。 The compound (A) also preferably has an aromatic group, whereby the cohesiveness of the components constituting the pattern is further increased, and the resolution and roughness performance tend to be improved.
In this case, the compound (A) may have an aromatic group in the structure represented by the general formula (1) or (2), and is represented by the general formula (1) or (2). It may have an aromatic group outside the structure. In the former case, the aromatic group is included in at least one of R in the general formula (1) and R and R ′ in the general formula (2).
　また、特にポジ型パターンを形成する場合、一般式（１）のＲ、及び、一般式（２）のＲ及びＲ’の少なくとも一方は、電子求引性基を有する１価の有機基であることも好ましい。これにより、露光部においては、一般式（１）又は（２）で表される構造における－ＮＲ－と－ＣＸ－間の結合が、光酸発生剤から発生する酸によって切断され、レジスト膜を構成する成分の凝集が解除される傾向となり、露光部が現像されやすくなるためである。 In particular, when a positive pattern is formed, at least one of R in the general formula (1) and R and R ′ in the general formula (2) is a monovalent organic group having an electron withdrawing group. It is also preferable. Thereby, in the exposed portion, the bond between —NR— and —CX— in the structure represented by the general formula (1) or (2) is cleaved by the acid generated from the photoacid generator, and the resist film is removed. This is because aggregation of constituent components tends to be released and the exposed portion is easily developed.
　電子求引性基としては、ハメット則のσｐ値が０以上である基が好ましい。σｐ値が正の置換基としては、フッ素（０．０６）、塩素（０．３０）、臭素（０．２７）、ヨウ素（０．３０）等のハロゲン原子、－ＣＨＯ（０．２２）、－ＣＯＣＨ３（０．５０）、－ＣＯＣ６Ｈ５（０．４６）、－ＣＯＮＨ２（０．３６）、－ＣＯＯ－（０．３０）、－ＣＯＯＨ（０．４１）、－ＣＯＯＣＨ３（０．３９）、－ＣＯＯＣ２Ｈ５（０．４５）等のカルボニルを有する基、－ＳＯＣＨ３（０．４９）、－ＳＯ２ＣＨ３（０．７２）、－ＳＯ２Ｃ６Ｈ５（０．６８）、－ＳＯ２ＣＦ３（０．９３）、－ＳＯ２ＮＨ２（０．５７）、－ＳＯ２ＯＣ６Ｈ５（０．２３）、－ＳＯ３－（０．０９）、－ＳＯ３Ｈ（０．５０）等のスルホニル若しくはスルフィニルを有する基、－ＣＮ（０．６６）、－ＮＯ２（０．７８）、－Ｎ（ＣＨ３）３＋（０．８２）、－Ｎ（ＣＦ３）２（０．５３）等の含窒素置換基、－ＣＣｌ３（０．４６）、－ＣＨ２Ｃｌ（０．１８）、－ＣＨＣｌ２（０．３２）、－ＣＦ３（０．５４）等のハロゲン原子置換アルキル基が挙げられる。ここで、カッコ内の数値はσｐ値である。
　ハメットのσｐ値は、例えば、Ｃ．Ｈａｒｓｃｈ他、Ｊ．Ｍｅｄ．Ｃｈｅｍ．，１６，１２０７（１９７３）、同，２０，３０４（１９７７）、Ｃｈｅｍ．Ｒｅｖ．９１，１６５（１９９１）などにも記載されている。 The electron withdrawing group is preferably a group having a Hammett's rule σp value of 0 or more. Examples of the substituent having a positive σp value include halogen atoms such as fluorine (0.06), chlorine (0.30), bromine (0.27) and iodine (0.30), —CHO (0.22), —COCH 3 (0.50), —COC 6 H 5 (0.46), —CONH 2 (0.36), —COO— (0.30), —COOH (0.41), —COOCH 3 ( 0.39), a group having a carbonyl such as —COOC 2 H 5 (0.45), —SOCH 3 (0.49), —SO 2 CH 3 (0.72), —SO 2 C 6 H 5 ( 0.68), —SO 2 CF 3 (0.93), —SO 2 NH 2 (0.57), —SO 2 OC 6 H 5 (0.23), —SO 3 — (0.09), —SO 3 H (0.50) sulfonyl or a group having a sulfinyl, such as, -CN (0.66), - O 2 (0.78), - N (CH 3) 3 + (0.82), - N (CF 3) 2 (0.53) nitrogen-containing substituents such as, -CCl 3 (0.46), And halogen atom-substituted alkyl groups such as —CH 2 Cl (0.18), —CHCl 2 (0.32), and —CF 3 (0.54). Here, the numerical value in parentheses is the σp value.
Hammett's σp value is, for example, C.I. Harsch et al. Med. Chem. 16, 1207 (1973), 20, 304 (1977), Chem. Rev. 91, 165 (1991).
　また、化合物（Ａ）は、極性基が酸の作用により分解し脱離する脱離基で保護された構造（酸分解性基）を有していても有さなくてもよいが、特に、ネガ型パターンを形成する場合においては、化合物（Ａ）は、酸分解性基を有さないことが好ましい。これにより、露光部において、化合物（Ａ）が、光酸発生剤から発生する酸により分解されず、パターンを構成する成分の凝集性が低下しない傾向となり、優れた解像性とラフネス性能とが得られやすいためである。 Further, the compound (A) may or may not have a structure (acid-decomposable group) protected with a leaving group that is decomposed and eliminated by the action of an acid. In the case of forming a negative pattern, the compound (A) preferably has no acid-decomposable group. As a result, in the exposed area, the compound (A) is not decomposed by the acid generated from the photoacid generator, and the cohesiveness of the components constituting the pattern tends not to decrease, and excellent resolution and roughness performance are obtained. It is because it is easy to obtain.
　化合物（Ａ）は、一般式（１）で表される構造を３個以上有することも好ましい。 The compound (A) preferably has three or more structures represented by the general formula (1).
　この場合、化合物（Ａ）は、下記一般式（ａ）で表される化合物であることが好ましい。 In this case, the compound (A) is preferably a compound represented by the following general formula (a).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　Ｌは３価の連結基を表し、Ｙ１、Ｙ２及びＹ３は、それぞれ独立して、上記一般式（１）で表される構造を有する１価の有機基を表す。 L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the general formula (1).
　Ｙ１、Ｙ２及びＹ３としての１価の有機基は、好ましくは炭素数１～３０であり、例えば、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、アルコキシ基、アリールオキシ基などを挙げることができる。これらの基は更に置換基を有していてもよい。
　置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、アルコキシカルボニル基（炭素数２～６）などが挙げられ、炭素数８以下が好ましい。 The monovalent organic group as Y 1 , Y 2 and Y 3 preferably has 1 to 30 carbon atoms. For example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryloxy group Examples include groups. These groups may further have a substituent.
Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like. C8 or less is preferable.
　一般式（１）で表される構造を有する１価の有機基は、典型的には、基中に、一般式（１）で表される構造を有するものであり、この場合、上記１価の有機基の具体例においては、１価の有機基を構成する原子（典型的には、炭素原子）が、一般式（１）で表される構造に置き換えられてなるものである。 The monovalent organic group having a structure represented by the general formula (1) typically has a structure represented by the general formula (1) in the group. In the specific example of the organic group, an atom (typically a carbon atom) constituting the monovalent organic group is replaced with a structure represented by the general formula (1).
　Ｌとしての３価の連結基の具体例としては、上記したＹ１、Ｙ２及びＹ３としての１価の有機基の具体例から、更に、２個の水素原子が除去された基を挙げることができる。 Specific examples of the trivalent linking group as L include groups in which two hydrogen atoms are further removed from the specific examples of the monovalent organic group as Y 1 , Y 2 and Y 3 described above. be able to.
　化合物（Ａ）は、低分子化合物の形態であっても良く、重合体の形態（重合体（典型的には、重合体の一部）に組み込まれた形態）であっても良い。また、低分子化合物の形態と重合体の形態を併用しても良い。
　化合物（Ａ）が、低分子化合物の形態である場合、実質的に、分子量分布を有さないことが好ましい。
　また、化合物（Ａ）が、低分子化合物の形態である場合、現像欠陥の発生が抑制されるという観点から、分子量が３０００以下であることが好ましく、分子量が２０００以下であることがより好ましく、１５００以下であることが更に好ましく、１０００以下であることが最も好ましい。また、化合物（Ａ）の揮発が抑制されるという観点から、化合物（Ａ）の分子量は、４５０以上であることが好ましい。 The compound (A) may be in the form of a low molecular compound or may be in the form of a polymer (a form incorporated in a polymer (typically part of the polymer)). Moreover, you may use together the form of a low molecular compound, and the form of a polymer.
When the compound (A) is in the form of a low molecular compound, it is preferable that the compound (A) has substantially no molecular weight distribution.
In addition, when the compound (A) is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, from the viewpoint of suppressing the occurrence of development defects. More preferably, it is 1500 or less, and most preferably 1000 or less. Moreover, it is preferable that the molecular weight of a compound (A) is 450 or more from a viewpoint that volatilization of a compound (A) is suppressed.
　化合物（Ａ）としては、カーバメート系化合物（カーバメート結合を有する化合物）、ウレア系化合物（ウレア結合を有する化合物）、アミド系化合物（アミド結合を有する化合物）、バルビツール酸系化合物（バルビツール酸構造を有する化合物）、イミド系化合物（イミド結合を有する化合物）、シアヌル酸系化合物（シアヌル酸構造を有する化合物）を挙げることができる。 As the compound (A), carbamate compounds (compounds having carbamate bonds), urea compounds (compounds having urea bonds), amide compounds (compounds having amide bonds), barbituric acid compounds (barbituric acid structure) A compound having a cyanuric acid structure), an imide compound (a compound having an imide bond), and a cyanuric acid compound (a compound having a cyanuric acid structure).
　化合物（Ａ）の具体例を以下に示すが、本発明は、これに限定されるものではない。 Specific examples of the compound (A) are shown below, but the present invention is not limited thereto.
〔カーバメート系化合物〕 [Carbamate compounds]
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
〔ウレア系化合物〕 [Urea compounds]
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
〔アミド系化合物〕 [Amide compounds]
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
〔バルビツール酸系化合物〕 [Barbituric acid compounds]
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
〔イミド系化合物〕 [Imide compound]
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
〔シアヌル酸系化合物〕 [Cyanuric acid compounds]
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　以下、化合物（Ａ）の具体例の代表的なものについて、分子量とｐＫａを示す。 Hereinafter, molecular weight and pKa are shown for typical examples of the compound (A).
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　化合物（Ａ）が重合体の形態である場合、化合物（Ａ）は、後述の樹脂（Ｂ）中に組み込まれていても良い。
　化合物（Ａ）が重合体の形態である場合、化合物（Ａ）は、下記一般式（Ｉ）又は（ＩＩ）で表される繰り返し単位を有することも好ましい。 When the compound (A) is in the form of a polymer, the compound (A) may be incorporated in the resin (B) described later.
When compound (A) is in the form of a polymer, compound (A) also preferably has a repeating unit represented by the following general formula (I) or (II).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　一般式（Ｉ）において、
　Ｘａ１は、水素原子、置換基を有していてもよいアルキル基を表す。
　Ｔは、単結合又は２価の連結基を表す。複数のＴは、互いに同一であっても異なっていてもよい。
　Ａは、上記一般式（１）で表される構造を有する基を表す。 In general formula (I):
Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group. Several T may mutually be same or different.
A represents a group having a structure represented by the general formula (1).
　Ｘａ１により表される、置換基を有していてもよいアルキル基としては、例えば、メチル基又は－ＣＨ２－Ｒ１１で表される基が挙げられる。Ｒ１１は、ハロゲン原子（フッ素原子など）、ヒドロキシル基又は１価の有機基を表し、例えば、炭素数５以下のアルキル基、炭素数５以下のアシル基が挙げられ、好ましくは炭素数３以下のアルキル基であり、更に好ましくはメチル基である。Ｘａ１は、一態様において、好ましくは水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基等である。
　Ｔの２価の連結基としては、アルキレン基、－ＣＯＯ－Ｒｔ－基、－Ｏ－Ｒｔ－基等が挙げられる。式中、Ｒｔは、アルキレン基又はシクロアルキレン基を表す。
　Ｔは、単結合又は－ＣＯＯ－Ｒｔ－基が好ましい。Ｒｔは、炭素数１～５のアルキレン基が好ましく、－ＣＨ２－基、－（ＣＨ２）２－基、－（ＣＨ２）３－基がより好ましい。 Examples of the optionally substituted alkyl group represented by Xa 1 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. In one embodiment, 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, —COO—Rt— group, —O—Rt— group, and the like. In the formula, 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.
　一般式（ＩＩ）において、
　Ｒ６１、Ｒ６２及びＲ６３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、Ｒ６２はＡｒ６と結合して環を形成していてもよく、その場合のＲ６２は単結合又はアルキレン基を表す。
　Ｘ６は、単結合、－ＣＯＯ－、又は－ＣＯＮＲ６４－を表す。Ｒ６４は、水素原子又はアルキル基を表す。複数のＸ６は、互いに同一であっても異なっていてもよい。
　Ｌ６は、単結合又はアルキレン基を表す。
　Ａｒ６は、（ｎ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｎ＋２）価の芳香環基を表す。
　Ａは、上記一般式（１）で表される構造を有する基を表す。
　ｎは、１～４の整数を表す。ｎが２以上の整数である場合、複数のＡは、互いに同一であっても異なっていてもよい。 In general formula (II):
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. However, 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. The plurality of X 6 may be the same as or different from each other.
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.
A represents a group having a structure represented by the general formula (1).
n represents an integer of 1 to 4. When n is an integer greater than or equal to 2, several A may mutually be same or different.
　上記各基は置換基を有していてもよく、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、アルコキシカルボニル基（炭素数２～６）などが挙げられ、炭素数８以下が好ましい。 Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group. Examples thereof include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
　化合物（Ａ）は、重合体の主鎖中に組み込まれても、重合体の側鎖中に組みこまれても良いが、化合物（Ａ）が重合体の側鎖に組み込まれていると、「特に、超微細（例えば、線幅５０ｎｍ以下）のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成することができる」という本願発明の効果をより確実に発現できる傾向となるため、好ましい。 Compound (A) may be incorporated in the main chain of the polymer or in the side chain of the polymer, but when compound (A) is incorporated in the side chain of the polymer, “Especially, in the formation of an ultrafine pattern (for example, a line width of 50 nm or less), a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.” Since it tends to be expressed more reliably, it is preferable.
　一般式（１）で表される構造を有する繰り返し単位（例えば、一般式（Ｉ）又は（ＩＩ）で表される繰り返し単位）の含有量は、重合体の全繰り返し単位に対して、１～３０ｍｏｌ％であることが好ましく、５～３０ｍｏｌ％であることがより好ましく、１０～２５ｍｏｌ％であることが更に好ましい。 The content of the repeating unit having the structure represented by the general formula (1) (for example, the repeating unit represented by the general formula (I) or (II)) is 1 to It is preferably 30 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%.
　以下、化合物（Ａ）が重合体の形態における、化合物（Ａ）の具体例を示す。 Hereinafter, specific examples of the compound (A) in the form of the polymer (A) are shown.
〔カーバメート系化合物〕 [Carbamate compounds]
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
〔ウレア系化合物〕 [Urea compounds]
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
〔アミド系化合物〕 [Amide compounds]
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
〔バルビツール酸系化合物〕 [Barbituric acid compounds]
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
〔イミド系化合物〕 [Imide compound]
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
〔シアヌル酸系化合物〕 [Cyanuric acid compounds]
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　特に、化合物（Ａ）が低分子化合物の形態である場合、化合物（Ａ）の含有量は、後述の樹脂（Ｂ）の含有量に対して１～３０質量％であることが好ましく、５～３０質量％であることがより好ましく、１０～２５質量％であることが更に好ましい。 In particular, when the compound (A) is in the form of a low molecular compound, the content of the compound (A) is preferably 1 to 30% by mass with respect to the content of the resin (B) described later. It is more preferably 30% by mass, and further preferably 10 to 25% by mass.
　特に、化合物（Ａ）が低分子化合物の形態である場合、化合物（Ａ）の含有量は、感活性光線又は感放射線性組成物の全固形分に対して１～３０質量％であることが好ましく、３～２５質量％であることがより好ましく、５～２０質量％であることが更に好ましい。 In particular, when the compound (A) is in the form of a low molecular compound, the content of the compound (A) is 1 to 30% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive composition. Preferably, it is 3 to 25% by mass, more preferably 5 to 20% by mass.
　特に、化合物（Ａ）が重合体の形態である場合、化合物（Ａ）の含有量は、感活性光線又は感放射線性組成物の全固形分に対して、５０～９９．９質量％であることが好ましく、６０～９９．０質量％であることがより好ましい。
　また、化合物（Ａ）が重合体の形態である場合、化合物（Ａ）の重量平均分子量は、ＧＰＣ法によりポリスチレン換算値として、好ましくは１，０００～２００，０００であり、更に好ましくは３，０００～２０，０００、最も好ましくは５，０００～１５，０００である。化合物（Ａ）の分散度（分子量分布）は、通常１～５であり、好ましくは１～３、更に好ましくは１．２～３．０、特に好ましくは１．１～２．０の範囲のものが使用される。 In particular, when the compound (A) is in the form of a polymer, the content of the compound (A) is 50 to 99.9% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive composition. It is preferably 60 to 99.0% by mass.
When the compound (A) is in the form of a polymer, the weight average molecular weight of the compound (A) is preferably 1,000 to 200,000 as a polystyrene conversion value by GPC method, more preferably 3, 000 to 20,000, most preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of the compound (A) is usually from 1 to 5, preferably from 1 to 3, more preferably from 1.2 to 3.0, particularly preferably from 1.1 to 2.0. Things are used.
＜（Ｂ）樹脂＞
　感活性光線又は感放射線性組成物は、樹脂（Ｂ）を含有することが好ましく、樹脂（Ｂ）は、芳香族基を有することが好ましい。
　樹脂（Ｂ）は、後述の種々の繰り返し単位を有することができる。 <(B) Resin>
The actinic ray-sensitive or radiation-sensitive composition preferably contains the resin (B), and the resin (B) preferably has an aromatic group.
The resin (B) can have various repeating units described later.
〔芳香環基を有する繰り返し単位（ａ）〕
　樹脂（Ｂ）は、好ましい一実施形態において、芳香環基を有する繰り返し単位（ａ）を有する。
　芳香環基を有する繰り返し単位（ａ）としては、フェノール性水酸基を有する繰り返し単位を好適に挙げることができる。
　本明細書において、フェノール性水酸基とは、芳香環基の水素原子をヒドロキシ基で置換してなる基である。該芳香環基の芳香環は単環又は多環の芳香環であり、ベンゼン環やナフタレン環等が挙げられる。 [Repeating unit having an aromatic ring group (a)]
In a preferred embodiment, the resin (B) has a repeating unit (a) having an aromatic ring group.
As the repeating unit (a) having an aromatic ring group, a repeating unit having a phenolic hydroxyl group can be preferably exemplified.
In this specification, 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.
　特に、感活性光線又は感放射線性組成物が、電子線又は極紫外線露光用である場合や、後述の架橋剤を含有する場合（例えば、感活性光線又は感放射線性組成物が、アルカリ現像用のネガ型感活性光線又は感放射線性組成物である場合）には、樹脂（Ｂ）は、フェノール性水酸基を有する繰り返し単位を有することが好ましい。 In particular, when the actinic ray or radiation sensitive composition is for electron beam or extreme ultraviolet exposure, or contains a crosslinking agent described later (for example, the actinic ray or radiation sensitive composition is used for alkali development. In the case of a negative type actinic ray or radiation sensitive composition), the resin (B) preferably has a repeating unit having a phenolic hydroxyl group.
　フェノール性水酸基を有する繰り返し単位としては、例えば、下記一般式（Ｉ）又は（Ｉ－１）で表される繰り返し単位が挙げられる。 Examples of the repeating unit having a phenolic hydroxyl group include a repeating unit represented by the following general formula (I) or (I-1).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式中、
　Ｒ４１、Ｒ４２及びＲ４３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。但し、Ｒ４２はＡｒ４と結合して環を形成していてもよく、その場合のＲ４２は単結合又はアルキレン基を表す。
　Ｘ４は、単結合、－ＣＯＯ－、又は－ＣＯＮＲ６４－を表し、Ｒ６４は、水素原子又はアルキル基を表す。
　Ｌ４は、それぞれ独立して単結合又は２価の連結基を表す。
　Ａｒ４は、（ｎ＋１）価の芳香環基を表し、Ｒ４２と結合して環を形成する場合には（ｎ＋２）価の芳香環基を表す。
　ｎは、１～５の整数を表す。
　一般式（Ｉ）又は（Ｉ－１）の繰り返し単位を高極性化する目的では、ｎが２以上の整数、又はＸ４が－ＣＯＯ－、又は－ＣＯＮＲ６４－であることも好ましい。 Where
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. However, 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.
For the purpose of making the repeating unit of the general formula (I) or (I-1) highly polar, it is also preferable that n is an integer of 2 or more, or X 4 is —COO— or —CONR 64 —.
　一般式（Ｉ）及び（Ｉ－１）におけるＲ４１、Ｒ４２、Ｒ４３のアルキル基としては、好ましくは置換基を有していてもよいメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、ドデシル基など炭素数２０以下のアルキル基が挙げられ、より好ましくは炭素数８以下のアルキル基、特に好ましくは炭素数３以下のアルキル基が挙げられる。 In the general formulas (I) and (I-1), 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.
　一般式（Ｉ）及び（Ｉ－１）におけるＲ４１、Ｒ４２、Ｒ４３のシクロアルキル基としては、単環型でも、多環型でもよい。好ましくは置換基を有していてもよいシクロプロピル基、シクロペンチル基、シクロヘキシル基などの炭素数３～８個で単環型のシクロアルキル基が挙げられる。
　一般式（Ｉ）及び（Ｉ－１）におけるＲ４１、Ｒ４２、Ｒ４３のハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、フッ素原子が特に好ましい。
　一般式（Ｉ）及び（Ｉ－１）におけるＲ４１、Ｒ４２、Ｒ４３のアルコキシカルボニル基に含まれるアルキル基としては、上記Ｒ４１、Ｒ４２、Ｒ４３におけるアルキル基と同様のものが好ましい。 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.
As the 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. .
　上記各基における好ましい置換基としては、例えば、アルキル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、ヒドロキシル基、カルボキシル基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基、ニトロ基等を挙げることができ、置換基の炭素数は８以下が好ましい。 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.
　Ａｒ４は、（ｎ＋１）価の芳香環基を表す。ｎが１である場合における２価の芳香環基は、置換基を有していてもよく、例えば、フェニレン基、トリレン基、ナフチレン基、アントラセニレン基などの炭素数６～１８のアリーレン基、あるいは、例えば、チオフェン、フラン、ピロール、ベンゾチオフェン、ベンゾフラン、ベンゾピロール、トリアジン、イミダゾール、ベンゾイミダゾール、トリアゾール、チアジアゾール、チアゾール等のヘテロ環を含む芳香環基を好ましい例として挙げることができる。 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が２以上の整数である場合における（ｎ＋１）価の芳香環基の具体例としては、２価の芳香環基の上記した具体例から、（ｎ－１）個の任意の水素原子を除してなる基を好適に挙げることができる。
　（ｎ＋１）価の芳香環基は、更に置換基を有していてもよい。 Specific examples of the (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.
　上述したアルキル基、シクロアルキル基、アルコキシカルボニル基及び（ｎ＋１）価の芳香環基が有し得る置換基としては、例えば、一般式（Ｉ）におけるＲ４１、Ｒ４２、Ｒ４３で挙げたアルキル基、メトキシ基、エトキシ基、ヒドロキシエトキシ基、プロポキシ基、ヒドロキシプロポキシ基、ブトキシ基などのアルコキシ基；フェニル基などのアリール基；等が挙げられる。
　Ｘ４により表わされる－ＣＯＮＲ６４－（Ｒ６４は、水素原子、アルキル基を表す）におけるＲ６４のアルキル基としては、好ましくは置換基を有していてもよいメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、ドデシル基など炭素数２０以下のアルキル基が挙げられ、より好ましくは炭素数８以下のアルキル基が挙げられる。
　Ｘ４としては、単結合、－ＣＯＯ－、－ＣＯＮＨ－が好ましく、単結合、－ＣＯＯ－がより好ましい。 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.
-CONR 64 represented by X 4 - (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. Can be mentioned.
X 4 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
　Ｌ４としての２価の連結基としては、アルキレン基であることが好ましく、アルキレン基としては、好ましくは置換基を有していてもよいメチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、オクチレン基等の炭素数１～８個のものが挙げられる。
　Ａｒ４としては、置換基を有していてもよい炭素数６～１８の芳香環基がより好ましく、ベンゼン環基、ナフタレン環基、ビフェニレン環基が特に好ましい。
　一般式（Ｉ）で表される繰り返し単位は、ヒドロキシスチレン構造を備えていることが好ましい。即ち、Ａｒ４は、ベンゼン環基であることが好ましい。 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.
As 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.
　樹脂（Ｂ）が有するフェノール性水酸基を有する繰り返し単位としては、好ましくは、下記一般式（ｐ１）で表される繰り返し単位が挙げられる。 The repeating unit having a phenolic hydroxyl group contained in the resin (B) is preferably a repeating unit represented by the following general formula (p1).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　一般式（ｐ１）におけるＲは、水素原子、ハロゲン原子又は１～４個の炭素原子を有する直鎖若しくは分岐のアルキル基を表す。複数のＲは、各々同じでも異なっていてもよい。一般式（ｐ１）中のＲとしては水素原子が特に好ましい。 R in the general formula (p1) 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.
　一般式（ｐ１）におけるＡｒは芳香族環を表し、例えば、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環、フェナントレン環などの炭素数６～１８の置換基を有していてもよい芳香族炭化水素環、又は、例えば、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、チアゾール環等のヘテロ環を含む芳香環ヘテロ環を挙げることができる。中でも、ベンゼン環が最も好ましい。 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. And aromatic ring heterocycles. Of these, a benzene ring is most preferable.
　一般式（ｐ１）におけるｍは、１～５の整数を表し、好ましくは１である。 M in the general formula (p1) represents an integer of 1 to 5, preferably 1.
　以下、樹脂（Ｂ）が有するフェノール性水酸基を有する繰り返し単位の具体例を示すが、本発明は、これに限定されるものではない。式中、ａは１又は２を表す。 Hereinafter, although the specific example of the repeating unit which has the phenolic hydroxyl group which resin (B) has is shown, this invention is not limited to this. In the formula, a represents 1 or 2.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　樹脂（Ｂ）は、フェノール性水酸基を有する繰り返し単位（ａ）を１種で有していても、２種以上で有していてもよい。 Resin (B) may have one or more repeating units (a) having a phenolic hydroxyl group, or two or more.
　フェノール性水酸基を有する繰り返し単位（ａ）の含有量は、樹脂（Ｂ）の全繰り返し単位に対して、１０～９５モル％であることが好ましく、２０～９０モル％であることがより好ましく、３０～８５モル％であることが更に好ましい。 The content of the repeating unit (a) having a phenolic hydroxyl group is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, based on all repeating units of the resin (B). More preferably, it is 30 to 85 mol%.
　芳香環基を有する繰り返し単位（ａ）は、下記一般式（Ｘ）で表される繰り返し単位であってもよい。 The repeating unit (a) having an aromatic ring group may be a repeating unit represented by the following general formula (X).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　一般式（Ｘ）中、
　Ｒ６１、Ｒ６２及びＲ６３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、Ｒ６３はＡｒと結合して環を形成していてもよく、その場合のＲ６２は単結合又はアルキレン基を表す。
　Ａｒは、（ｎ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｎ＋２）価の芳香環基を表す。
　Ｒ７は、それぞれ独立に、炭素数１～１０の直鎖状、分岐状又は環状のアルキル基、アルコキシ基又はアシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ又は－ＣＯＯＲ：Ｒは炭素数１～６のアルキル基又はフッ素化アルキル基）、又はカルボキシル基を表す。
　ｎは、０以上の整数を表す。 In general formula (X),
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. However, R 63 may be bonded to Ar to form a ring, in which case R 62 represents a single bond or an alkylene group.
Ar represents an (n + 1) -valent aromatic ring group, and when bonded to R 62 to form a ring, represents an (n + 2) -valent aromatic ring group.
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.
　下記一般式（Ｘ）は、下記一般式（Ｖ）又は下記一般式（ＶＩ）で表される繰り返し単位であることも好ましい。 The following general formula (X) is also preferably a repeating unit represented by the following general formula (V) or the following general formula (VI).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式中、ｎ３は０～４の整数を表す。ｎ４は０～６の整数を表す。
　Ｘ４は、メチレン基、酸素原子又は硫黄原子である。
　Ｒ７は、上記一般式（Ｘ）のＲ７と同義である。 In the formula, 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).
　一般式（Ｘ）で表される繰り返し単位の具体例を下記に示すが、これらに限定されない。 Specific examples of the repeating unit represented by the general formula (X) are shown below, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　樹脂（Ｂ）は、一般式（Ｘ）で表される繰り返し単位（ａ）を１種で有していても、２種以上で有していてもよい。 Resin (B) may have one type of repeating unit (a) represented by general formula (X) or two or more types.
　一般式（Ｘ）で表される繰り返し単位の含有量は、樹脂（Ｂ）の全繰り返し単位に対して、５～５０モル％であることが好ましく、５～４０モル％であることがより好ましく、５～３０モル％であることが更に好ましい。 The content of the repeating unit represented by the general formula (X) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on all the repeating units of the resin (B). More preferably, it is 5 to 30 mol%.
　また、芳香環基を有する繰り返し単位（ａ）は、後述する極性基が酸の作用により分解し脱離する脱離基で保護された構造を有する繰り返し単位（ｃ）において、芳香環基を有するものであっても良い。 The repeating unit (a) having an aromatic ring group has an aromatic ring group in the repeating unit (c) having a structure in which a polar group described later is protected by a leaving group that decomposes and leaves by the action of an acid. It may be a thing.
　樹脂（Ｂ）は、芳香環基を有する繰り返し単位（ａ）を１種で有していても、２種以上で有していてもよい。 Resin (B) may have one type of repeating unit (a) having an aromatic ring group or two or more types.
　芳香環基を有する繰り返し単位（ａ）の含有量は、樹脂（Ｂ）の全繰り返し単位に対して、５～１００モル％であることが好ましく、７～９８モル％であることがより好ましく、８～９６モル％であることが更に好ましい。 The content of the repeating unit (a) having an aromatic ring group is preferably 5 to 100 mol%, more preferably 7 to 98 mol%, based on all repeating units of the resin (B), More preferably, it is 8 to 96 mol%.
〔極性基が酸の作用により分解し脱離する脱離基で保護された構造を有する繰り返し単位（ｂ）〕
　樹脂（Ｂ）は、好ましい一実施形態において、極性基が酸の作用により分解し脱離する脱離基で保護された構造を有する繰り返し単位（ｂ）を有する。
　極性基が酸の作用により分解し脱離する脱離基で保護された構造（酸分解性基）を有する繰り返し単位（ｂ）における極性基としては、カルボキシル基、アルコール性水酸基、フェノール性水酸基、及び、スルホン酸基等が挙げられる。この中でも、極性基は、カルボキシル基、アルコール性水酸基、又は、フェノール性水酸基であることが好ましく、カルボキシル基、又は、フェノール性水酸基であることが更に好ましい。
　尚、樹脂（Ｂ）が、酸分解性基を有する繰り返し単位を有すると、酸の作用によりアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
　よって、酸分解性基を有する繰り返し単位を有する樹脂（Ｂ）は、アルカリ現像液を用いたポジ型パターン形成や、有機系現像液を用いたネガ型パターン形成において、好適に用いられ得る。 [Repeating unit (b) having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid]
In a preferred embodiment, the resin (B) has a repeating unit (b) 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 (b) 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. Among these, 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.
When the resin (B) 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.
Therefore, the resin (B) having a repeating unit having an acid-decomposable group can be suitably used in the formation of a positive pattern using an alkali developer or the formation of a negative pattern using an organic developer.
　酸の作用により分解し脱離する脱離基としては、例えば、式（Ｙ１）～（Ｙ４）で表される基を挙げることができる。
式（Ｙ１）：－Ｃ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ２）：－Ｃ（＝Ｏ）ＯＣ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ３）：－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３８）
式（Ｙ４）：－Ｃ（Ｒｎ）（Ｈ）（Ａｒ） Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): —C (Rx 1 ) (Rx 2 ) (Rx 3 )
Formula (Y2): —C (═O) OC (Rx 1 ) (Rx 2 ) (Rx 3 )
Formula (Y3): —C (R 36 ) (R 37 ) (OR 38 )
Formula (Y4): —C (Rn) (H) (Ar)
　式（Ｙ１）、（Ｙ２）中、Ｒｘ１～Ｒｘ３は、各々独立に、アルキル基（直鎖若しくは分岐）又はシクロアルキル基（単環若しくは多環）を表す。ただし、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖若しくは分岐）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　より好ましくは、Ｒｘ１～Ｒｘ３が各々独立に、直鎖又は分岐のアルキル基を表す繰り返し単位であり、更に好ましくは、Ｒｘ１～Ｒｘ３が各々独立に、直鎖のアルキル基を表す繰り返し単位である。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環若しくは多環を形成してもよい。
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基などの炭素数１～４のものが好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数５～６の単環のシクロアルキル基が特に好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　一般式（Ｙ１）、（Ｙ２）で表される繰り返し単位は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 In the formulas (Y1) and (Y2), 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.
Repeat More preferably, independently is Rx 1 ~ Rx 3 each a repeating unit represents a linear or branched alkyl group, more preferably, that each independently is Rx 1 ~ Rx 3, represents 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. Groups are preferred.
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 polycyclic 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.
　式（Ｙ３）中、Ｒ３６～Ｒ３８は、各々独立に、水素原子又は１価の有機基を表す。Ｒ３７とＲ３８とは、互いに結合して環を形成してもよい。１価の有機基としては、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等が挙げられる。Ｒ３６は水素原子であることも好ましい。 In the formula (Y3), 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. Examples of 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.
　好ましい式（Ｙ３）としては下記一般式（Ｙ３－１）で表される構造がより好ましい。 As the preferred formula (Y3), a structure represented by the following general formula (Y3-1) is more preferred.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　ここで、Ｌ１及びＬ２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又はアルキレン基とアリール基とを組み合わせた基を表す。
　Ｍは、単結合又は２価の連結基を表す。
　Ｑは、アルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。
　Ｌ１及びＬ２うち少なくとも１つは水素原子であり、少なくとも１つはアルキル基、シクロアルキル基、アリール基、又はアルキレン基とアリール基とを組み合わせた基であることが好ましい。
　Ｑ、Ｍ、Ｌ１の少なくとも２つが結合して環（好ましくは、５員若しくは６員環）を形成してもよい。
　パターン倒れ性能の向上にはＬ２が２級又は３級アルキル基であることが好ましく、３級アルキル基がより好ましい。２級アルキル基は、イソプロピル基、シクロヘキシル基やノルボルニル基、３級アルキル基は、ｔｅｒｔ－ブチル基やアダマンタンを挙げることができる。これらの態様では、Ｔｇや活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。 Here, 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).
For improving the pattern collapse performance, 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. In these aspects, since Tg and activation energy become high, in addition to ensuring the film strength, fogging can be suppressed.
　式（Ｙ４）中、Ａｒは、芳香環基を表す。Ｒｎは、アルキル基、シクロアルキル基又はアリール基を表す。ＲｎとＡｒとは互いに結合して非芳香族環を形成してもよい。Ａｒはより好ましくはアリール基である。 In the formula (Y4), 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.
　樹脂（Ｂ）が有する、酸の作用により分解して極性基を生じる基を有する繰り返し単位としては、下記一般式（ＡＩ）又は（ＡＩＩ）で表される繰り返し単位が好ましい。 Resin (B) has a repeating unit represented by the following general formula (AI) or (AII) as the repeating unit having a group that decomposes by the action of an acid to generate a polar group.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　一般式（ＡＩ）において、
　Ｘａ１は、水素原子、置換基を有していてもよいアルキル基を表す。
　Ｔは、単結合又は２価の連結基を表す。
　Ｙは酸で脱離する基を表す。Ｙは式（Ｙ１）～（Ｙ４）であることが好ましい。 In general formula (AI):
Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Y represents a group capable of leaving with an acid. Y is preferably a formula (Y1) to (Y4).
　Ｘａ１により表される、置換基を有していてもよいアルキル基としては、例えば、メチル基又は－ＣＨ２－Ｒ１１で表される基が挙げられる。Ｒ１１は、ハロゲン原子（フッ素原子など）、ヒドロキシル基又は１価の有機基を表し、例えば、炭素数５以下のアルキル基、炭素数５以下のアシル基が挙げられ、好ましくは炭素数３以下のアルキル基であり、更に好ましくはメチル基である。Ｘａ１は、一態様において、好ましくは水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基等である。
　Ｔの２価の連結基としては、アルキレン基、－ＣＯＯ－Ｒｔ－基、－Ｏ－Ｒｔ－基等が挙げられる。式中、Ｒｔは、アルキレン基又はシクロアルキレン基を表す。
　Ｔは、単結合又は－ＣＯＯ－Ｒｔ－基が好ましい。Ｒｔは、炭素数１～５のアルキレン基が好ましく、－ＣＨ２－基、－（ＣＨ２）２－基、－（ＣＨ２）３－基がより好ましい。 Examples of the optionally substituted alkyl group represented by Xa 1 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. In one embodiment, 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, —COO—Rt— group, —O—Rt— group, and the like. In the formula, 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.
　一般式（ＡＩＩ）中、
　Ｒ６１、Ｒ６２及びＲ６３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、Ｒ６２はＡｒ６と結合して環を形成していてもよく、その場合のＲ６２は単結合又はアルキレン基を表す。
　Ｘ６は、単結合、－ＣＯＯ－、又は－ＣＯＮＲ６４－を表す。Ｒ６４は、水素原子又はアルキル基を表す。
　Ｌ６は、単結合又はアルキレン基を表す。
　Ａｒ６は、（ｎ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｎ＋２）価の芳香環基を表す。
　Ｙ２は、ｎ≧２の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙ２の少なくとも１つは、酸の作用により脱離する基を表す。Ｙ２としての酸の作用により脱離する基は、式（Ｙ１）～（Ｙ４）であることが好ましい。
　ｎは、１～４の整数を表す。 In general formula (AII),
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. However, 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 represented by formulas (Y1) to (Y4).
n represents an integer of 1 to 4.
　上記各基は置換基を有していてもよく、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、アルコキシカルボニル基（炭素数２～６）などが挙げられ、炭素数８以下が好ましい。 Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group. Examples thereof include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
　一般式（ＡＩ）で表される繰り返し単位としては、好ましくは、酸分解性（メタ）アクリル酸３級アルキルエステル系繰り返し単位（Ｘａ１が水素原子又はメチル基を表し、かつ、Ｔが単結合を表す繰り返し単位）である。 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).
　上記一般式（ＡＩＩ）で表される繰り返し単位は、下記一般式（ＡＩＩＩ）で表される繰り返し単位であることが好ましい。 The repeating unit represented by the general formula (AII) is preferably a repeating unit represented by the following general formula (AIII).
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　一般式（ＡＩＩＩ）において、
　Ａｒ３は、芳香環基を表す。
　Ｙ２は、ｎ≧２の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙ２の少なくとも１つは、酸の作用により脱離する基を表す。Ｙ２としての酸の作用により脱離する基は、式（Ｙ１）～（Ｙ４）であることが好ましい。
　ｎは、１～４の整数を表す。 In 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 represented by formulas (Y1) to (Y4).
n represents an integer of 1 to 4.
　Ａｒ６及びＡｒ３が表す芳香環基は、ベンゼン環基又はナフタレン環基であることが好ましく、ベンゼン環基であることがより好ましい。 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.
　酸分解性基を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。
　具体例中、Ｒｘは、水素原子、ＣＨ３、ＣＦ３、又はＣＨ２ＯＨを表す。Ｒｘａ、Ｒｘｂは各々炭素数１～４のアルキル基を表す。Ｚは、極性基を含む置換基を表し、複数存在する場合は各々独立である。ｐは０又は正の整数を表す。Ｚにより表される極性基を含む置換基としては、例えば、水酸基、シアノ基、アミノ基、アルキルアミド基又はスルホンアミド基を有する、直鎖又は分岐のアルキル基、シクロアルキル基が挙げられ、好ましくは、水酸基を有するアルキル基である。分岐状アルキル基としてはイソプロピル基が特に好ましい。 Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.
In specific examples, 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.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　上記酸分解性基を有する繰り返し単位は、１種類であってもよいし、２種以上を併用してもよい。 The above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.
　樹脂（Ｂ）における酸分解性基を有する繰り返し単位の含有量（複数種類含有する場合はその合計）は、上記樹脂（Ｂ）中の全繰り返し単位に対して５モル％以上８０モル％以下であることが好ましく、５モル％以上７５モル％以下であることがより好ましく、１０モル％以上６５モル％以下であることが更に好ましい。 The content of the repeating unit having an acid-decomposable group in the resin (B) (when there are a plurality of types) is 5 mol% to 80 mol% with respect to all the repeating units in the resin (B). It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.
　尚、本願明細書において、酸分解性基と芳香環基とを有する繰り返し単位は、酸分解性基を有する繰り返し単位にも、芳香環基を有する繰り返し単位にも、該当するものとする。 In the present specification, the repeating unit having an acid-decomposable group and an aromatic ring group corresponds to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.
〔ラクトン基又はスルトン基を有する繰り返し単位〕
　樹脂（Ｂ）は、ラクトン基又はスルトン（環状スルホン酸エステル）基を有する繰り返し単位を含有することも好ましい。ラクトン基又はスルトン基としては、ラクトン構造又はスルトン構造を含有していればいずれの基でも用いることができるが、好ましくは５～７員環ラクトン構造又はスルトン構造を含有する基であり、５～７員環ラクトン構造又はスルトン構造にビシクロ構造、スピロ構造を形成する形で他の環構造が縮環しているものが好ましい。
　下記一般式（ＬＣ１－１）～（ＬＣ１－１７）のいずれかで表されるラクトン構造又は下記一般式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造を有する基を有する繰り返し単位を有することがより好ましい。また、ラクトン構造又はスルトン構造を有する基が主鎖に直接結合していてもよい。好ましいラクトン構造又はスルトン構造としては一般式（ＬＣ１－１）、（ＬＣ１－４）、（ＬＣ１－５）、（ＬＣ１－６）、（ＬＣ１－１３）、（ＬＣ１－１４）で表される基である。 [Repeating unit having a lactone group or a sultone group]
The resin (B) also preferably contains a repeating unit having a lactone group or a sultone (cyclic sulfonate ester) group. As 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.
A group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have a repeating unit having Further, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. 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.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　ラクトン構造部分又はスルトン構造部分は、置換基（Ｒｂ2）を有していても有していなくてもよい。好ましい置換基（Ｒｂ2）としては、炭素数１～８のアルキル基、炭素数４～７のシクロアルキル基、炭素数１～８のアルコキシ基、炭素数１～８のアルコキシカルボニル基、カルボキシル基、ハロゲン原子、水酸基、シアノ基、酸分解性基などが挙げられる。ｎ２は、０～４の整数を表す。ｎ２が２以上の時、複数存在するＲｂ2は、同一でも異なっていてもよく、また、複数存在するＲｂ2同士が結合して環を形成してもよい。 The lactone structure part or sultone structure part 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.
　一般式（ＬＣ１－１）～（ＬＣ１－１７）のいずれかで表されるラクトン構造又は一般式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造を有する基を有する繰り返し単位としては、例えば、下記一般式（ＡＩ）で表される繰り返し単位等を挙げることができる。 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 (AI).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　一般式（ＡＩ）中、Ｒｂ0は、水素原子、ハロゲン原子、又は炭素数１～４のアルキル基を表す。
　Ｒｂ0のアルキル基が有していてもよい好ましい置換基としては、水酸基、ハロゲン原子が挙げられる。
　Ｒｂ0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子を挙げることができる。Ｒｂ0は、水素原子又はメチル基が好ましい。
　Ａｂは、単結合、アルキレン基、単環又は多環の脂環炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた２価の基を表す。好ましくは、単結合、－Ａｂ1－ＣＯ2－で表される連結基である。Ａｂ1は、直鎖、分岐アルキレン基、単環又は多環のシクロアルキレン基であり、好ましくは、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、ノルボルニレン基である。
　Ｖは、一般式（ＬＣ１－１）～（ＬＣ１－１７）及び（ＳＬ１－１）～（ＳＬ１－３）のうちのいずれかで示される基を表す。 In general formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group represented by Rb 0 may have include a hydroxyl group and a halogen atom.
Examples of 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. Preferred 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).
　ラクトン基又はスルトン基を有する繰り返し単位は、通常、光学異性体が存在するが、いずれの光学異性体を用いてもよい。また、１種の光学異性体を単独で用いても、複数の光学異性体を混合して用いてもよい。１種の光学異性体を主に用いる場合、その光学純度（ｅｅ）が９０％以上のものが好ましく、より好ましくは９５％以上である。 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. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
　ラクトン基又はスルトン基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。 Specific examples of the repeating unit having a lactone group or a sultone group are given below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　ラクトン基又はスルトン基を有する繰り返し単位の含有量は、樹脂（Ｂ）中の全繰り返し単位に対し、１～３０モル％が好ましく、より好ましくは５～２５モル％、更に好ましくは５～２０モル％である。 The content of the repeating unit having a lactone group or a sultone group is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, still more preferably 5 to 20 mol%, based on all repeating units in the resin (B). %.
〔その他の繰り返し単位〕
　樹脂（Ｂ）は、その他の繰り返し単位として、極性基を有する有機基を含有する繰り返し単位、特に、極性基で置換された脂環炭化水素構造を有する繰り返し単位を更に有することができる。
　これにより基板密着性、現像液親和性が向上する。極性基で置換された脂環炭化水素構造の脂環炭化水素構造としてはアダマンチル基、ジアマンチル基、ノルボルナン基が好ましい。極性基としては水酸基、シアノ基が好ましい。極性基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。 [Other repeat units]
The resin (B) can further have, as other repeating units, 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.
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.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　樹脂（Ｂ）が、極性基を有する有機基を含有する繰り返し単位を有する場合、その含有量は、樹脂（Ｂ）中の全繰り返し単位に対し、１～３０モル％が好ましく、より好ましくは５～２５モル％、更に好ましくは５～２０モル％である。 When the resin (B) has a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 30 mol%, more preferably 5%, based on all repeating units in the resin (B). It is ˜25 mol%, more preferably 5 to 20 mol%.
　また、樹脂（Ｂ）は、その他の繰り返し単位として、活性光線又は放射線の照射により酸を発生する基（光酸発生基）を有する繰り返し単位を含むこともできる。この場合、この光酸発生基を有する繰り返し単位が、後述する活性光線又は放射線の照射により酸を発生する化合物にあたると考えることができる。
　このような繰り返し単位としては、例えば、下記一般式（４）で表される繰り返し単位が挙げられる。 Moreover, resin (B) can also contain the repeating unit which has the group (photo-acid generating group) which generate | occur | produces an acid by irradiation of actinic light or a radiation as another repeating unit. In this case, it can be considered that the repeating unit having this photoacid-generating group corresponds to a compound 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).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　Ｒ４１は、水素原子又はメチル基を表す。Ｌ４１は、単結合又は２価の連結基を表す。Ｌ４２は、２価の連結基を表す。Ｗは、活性光線又は放射線の照射により分解して側鎖に酸を発生させる構造部位を表す。 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.
　そのほか、一般式（４）で表される繰り返し単位としては、例えば、特開２０１４－０４１３２７号公報の段落［００９４］～［０１０５］に記載された繰り返し単位が挙げられる。 In addition, 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.
　樹脂（Ｂ）が光酸発生基を有する繰り返し単位を含有する場合、光酸発生基を有する繰り返し単位の含有量は、樹脂（Ｂ）中の全繰り返し単位に対し、１～４０モル％が好ましく、より好ましくは５～３５モル％、更に好ましくは５～３０モル％である。 When the resin (B) contains a repeating unit having a photoacid-generating group, 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 (B). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
　樹脂（Ｂ）は、側鎖に珪素原子を有する繰り返し単位を有していてもよい。
　側鎖に珪素原子を有する繰り返し単位としては、例えば、珪素原子を有する（メタ）アクリレート系繰り返し単位、珪素原子を有するビニル系繰り返し単位などが挙げられる。側鎖に珪素原子を有する繰り返し単位は、典型的には、側鎖に珪素原子を有する基を有する繰り返し単位であり、珪素原子を有する基としては、例えば、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、トリシクロヘキシルシリル基、トリストリメチルシロキシシリル基、トリストリメチルシリルシリル基、メチルビストリメチルシリルシリル基、メチルビストリメチルシロキシシリル基、ジメチルトリメチルシリルシリル基、ジメチルトリメチルシロキシシリル基、又は下記のような環状若しくは直鎖状ポリシロキサン、又はカゴ型あるいははしご型若しくはランダム型シルセスキオキサン構造などが挙げられる。式中、Ｒ、及び、Ｒ１は各々独立に、１価の置換基を表す。＊は、結合手を表す。 The resin (B) may have a repeating unit having a silicon atom in the side chain.
Examples of the repeating unit having a silicon atom in the side chain include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom. 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. In the formula, R and R 1 each independently represents a monovalent substituent. * Represents a bond.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　上記の基を有する繰り返し単位は、例えば、上記の基を有するアクリレート又はメタクリレート化合物に由来する繰り返し単位や、上記の基とビニル基とを有する化合物に由来する繰り返し単位を好適に挙げることができる。 As the 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.
　側鎖に珪素原子を有する繰り返し単位は、シルセスキオキサン構造を有する繰り返し単位であることが好ましい。
　シルセスキオキサン構造としては、例えば、カゴ型シルセスキオキサン構造、はしご型シルセスキオキサン構造（ラダー型シルセスキオキサン構造）、ランダム型シルセスキオキサン構造などが挙げられる。なかでも、カゴ型シルセスキオキサン構造が好ましい。
　ここで、カゴ型シルセスキオキサン構造とは、カゴ状骨格を有するシルセスキオキサン構造である。カゴ型シルセスキオキサン構造は、完全カゴ型シルセスキオキサン構造であっても、不完全カゴ型シルセスキオキサン構造であってもよいが、完全カゴ型シルセスキオキサン構造であることが好ましい。
　また、はしご型シルセスキオキサン構造とは、はしご状骨格を有するシルセスキオキサン構造である。
　また、ランダム型シルセスキオキサン構造とは、骨格がランダムのシルセスキオキサン構造である。 The repeating unit having a silicon atom in the side chain is preferably a repeating unit having a silsesquioxane structure.
Examples of 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. Of these, a cage-type silsesquioxane structure is preferable.
Here, 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. preferable.
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.
　上記カゴ型シルセスキオキサン構造は、下記式（Ｓ）で表されるシロキサン構造であることが好ましい。 The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　上記式（Ｓ）中、Ｒは、１価の有機基を表す。複数あるＲは、同一であっても、異なってもよい。
　上記有機基は特に制限されないが、具体例としては、 ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アミノ基、メルカプト基、ブロック化メルカプト基（例えば、アシル基でブロック（保護）されたメルカプト基）、アシル基、イミド基、ホスフィノ基、ホスフィニル基、シリル基、ビニル基、ヘテロ原子を有していてもよい炭化水素基、（メタ）アクリル基含有基及びエポキシ基含有基などが挙げられる。
　上記ヘテロ原子を有していてもよい炭化水素基のヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子などが挙げられる。
　上記ヘテロ原子を有していてもよい炭化水素基の炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、又はこれらを組み合わせた基などが挙げられる。
　上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状又は分岐状のアルキル基（特に、炭素数１～３０）、直鎖状又は分岐状のアルケニル基（特に、炭素数２～３０）、直鎖状又は分岐状のアルキニル基（特に、炭素数２～３０）などが挙げられる。
　上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数６～１８の芳香族炭化水素基などが挙げられる。 In the above formula (S), R represents a monovalent organic group. A plurality of R may be the same or different.
The organic group is not particularly limited, and specific examples include a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, a blocked mercapto group (for example, a mercapto group blocked (protected) with an acyl group) ), An acyl group, an imide group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group optionally having a hetero atom, a (meth) acryl group-containing group, and an epoxy group-containing group.
Examples of the 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.
Examples of the hydrocarbon group of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group 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, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group 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.
　樹脂（Ｂ）は、常法に従って（例えばラジカル重合）合成することができる。例えば、一般的合成方法としては、モノマー種及び開始剤を溶剤に溶解させ、加熱することにより重合を行う一括重合法、加熱溶剤にモノマー種と開始剤の溶液を１～１０時間かけて滴下して加える滴下重合法などが挙げられ、滴下重合法が好ましい。
　反応溶媒としては、例えば、テトラヒドロフラン、１，４－ジオキサン、ジイソプロピルエーテルなどのエーテル類；メチルエチルケトン、メチルイソブチルケトンなどのケトン類；酢酸エチルなどのエステル溶媒；ジメチルホルムアミド、ジメチルアセトアミドなどのアミド溶剤；後述のプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノンなどの感活性光線又は感放射線性組成物を溶解する溶媒；等が挙げられる。より好ましくは感活性光線又は感放射線性組成物に用いられる溶剤と同一の溶剤を用いて重合することが好ましい。これにより保存時のパーティクルの発生が抑制できる。 The resin (B) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, 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.
Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent capable of dissolving an actinic ray-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
　重合反応は窒素やアルゴンなど不活性ガス雰囲気下で行われることが好ましい。重合開始剤としては市販のラジカル開始剤（アゾ系開始剤、パーオキサイドなど）を用いて重合を開始させる。ラジカル開始剤としてはアゾ系開始剤が好ましく、エステル基、シアノ基、カルボキシル基を有するアゾ系開始剤が好ましい。好ましい開始剤としては、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル、ジメチル２，２’－アゾビス（２－メチルプロピオネート）などが挙げられる。所望により開始剤を追加、あるいは分割で添加し、反応終了後、溶剤に投入して粉体あるいは固形回収等の方法で所望のポリマーを回収する。反応の濃度は５～５０質量％であり、好ましくは１０～４５質量％である。
　反応温度は、通常１０℃～１５０℃であり、好ましくは３０℃～１２０℃、更に好ましくは６０～１００℃である。
　精製は、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液液抽出法、特定の分子量以下のもののみを抽出除去する限外ろ過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈殿法や、濾別した樹脂スラリーを貧溶媒で洗浄する等の固体状態での精製方法等の通常の方法を適用できる。 The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical 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. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 45% by mass.
The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. In a solid state such as reprecipitation method by removing the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.
　樹脂（Ｂ）の重量平均分子量は、ＧＰＣ法によりポリスチレン換算値として、好ましくは１，０００～２００，０００であり、更に好ましくは３，０００～２０，０００、最も好ましくは５，０００～１５，０００である。重量平均分子量を、１，０００～２００，０００とすることにより、耐熱性やドライエッチング耐性の劣化を防ぐことができ、かつ現像性が劣化したり、粘度が高くなって製膜性が劣化したりすることを防ぐことができる。
　樹脂（Ｂ）の重量平均分子量の特に好ましい別の形態は、ＧＰＣ法によるポリスチレン換算値で３，０００～９，５００である。
　分散度（分子量分布）は、通常１～５であり、好ましくは１～３、更に好ましくは１．２～３．０、特に好ましくは１．２～２．０の範囲のものが使用される。分散度の小さいものほど、解像度、レジスト形状が優れ、かつレジストパターンの側壁がスムーズであり、ラフネス性に優れる。 The weight average molecular weight of the resin (B) 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 the GPC method. 000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased and film forming property is deteriorated. Can be prevented.
Another particularly preferable form of the weight average molecular weight of the resin (B) is 3,000 to 9,500 in terms of polystyrene by GPC method.
The degree of dispersion (molecular weight distribution) 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.
　感活性光線又は感放射線性組成物において、樹脂（Ｂ）の含有量は、全固形分中５０～９９．９質量％が好ましく、より好ましくは６０～９９．０質量％である。
　また、感活性光線又は感放射線性組成物において、樹脂（Ｂ）は、１種で使用してもよいし、複数併用してもよい。 In the actinic ray-sensitive or radiation-sensitive composition, the content of the resin (B) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.
In the actinic ray-sensitive or radiation-sensitive composition, the resin (B) may be used alone or in combination.
＜活性光線又は放射線により酸を発生する化合物＞
　感活性光線又は感放射線性組成物は、活性光線又は放射線により酸を発生する化合物（「光酸発生剤《ＰＡＧ：Ｐｈｏｔｏ　Ａｃｉｄ　Ｇｅｎｅｒａｔｏｒ》」ともいう）を含有する。
　光酸発生剤は、低分子化合物の形態であっても良く、重合体の一部に組み込まれた形態であっても良い。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用しても良い。
　光酸発生剤が、低分子化合物の形態である場合、分子量が３０００以下であることが好ましく、２０００以下であることがより好ましく、１０００以下であることが更に好ましい。
　光酸発生剤が、重合体の一部に組み込まれた形態である場合、樹脂（Ｂ）の一部に組み込まれても良く、樹脂（Ｂ）とは異なる樹脂に組み込まれても良い。
　本発明において、光酸発生剤が、低分子化合物の形態であることが好ましい。
　光酸発生剤としては、公知のものであれば特に限定されないが、活性光線又は放射線、好ましくは電子線又は極紫外線の照射により、有機酸、例えば、スルホン酸、ビス（アルキルスルホニル）イミド、又はトリス（アルキルスルホニル）メチドの少なくともいずれかを発生する化合物が好ましい。
　より好ましくは下記一般式（ＺＩ）、（ＺＩＩ）、（ＺＩＩＩ）で表される化合物を挙げることができる。 <Compound that generates acid by actinic ray or radiation>
The actinic ray-sensitive or radiation-sensitive composition contains a compound that generates an acid by actinic rays or radiation (also referred to as “photoacid generator << PAG: Photo Acid Generator”).
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.
When 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.
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 (B) or in a resin different from the resin (B).
In the present invention, the photoacid generator is preferably in the form of a low molecular compound.
The photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred.
More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　上記一般式（ＺＩ）において、
　Ｒ２０１、Ｒ２０２及びＲ２０３は、各々独立に、有機基を表す。
　Ｒ２０１、Ｒ２０２及びＲ２０３としての有機基の炭素数は、一般的に１～３０、好ましくは１～２０である。
　また、Ｒ２０１～Ｒ２０３のうち２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、カルボニル基を含んでいてもよい。Ｒ２０１～Ｒ２０３の内の２つが結合して形成する基としては、アルキレン基（例えば、ブチレン基、ペンチレン基）を挙げることができる。
　Ｚ－は、非求核性アニオン（求核反応を起こす能力が著しく低いアニオン）を表す。 In the general formula (ZI),
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).
　非求核性アニオンとしては、例えば、スルホン酸アニオン（脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、カンファースルホン酸アニオンなど）、カルボン酸アニオン（脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、アラルキルカルボン酸アニオンなど）、スルホニルイミドアニオン、ビス（アルキルスルホニル）イミドアニオン、トリス（アルキルスルホニル）メチドアニオン等を挙げられる。 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.
　脂肪族スルホン酸アニオン及び脂肪族カルボン酸アニオンにおける脂肪族部位は、アルキル基であってもシクロアルキル基であってもよく、好ましくは炭素数１～３０の直鎖又は分岐のアルキル基及び炭素数３～３０のシクロアルキル基が挙げられる。 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.
　芳香族スルホン酸アニオン及び芳香族カルボン酸アニオンにおける芳香族基としては、好ましくは炭素数６～１４のアリール基、例えば、フェニル基、トリル基、ナフチル基等を挙げることができる。 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.
　上記で挙げたアルキル基、シクロアルキル基及びアリール基は、置換基を有していてもよい。この具体例としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（好ましくは炭素数１～１５）、シクロアルキル基（好ましくは炭素数３～１５）、アリール基（好ましくは炭素数６～１４）、アルコキシカルボニル基（好ましくは炭素数２～７）、アシル基（好ましくは炭素数２～１２）、アルコキシカルボニルオキシ基（好ましくは炭素数２～７）、アルキルチオ基（好ましくは炭素数１～１５）、アルキルスルホニル基（好ましくは炭素数１～１５）、アルキルイミノスルホニル基（好ましくは炭素数１～１５）、アリールオキシスルホニル基（好ましくは炭素数６～２０）、アルキルアリールオキシスルホニル基（好ましくは炭素数７～２０）、シクロアルキルアリールオキシスルホニル基（好ましくは炭素数１０～２０）、アルキルオキシアルキルオキシ基（好ましくは炭素数５～２０）、シクロアルキルアルキルオキシアルキルオキシ基（好ましくは炭素数８～２０）等を挙げることができる。各基が有するアリール基及び環構造については、置換基として更にアルキル基（好ましくは炭素数１～１５）を挙げることができる。 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). 7), 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. . Regarding the aryl group and ring structure of each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
　アラルキルカルボン酸アニオンにおけるアラルキル基としては、好ましくは炭素数７～１２のアラルキル基、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、ナフチルブチル基等を挙げることができる。 As the 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.
　スルホニルイミドアニオンとしては、例えば、サッカリンアニオンを挙げることができる。 Examples of the sulfonylimide anion include saccharin anion.
　ビス（アルキルスルホニル）イミドアニオン、トリス（アルキルスルホニル）メチドアニオンにおけるアルキル基は、炭素数１～５のアルキル基が好ましい。これらのアルキル基の置換基としてはハロゲン原子、ハロゲン原子で置換されたアルキル基、アルコキシ基、アルキルチオ基、アルキルオキシスルホニル基、アリールオキシスルホニル基、シクロアルキルアリールオキシスルホニル基等を挙げることができ、フッ素原子又はフッ素原子で置換されたアルキル基が好ましい。
　また、ビス（アルキルスルホニル）イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。 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. Examples of 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.
　その他の非求核性アニオンとしては、例えば、弗素化燐（例えば、ＰＦ６ －）、弗素化硼素（例えば、ＢＦ４ －）、弗素化アンチモン（例えば、ＳｂＦ６ －）等を挙げることができる。 Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF 6 − ), fluorinated boron (eg, BF 4 − ), fluorinated antimony (eg, SbF 6 − ), and the like. .
　非求核性アニオンとしては、スルホン酸の少なくともα位がフッ素原子で置換された脂肪族スルホン酸アニオン、フッ素原子又はフッ素原子を有する基で置換された芳香族スルホン酸アニオン、アルキル基がフッ素原子で置換されたビス（アルキルスルホニル）イミドアニオン、アルキル基がフッ素原子で置換されたトリス（アルキルスルホニル）メチドアニオンが好ましい。非求核性アニオンとして、より好ましくはパーフロロ脂肪族スルホン酸アニオン（更に好ましくは炭素数４～８）、フッ素原子を有するベンゼンスルホン酸アニオン、更により好ましくはノナフロロブタンスルホン酸アニオン、パーフロロオクタンスルホン酸アニオン、ペンタフロロベンゼンスルホン酸アニオン、３，５－ビス（トリフロロメチル）ベンゼンスルホン酸アニオンである。 Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-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. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.
　酸強度の観点からは、発生酸のｐＫａが－１以下であることが、感度向上のために好ましい。 From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.
　また、非求核性アニオンとしては、以下の一般式（ＡＮ１）で表されるアニオンも好ましい態様として挙げられる。 Also, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　式中、
　Ｘｆは、それぞれ独立に、フッ素原子、又は少なくとも１つのフッ素原子で置換されたアルキル基を表す。
　Ｒ１、Ｒ２は、それぞれ独立に、水素原子、フッ素原子、又は、アルキル基を表し、複数存在する場合のＲ１、Ｒ２は、それぞれ同一でも異なっていてもよい。
　Ｌは、２価の連結基を表し、複数存在する場合のＬは同一でも異なっていてもよい。
　Ａは、環状の有機基を表す。
　ｘは１～２０の整数を表し、ｙは０～１０の整数を表し、ｚは０～１０の整数を表す。 Where
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, and z represents an integer of 0 to 10.
　一般式（ＡＮ１）について、更に詳細に説明する。
　Ｘｆのフッ素原子で置換されたアルキル基におけるアルキル基としては、好ましくは炭素数１～１０であり、より好ましくは炭素数１～４である。また、Ｘｆのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基であることが好ましい。
　Ｘｆとして好ましくは、フッ素原子又は炭素数１～４のパーフルオロアルキル基である。Ｘｆの具体的としては、フッ素原子、ＣＦ３、Ｃ２Ｆ５、Ｃ３Ｆ７、Ｃ４Ｆ９、ＣＨ２ＣＦ３、ＣＨ２ＣＨ２ＣＦ３、ＣＨ２Ｃ２Ｆ５、ＣＨ２ＣＨ２Ｃ２Ｆ５、ＣＨ２Ｃ３Ｆ７、ＣＨ２ＣＨ２Ｃ３Ｆ７、ＣＨ２Ｃ４Ｆ９、ＣＨ２ＣＨ２Ｃ４Ｆ９が挙げられ、中でもフッ素原子、ＣＦ３が好ましい。特に、双方のＸｆがフッ素原子であることが好ましい。 The general formula (AN1) will be described in more detail.
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. Specific examples of Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 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.
　Ｒ１、Ｒ２のアルキル基は、置換基（好ましくはフッ素原子）を有していてもよく、炭素数１～４のものが好ましい。更に好ましくは炭素数１～４のパーフルオロアルキル基である。Ｒ１、Ｒ２の置換基を有するアルキル基の具体例としては、ＣＦ３、Ｃ２Ｆ５、Ｃ３Ｆ７、Ｃ４Ｆ９、Ｃ５Ｆ１１、Ｃ６Ｆ１３、Ｃ７Ｆ１５、Ｃ８Ｆ１７、ＣＨ２ＣＦ３、ＣＨ２ＣＨ２ＣＦ３、ＣＨ２Ｃ２Ｆ５、ＣＨ２ＣＨ２Ｃ２Ｆ５、ＣＨ２Ｃ３Ｆ７、ＣＨ２ＣＨ２Ｃ３Ｆ７、ＣＨ２Ｃ４Ｆ９、ＣＨ２ＣＨ２Ｃ４Ｆ９が挙げられ、中でもＣＦ３が好ましい。
　Ｒ１、Ｒ２としては、好ましくはフッ素原子又はＣＦ３である。 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. , C 8 F 17, 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 and CH 2 CH 2 C 4 F 9 can be mentioned, among which CF 3 is preferable.
R 1 and R 2 are preferably a fluorine atom or CF 3 .
　ｘは１～１０が好ましく、１～５がより好ましい。
　ｙは０～４が好ましく、０がより好ましい。
　ｚは０～５が好ましく、０～３がより好ましい。
　Ｌの２価の連結基としては特に限定されず、―ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－Ｏ－、－Ｓ―、－ＳＯ―、―ＳＯ２－、アルキレン基、シクロアルキレン基、アルケニレン基又はこれらの複数が連結した連結基などを挙げることができ、総炭素数１２以下の連結基が好ましい。このなかでも―ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－Ｏ－が好ましく、―ＣＯＯ－、－ＯＣＯ－がより好ましい。 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. Of these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
　Ａの環状の有機基としては、環状構造を有するものであれば特に限定されず、脂環基、アリール基、複素環基（芳香族性を有するものだけでなく、芳香族性を有さないものも含む）等が挙げられる。
　脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの単環のシクロアルキル基、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基等の炭素数７以上のかさ高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、ＭＥＥＦ向上の観点から好ましい。
　アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、アントラセン環が挙げられる。
　複素環基としては、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、ピリジン環由来のものが挙げられる。中でもフラン環、チオフェン環、ピリジン環由来のものが好ましい。 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. Among them, 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. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
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.
　また、環状の有機基としては、ラクトン構造も挙げることができ、具体例としては、前述の一般式（ＬＣ１－１）～（ＬＣ１－１７）で表されるラクトン構造を挙げることができる。 In addition, examples of the cyclic organic group also include a lactone structure, and specific examples include lactone structures represented by the above-described general formulas (LC1-1) to (LC1-17).
　上記環状の有機基は、置換基を有していてもよく、上記置換基としては、アルキル基（直鎖、分岐、環状のいずれであっても良く、炭素数１～１２が好ましい）、シクロアルキル基（単環、多環、スピロ環のいずれであっても良く、炭素数３～２０が好ましい）、アリール基（炭素数６～１４が好ましい）、ヒドロキシ基、アルコキシ基、エステル基、アミド基、ウレタン基、ウレイド基、チオエーテル基、スルホンアミド基、スルホン酸エステル基等が挙げられる。尚、環状の有機基を構成する炭素（環形成に寄与する炭素）はカルボニル炭素であっても良い。 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 carbonyl carbon.
　Ｒ２０１、Ｒ２０２及びＲ２０３の有機基としては、アリール基、アルキル基、シクロアルキル基などが挙げられる。
　Ｒ２０１、Ｒ２０２及びＲ２０３のうち、少なくとも１つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基、ピロール残基などのヘテロアリール基も可能である。Ｒ２０１～Ｒ２０３のアルキル基及びシクロアルキル基としては、好ましくは、炭素数１～１０の直鎖又は分岐アルキル基、炭素数３～１０のシクロアルキル基を挙げることができる。アルキル基として、より好ましくはメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基等を挙げることができる。シクロアルキル基として、より好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基等を挙げることができる。これらの基は更に置換基を有していてもよい。その置換基としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（好ましくは炭素数１～１５）、シクロアルキル基（好ましくは炭素数３～１５）、アリール基（好ましくは炭素数６～１４）、アルコキシカルボニル基（好ましくは炭素数２～７）、アシル基（好ましくは炭素数２～１２）、アルコキシカルボニルオキシ基（好ましくは炭素数２～７）等が挙げられるが、これらに限定されるものではない。 Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
Of R 201 , R 202 and R 203 , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can 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. Examples of the substituent 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.
　一般式（ＺＩＩ）、（ＺＩＩＩ）中、
　Ｒ２０４～Ｒ２０７は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。 In general formulas (ZII) and (ZIII),
R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
　Ｒ２０４～Ｒ２０７のアリール基、アルキル基、シクロアルキル基としては、前述の化合物（ＺＩ）におけるＲ２０１～Ｒ２０３のアリール基、アルキル基、シクロアルキル基として説明したアリール基と同様である。
　Ｒ２０４～Ｒ２０７のアリール基、アルキル基、シクロアルキル基は、置換基を有していてもよい。この置換基としても、前述の化合物（ＺＩ）におけるＲ２０１～Ｒ２０３のアリール基、アルキル基、シクロアルキル基が有していてもよいものが挙げられる。 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 aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
　Ｚ－は、非求核性アニオンを表し、一般式（ＺＩ）に於けるＺ－の非求核性アニオンと同様のものを挙げることができる。 Z − represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z − in formula (ZI).
　一般式（ＡＮ１）で表されるアニオンのＡ以外の部分、すなわち、－Ｏ３Ｓ－｛Ｃ（Ｘｆ）（Ｘｆ）｝ｘ－｛（Ｒ１）（Ｒ２）｝ｙ－（Ｌ）ｚ－で表される基の好ましい例としては、－Ｏ３Ｓ－ＣＦ２－ＣＨ２－ＯＣＯ－、－Ｏ３Ｓ－ＣＦ２－ＣＨＦ－ＣＨ２－ＯＣＯ－、－Ｏ３Ｓ－ＣＦ２－ＣＯＯ－、－Ｏ３Ｓ－ＣＦ２－ＣＦ２－ＣＨ２－、及び、－Ｏ３Ｓ－ＣＦ２－ＣＨ（ＣＦ３）－ＯＣＯ－等が挙げられる。 Portions other than A anions represented by the general formula (AN1), i.e., - O 3 S- {C ( Xf) (Xf)} x - {(R 1) (R 2)} y- (L) z - preferred examples of the group represented by the, - O 3 S-CF 2 -CH 2 -OCO-, - O 3 S-CF 2 -CHF-CH 2 -OCO-, - O 3 S-CF 2 - COO-, - O 3 S-CF 2 -CF 2 -CH 2 -, and, - O 3 S-CF 2 -CH (CF 3) -OCO- , and the like.
　本発明においては、上記光酸発生剤は、露光で発生した酸の非露光部への拡散を抑制し解像性を良好にする観点から、電子線又は極紫外線の照射により、体積１３０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることが好ましく、体積１９０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることがより好ましく、体積２７０Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることが更に好ましく、体積４００Å３以上の大きさの酸（より好ましくはスルホン酸）を発生する化合物であることが特に好ましい。ただし、感度や塗布溶剤溶解性の観点から、上記体積は、２０００Å３以下であることが好ましく、１５００Å３以下であることが更に好ましい。上記体積の値は、富士通株式会社製の「ＷｉｎＭＯＰＡＣ」を用いて求めた。すなわち、まず、各例に係る酸の化学構造を入力し、次に、この構造を初期構造としてＭＭ３法を用いた分子力場計算により、各酸の最安定立体配座を決定し、その後、これら最安定立体配座についてＰＭ３法を用いた分子軌道計算を行うことにより、各酸の「ａｃｃｅｓｓｉｂｌｅ　ｖｏｌｕｍｅ」を計算することができる。
　１Åは１×１０－１０ｍである。 In the present invention, 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 preferable that the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid). more preferably 270 Å 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 Å 3 or more in size is a compound capable of generating an Particularly preferred. However, from the viewpoint of sensitivity and coating solvent solubility, 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.
One foot is 1 × 10 −10 m.
　光酸発生剤としては、特開２０１４－４１３２８号公報段落［０３６８］～［０３７７］、特開２０１３－２２８６８１号公報段落［０２４０］～［０２６２］（対応する米国特許出願公開第２０１５／００４５３３号明細書の［０３３９］）が援用でき、これらの内容は本願明細書に組み込まれる。また、好ましい具体例として以下の化合物が挙げられるが、これらに限定されるものではない。 As the photoacid generator, paragraphs [0368] to [0377] of JP 2014-41328 A, paragraphs [0240] to [0262] of JP 2013-228881 A (corresponding US Patent Application Publication No. 2015/004533). [0339]) of the specification can be incorporated, the contents of which are incorporated herein. Moreover, although the following compounds are mentioned as a preferable specific example, it is not limited to these.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　光酸発生剤は、１種類単独で又は２種類以上を組み合わせて使用することができる。
　光酸発生剤の感活性光線又は感放射線性組成物中の含有量は、組成物の全固形分を基準として、０．１～５０質量％が好ましく、より好ましくは５～５０質量％、更に好ましくは８～４０質量％である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには光酸発生剤の含有率は高いほうが好ましく、更に好ましくは１０～４０質量％、最も好ましくは１０～３５質量％である。 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 actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. The content is preferably 8 to 40% by mass. In particular, in order to achieve both high sensitivity and high resolution at the time of electron beam or extreme ultraviolet exposure, the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
＜（Ｃ）架橋剤＞
　本発明の感活性光線又は感放射線性組成物は、架橋剤（以下、「化合物（Ｃ）」ともいう）を更に含有し得る。
　ここで、化合物（Ｃ）は、化合物（Ａ）とは異なる成分である。
　この場合、本発明の感活性光線又は感放射線性組成物は、通常、ネガ型の感活性光線又は感放射線性組成物である。
　架橋剤は、典型的には、酸の作用により樹脂（Ｂ）と架橋する化合物であり、酸架橋性基を有する化合物であり、ヒドロキシメチル基又はアルコキシメチル基を分子内に２個以上含む化合物である。また、ラフネス性能向上の観点からは、架橋剤がメチロール基を含んでいることが好ましい。
　化合物（Ｃ）は、低分子化合物の形態であっても良く、重合体の一部に組み込まれた形態であっても良い。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用しても良い。
　化合物（Ｃ）が、低分子化合物の形態である場合、分子量が３０００以下であることが好ましく、２０００以下であることがより好ましく、１０００以下であることが更に好ましい。 <(C) Crosslinking agent>
The actinic ray-sensitive or radiation-sensitive composition of the present invention may further contain a crosslinking agent (hereinafter also referred to as “compound (C)”).
Here, the compound (C) is a component different from the compound (A).
In this case, the actinic ray-sensitive or radiation-sensitive composition of the present invention is usually a negative actinic ray-sensitive or radiation-sensitive composition.
The cross-linking agent is typically a compound that cross-links with the resin (B) by the action of an acid, a compound having an acid cross-linkable group, and a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. It is. Further, from the viewpoint of improving the roughness performance, the crosslinking agent preferably contains a methylol group.
The compound (C) may be in the form of a low molecular compound or may be in a form 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.
When the compound (C) 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.
　まず、化合物（Ｃ）が低分子化合物である場合（以下、「化合物（Ｃ’）」ともいう）について説明する。化合物（Ｃ’）として、好ましくは、ヒドロキシメチル化又はアルコキシメチル化フェノール化合物、アルコキシメチル化メラミン系化合物、アルコキシメチルグリコールウリル系化合物及びアルコキシメチル化ウレア系化合物が挙げられる。特に好ましい化合物（Ｃ’）としては、分子内にベンゼン環を３～５個含み、更にヒドロキシメチル基又はアルコキシメチル基を合わせて２個以上有し、分子量が１２００以下のフェノール誘導体やアルコキシメチルグリコールウリル誘導体が挙げられる。
　アルコキシメチル基としては、メトキシメチル基、エトキシメチル基が好ましい。 First, the case where the compound (C) is a low molecular compound (hereinafter also referred to as “compound (C ′)”) will be described. The compound (C ′) is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound. Particularly preferred compounds (C ′) include phenol derivatives and alkoxymethyl glycols having 3 to 5 benzene rings in the molecule, and further having two or more hydroxymethyl groups or alkoxymethyl groups, and a molecular weight of 1200 or less. Examples include uril derivatives.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.
　上記化合物（Ｃ’）の例のうち、ヒドロキシメチル基を有するフェノール誘導体は、対応するヒドロキシメチル基を有さないフェノール化合物とホルムアルデヒドを塩基触媒下で反応させることによって得ることができる。また、アルコキシメチル基を有するフェノール誘導体は、対応するヒドロキシメチル基を有するフェノール誘導体とアルコールを酸触媒下で反応させることによって得ることができる。 Among the examples of the compound (C ′), a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no 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.
　別の好ましい化合物（Ｃ’）の例として、更にアルコキシメチル化メラミン系化合物、アルコキシメチルグリコールウリル系化合物類及びアルコキシメチル化ウレア系化合物のようなＮ－ヒドロキシメチル基又はＮ－アルコキシメチル基を有する化合物を挙げることができる。 Examples of another preferable compound (C ′) further have an N-hydroxymethyl group or an N-alkoxymethyl group such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds. A compound can be mentioned.
　このような化合物としては、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、テトラメトキシメチルグリコールウリル、１，３－ビスメトキシメチル－４，５－ビスメトキシエチレンウレア、ビスメトキシメチルウレア等が挙げられ、ＥＰ０，１３３，２１６Ａ号、西独特許第３，６３４，６７１号、同第３，７１１，２６４号、ＥＰ０，２１２，４８２Ａ号に開示されている。
　化合物（Ｃ’）の具体例の中で特に好ましいものを以下に挙げる。 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.
Of the specific examples of the compound (C ′), those particularly preferred are listed below.
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　式中、Ｌ１～Ｌ８は、各々独立に、ヒドロキシメチル基、又は、アルコキシメチル基を表す。
　本発明の一形態において、化合物（Ｃ’）は、下記一般式（Ｉ）で表される化合物であることが好ましい。 In the formula, L 1 to L 8 each independently represents a hydroxymethyl group or an alkoxymethyl group.
In one embodiment of the present invention, the compound (C ′) is preferably a compound represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
　一般式（Ｉ）中、
　Ｒ１及びＲ６は、各々独立に、水素原子、又は炭素数５以下の炭化水素基を表す。
　Ｒ２及びＲ５は、各々独立に、アルキル基、シクロアルキル基、アリール基、又はアシル基を表す。
　Ｒ３及びＲ４は、各々独立に、水素原子、又は炭素数２以上の有機基を表す。Ｒ３及びＲ４は、互いに結合して環を形成してもよい。 In general formula (I),
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.
　本発明の一形態において、Ｒ１及びＲ６は、好ましくは炭素数５以下の炭化水素基であり、より好ましくは炭素数４以下の炭化水素基であり、特に好ましくはメチル基、エチル基、プロピル基、イソプロピル基が挙げられる。 In one embodiment of the present invention, 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.
　Ｒ２及びＲ５により表されるアルキル基としては、例えば、炭素数１～６以下のアルキル基が好ましく、シクロアルキル基として、例えば、炭素数３～１２のシクロアルキル基が好ましく、アリール基としては、例えば、炭素数６～１２のアリール基が好ましく、アシル基としては、例えば、アルキル部位の炭素数が１～６のものが好ましい。
　本発明の一形態において、Ｒ２及びＲ５は、アルキル基であることが好ましく、より好ましくは炭素数１～６のアルキル基であることがより好ましく、メチル基であることが特に好ましい。 As the alkyl group represented by 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.
In one embodiment of the present invention, R 2 and R 5 are preferably alkyl groups, more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.
　Ｒ３及びＲ４により表される炭素数２以上の有機基としては、例えば、炭素数２以上のアルキル基、シクロアルキル基、アリール基等が挙げられ、また、Ｒ３及びＲ４が互いに結合して形成して以下に詳述する環を形成していることが好ましい。 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.
　Ｒ３及びＲ４が互いに結合して形成される環としては、例えば、芳香族若しくは非芳香族の炭化水素環、芳香族若しくは非芳香族の複素環、又は、これらの環が２つ以上組み合わされてなる多環縮合環を挙げることができる。 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.
　これらの環は置換基を有していてもよく、このような置換基としては、例えば、アルキル基、シクロアルキル基、アルコキシ基、カルボキシル基、アリール基、アルコキシメチル基、アシル基、アルコキシカルボニル基、ニトロ基、ハロゲン、又はヒドロキシ基等が挙げられる。 These rings may have a substituent. Examples of such a substituent 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.
　以下に、Ｒ３及びＲ４が互いに結合して形成する環の具体例を挙げる。式中の＊は、フェノール核との連結部位を表す。 Specific examples of the ring formed by combining R 3 and R 4 with each other are given below. * In a formula represents a connection part with a phenol nucleus.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　本発明の一形態において、一般式（Ｉ）中のＲ３及びＲ４が結合してベンゼン環を含む多環縮合環を形成していることが好ましく、フルオレン構造を形成していることがより好ましい。
　化合物（Ｃ’）は、例えば、一般式（Ｉ）中のＲ３及びＲ４が結合して、下記一般式（Ｉ－ａ）で表されるフルオレン構造を形成していることが好ましい。 In one embodiment of the present invention, R 3 and R 4 in the general formula (I) are preferably bonded to form a polycyclic fused ring containing a benzene ring, and more preferably a fluorene structure is formed. preferable.
In the compound (C ′), for example, R 3 and R 4 in the general formula (I) are preferably bonded to form a fluorene structure represented by the following general formula (Ia).
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
　式中、
　Ｒ７及びＲ８は、各々独立に、置換基を表す。置換基としては、例えば、アルキル基、シクロアルキル基、アルコキシ基、アリール基、アルコキシメチル基、アシル基、アルコキシカルボニル基、ニトロ基、ハロゲン、又はヒドロキシ基等が挙げられる。
　ｎ１及びｎ２は、各々独立に、０～４の整数を表し、好ましくは０又は１を表す。
　＊は、フェノール核との連結部位を表す。 Where
R 7 and R 8 each independently represents a substituent. Examples of the substituent 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.
　また、本発明の一形態において、化合物（Ｃ’）は、下記一般式（Ｉ－ｂ）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000067
 In one embodiment of the present invention, the compound (C ′) is preferably represented by the following general formula (Ib).
Figure JPOXMLDOC01-appb-C000067
　式中、
　Ｒ１ｂ及びＲ６ｂは、各々独立に、炭素数５以下のアルキル基を表す。
　Ｒ２ｂ及びＲ５ｂは、各々独立に、炭素数６以下のアルキル基又は炭素数３～１２のシクロアルキル基を表す。
　Ｚは、式中の炭素原子と共に環を形成するのに必要な原子群を表す。
　Ｚが式中の炭素原子と共に形成する環については、上述した一般式（Ｉ）の説明において、Ｒ３及びＲ４が互いに結合して形成する環について説明したものと同様である。 Where
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 (I).
　本発明の一形態において、化合物（Ｃ’）は、分子内に４つ以上の芳香環と、アルコキシメチル基及び／又はヒドロキシメチル基を合計で２つ有する化合物であることが好ましい。 In one embodiment of the present invention, the compound (C ′) is preferably a compound having a total of two or more aromatic rings and two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.
　次に、一般式（Ｉ）で表される化合物（Ｃ’）の製造方法について説明する。
　一般式（Ｉ）で表される化合物（Ｃ’）の母核となるビスフェノール化合物は、一般に、対応する２分子のフェノール化合物と、対応する１分子のケトンを、酸触媒存在下、脱水縮合反応することにより合成される。 Next, the manufacturing method of compound (C ') represented by general formula (I) is demonstrated.
In general, the bisphenol compound serving as the mother nucleus of the compound (C ′) represented by the general formula (I) is generally a dehydration condensation reaction between two corresponding molecules of a phenol compound and one corresponding molecule of a ketone in the presence of an acid catalyst. To be synthesized.
　得られたビスフェノール体をパラホルムアルデヒドとジメチルアミンで処理して、アミノメチル化することにより、下記一般式（Ｉ－Ｃ）で表される中間体を得る。続いて、アセチル化、脱アセチル化、アルキル化を経て、目的の酸架橋剤が得られる。 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.
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
　式中、Ｒ１、Ｒ３、Ｒ４及びＲ６は、一般式（Ｉ）中の各基と同義である。 In formula, R < 1 >, R < 3 >, R < 4 > and R < 6 > are synonymous with each group in general formula (I).
　本合成法は、従来の塩基性条件下にてヒドロキシメチル体を経由するような合成方法（たとえば、特開２００８－２７３８４４号公報）に比べてオリゴマーを生成しづらいため、パーティクル形成抑止効果がある。
　以下に、一般式（Ｉ）で表される化合物（Ｃ’）の具体例を示す。 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). .
Specific examples of the compound (C ′) represented by the general formula (I) are shown below.
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　本発明において、化合物（Ｃ’）は単独で用いてもよいし、２種以上組み合わせて用いてもよい。良好なパターン形状の観点からは、２種以上組み合わせて用いることが好ましい。 In the present invention, the compound (C ′) 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.
　化合物（Ｃ）が、重合体の一部に組み込まれた形態である場合、樹脂（Ｂ）の一部に組み込まれても良く、樹脂（Ｂ）とは異なる樹脂に組み込まれても良い。 When the compound (C) is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (B) or in a resin different from the resin (B).
　本発明に係る感活性光線又は感放射線性組成物は、化合物（Ｃ）を含有しても含有しなくても良いが、含有する場合、化合物（Ｃ）の含有量は、感活性光線又は感放射線性組成物の全固形分中、好ましくは０．５～３０質量％であり、より好ましくは１～１５質量％である。 The actinic ray-sensitive or radiation-sensitive composition according to the present invention may or may not contain the compound (C), but when it is contained, the content of the compound (C) The total solid content of the radiation composition is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass.
＜溶剤＞
　本発明において用いられる感活性光線又は感放射線性組成物は、溶剤（「レジスト溶剤」ともいう）を含んでいることが好ましい。この溶剤は、（Ｍ１）プロピレングリコールモノアルキルエーテルカルボキシレートと、（Ｍ２）プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン、及びアルキレンカーボネートからなる群より選択される少なくとも１つとの少なくとも一方を含んでいることが好ましい。尚、この溶剤は、成分（Ｍ１）及び（Ｍ２）以外の成分を更に含んでいてもよい。 <Solvent>
The actinic ray-sensitive or radiation-sensitive composition used in the present invention preferably contains a solvent (also referred to as “resist solvent”). This solvent comprises (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 the group is included. In addition, this solvent may further contain components other than component (M1) and (M2).
　本発明者らは、このような溶剤と上述した樹脂とを組み合わせて用いると、組成物の塗布性が向上すると共に、現像欠陥数の少ないパターンが形成可能となることを見出している。その理由は必ずしも明らかではないが、本発明者らは、これら溶剤は、上述した樹脂の溶解性、沸点、及び粘度のバランスが良いため、組成物膜の膜厚のムラやスピンコート中の析出物の発生などを抑制できることに起因していると考えている。 The present inventors have found that when such a solvent and the above-described resin are used in combination, the coating property of the composition is improved and a pattern with a small number of development defects can be formed. The reason for this is not necessarily clear, but the present inventors have found that these solvents have a good balance of solubility, boiling point, and viscosity of the resin described above. It is thought that it originates in being able to suppress generation | occurrence | production of a thing etc.
　成分（Ｍ１）としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、及び、プロピレングリコールモノエチルエーテルアセテートからなる群より選択される少なくとも１つが好ましく、プロピレングリコールモノメチルエーテルアセテートが特に好ましい。 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.
　成分（Ｍ２）としては、以下のものが好ましい。
　プロピレングリコールモノアルキルエーテルとしては、プロピレングリコールモノメチルエーテル又はプロピレングリコールモノエチルエーテルが好ましい。
　乳酸エステルとしては、乳酸エチル、乳酸ブチル、又は乳酸プロピルが好ましい。
　酢酸エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソアミル、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、又は酢酸３－メトキシブチルが好ましい。
　酪酸ブチルも好ましい。
　アルコキシプロピオン酸エステルとしては、３－メトキシプロピオン酸メチル（ＭＭＰ）、又は、３－エトキシプロピオン酸エチル（ＥＥＰ）が好ましい。
　鎖状ケトンとしては、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、アセトン、４－ヘプタノン、１－ヘキサノン、２－ヘキサノン、ジイソブチルケトン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、又はメチルアミルケトンが好ましい。
　環状ケトンとしては、メチルシクロヘキサノン、イソホロン、又はシクロヘキサノンが好ましい。
　ラクトンとしては、γ－ブチロラクトンが好ましい。
　アルキレンカーボネートとしては、プロピレンカーボネートが好ましい。 As the component (M2), the following are preferable.
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferable.
As the 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.
Also preferred is butyl butyrate.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
As the alkylene carbonate, propylene carbonate is preferable.
　成分（Ｍ２）としては、プロピレングリコールモノメチルエーテル、乳酸エチル、３－エトキシプロピオン酸エチル、メチルアミルケトン、シクロヘキサノン、酢酸ブチル、酢酸ペンチル、γ－ブチロラクトン又はプロピレンカーボネートがより好ましい。 Component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone or propylene carbonate.
　上記成分の他、炭素原子数が７以上（７～１４が好ましく、７～１２がより好ましく、７～１０が更に好ましい）、かつヘテロ原子数が２以下のエステル系溶剤を用いることが好ましい。 In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and further preferably 7 to 10) and a hetero atom number of 2 or less.
　炭素原子数が７以上かつヘテロ原子数が２以下のエステル系溶剤の好ましい例としては、酢酸アミル、酢酸２－メチルブチル、酢酸１-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ブチル、イソ酪酸イソブチル、プロピオン酸ヘプチル、ブタン酸ブチルなどが挙げられ、酢酸イソアミルを用いることが特に好ましい。 Preferred examples of 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, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.
　成分（Ｍ２）としては、引火点（以下、ｆｐともいう）が３７℃以上であるものを用いることが好ましい。このような成分（Ｍ２）としては、プロピレングリコールモノメチルエーテル（ｆｐ：４７℃）、乳酸エチル（ｆｐ：５３℃）、３－エトキシプロピオン酸エチル（ｆｐ：４９℃）、メチルアミルケトン（ｆｐ：４２℃）、シクロヘキサノン（ｆｐ：４４℃）、酢酸ペンチル（ｆｐ：４５℃）、２－ヒドロキシイソ酪酸メチル（ｆｐ：４５℃）、γ－ブチロラクトン（ｆｐ：１０１℃）又はプロピレンカーボネート（ｆｐ：１３２℃）が好ましい。これらのうち、プロピレングリコールモノエチルエーテル、乳酸エチル、酢酸ペンチル、又はシクロヘキサノンが更に好ましく、プロピレングリコールモノエチルエーテル又は乳酸エチルが特に好ましい。尚、ここで「引火点」とは、東京化成工業株式会社又はシグマアルドリッチ社の試薬カタログに記載されている値を意味している。 As the component (M2), one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used. Examples of such 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), γ-butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, the “flash point” means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.
　溶剤は、成分（Ｍ１）を含んでいることが好ましい。溶剤は、実質的に成分（Ｍ１）のみからなるか、又は、成分（Ｍ１）と他の成分との混合溶剤であることがより好ましい。後者の場合、溶剤は、成分（Ｍ１）と成分（Ｍ２）との双方を含んでいることが更に好ましい。 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).
　成分（Ｍ１）と成分（Ｍ２）との質量比は、１００：０乃至１５：８５の範囲内にあることが好ましく、１００：０乃至４０：６０の範囲内にあることがより好ましく、１００：０乃至６０：４０の範囲内にあることが更に好ましい。即ち、溶剤は、成分（Ｍ１）のみからなるか、又は、成分（Ｍ１）と成分（Ｍ２）との双方を含んでおりかつそれらの質量比が以下の通りであることが好ましい。即ち、後者の場合、成分（Ｍ２）に対する成分（Ｍ１）の質量比は、１５／８５以上であることが好ましく、４０／６０以上であることよりが好ましく、６０／４０以上であることが更に好ましい。このような構成を採用すると、現像欠陥数を更に減少させることが可能となる。 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.
　尚、溶剤が成分（Ｍ１）と成分（Ｍ２）との双方を含んでいる場合、成分（Ｍ２）に対する成分（Ｍ１）の質量比は、例えば、９９／１以下とする。 In addition, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.
　上述した通り、溶剤は、成分（Ｍ１）及び（Ｍ２）以外の成分を更に含んでいてもよい。この場合、成分（Ｍ１）及び（Ｍ２）以外の成分の含有量は、溶剤の全量に対して、５質量％乃至３０質量％の範囲内にあることが好ましい。 As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.
　感活性光線又は感放射線性組成物に占める溶剤の含有量は、全成分の固形分濃度が０．５～３０質量％となるように定めることが好ましく、１～２０質量％となるように定めることがより好ましい。こうすると、感活性光線又は感放射線性組成物の塗布性を更に向上させることができる。 The content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined such that the solid content concentration of all components is preferably 0.5 to 30% by mass, and is determined to be 1 to 20% by mass. It is more preferable. If it carries out like this, the applicability | paintability of actinic-ray-sensitive or radiation-sensitive composition can further be improved.
＜（Ｅ）塩基性化合物＞
　本発明の感活性光線又は感放射線性組成物は、露光から加熱までの経時による性能変化を低減するために、（Ｅ）塩基性化合物を含有することが好ましい。
　塩基性化合物としては、好ましくは、下記式（Ａ）～（Ｅ）で示される構造を有する化合物を挙げることができる。 <(E) Basic compound>
The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains (E) a basic compound in order to reduce changes in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
　一般式（Ａ）及び（Ｅ）中、Ｒ２００、Ｒ２０１及びＲ２０２は、同一でも異なってもよく、水素原子、アルキル基（好ましくは炭素数１～２０）、シクロアルキル基（好ましくは炭素数３～２０）又はアリール基（好ましくは炭素数６～２０）を表し、ここで、Ｒ２０１とＲ２０２は、互いに結合して環を形成してもよい。 In general formulas (A) and (E), R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably a carbon atom). 3 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.
　上記アルキル基について、置換基を有するアルキル基としては、炭素数１～２０のアミノアルキル基、炭素数１～２０のヒドロキシアルキル基、又は炭素数１～２０のシアノアルキル基が好ましい。
　Ｒ２０３、Ｒ２０４、Ｒ２０５及びＲ２０６は、同一でも異なってもよく、炭素数１～２０個のアルキル基を表す。
　これら一般式（Ａ）及び（Ｅ）中のアルキル基は、無置換であることがより好ましい。 Regarding the alkyl group, 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 (A) and (E) are more preferably unsubstituted.
　好ましい化合物として、グアニジン、アミノピロリジン、ピラゾール、ピラゾリン、ピペラジン、アミノモルホリン、アミノアルキルモルフォリン、ピペリジン等を挙げることができ、更に好ましい化合物として、イミダゾール構造、ジアザビシクロ構造、オニウムヒドロキシド構造、オニウムカルボキシレート構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び／又はエーテル結合を有するアルキルアミン誘導体、水酸基及び／又はエーテル結合を有するアニリン誘導体等を挙げることができる。 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.
　イミダゾール構造を有する化合物としてはイミダゾール、２、４、５－トリフェニルイミダゾール、ベンズイミダゾール等が挙げられる。ジアザビシクロ構造を有する化合物としては１、４－ジアザビシクロ［２，２，２］オクタン、１、５－ジアザビシクロ［４，３，０］ノナ－５－エン、１、８－ジアザビシクロ［５，４，０］ウンデカ－７－エン等が挙げられる。オニウムヒドロキシド構造を有する化合物としてはトリアリールスルホニウムヒドロキシド、フェナシルスルホニウムヒドロキシド、２－オキソアルキル基を有するスルホニウムヒドロキシド、具体的にはトリフェニルスルホニウムヒドロキシド、トリス（ｔ－ブチルフェニル）スルホニウムヒドロキシド、ビス（ｔ－ブチルフェニル）ヨードニウムヒドロキシド、フェナシルチオフェニウムヒドロキシド、２－オキソプロピルチオフェニウムヒドロキシド等が挙げられる。オニウムカルボキシレート構造を有する化合物としてはオニウムヒドロキシド構造を有する化合物のアニオン部がカルボキシレートになったものであり、例えばアセテート、アダマンタン－１－カルボキシレート、パーフロロアルキルカルボキシレート等が挙げられる。トリアルキルアミン構造を有する化合物としては、トリ（ｎ－ブチル）アミン、トリ（ｎ－オクチル）アミン等を挙げることができる。アニリン化合物としては、２，６－ジイソプロピルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジブチルアニリン、Ｎ，Ｎ－ジヘキシルアニリン等を挙げることができる。水酸基及び／又はエーテル結合を有するアルキルアミン誘導体としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、トリス（メトキシエトキシエチル）アミン等を挙げることができる。水酸基及び／又はエーテル結合を有するアニリン誘導体としては、Ｎ，Ｎ－ビス（ヒドロキシエチル）アニリン等を挙げることができる。 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. Examples of aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.
　好ましい塩基性化合物として、更に、フェノキシ基を有するアミン化合物、フェノキシ基を有するアンモニウム塩化合物を挙げることができる。 Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
　アミン化合物は、１級、２級、３級のアミン化合物を使用することができ、少なくとも１つのアルキル基が窒素原子に結合しているアミン化合物が好ましい。アミン化合物は、３級アミン化合物であることがより好ましい。アミン化合物は、少なくとも１つのアルキル基（好ましくは炭素数１～２０）が窒素原子に結合していれば、アルキル基の他に、シクロアルキル基（好ましくは炭素数３～２０）又はアリール基（好ましくは炭素数６～１２）が窒素原子に結合していてもよい。
　また、アミン化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に１つ以上、好ましくは３～９個、更に好ましくは４～６個である。オキシアルキレン基の中でもオキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）若しくはオキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくは－ＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、更に好ましくはオキシエチレン基である。 As the 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. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, 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). Preferably 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. Among the oxyalkylene groups, an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
　アンモニウム塩化合物は、１級、２級、３級、４級のアンモニウム塩化合物を使用することができ、少なくとも１つのアルキル基が窒素原子に結合しているアンモニウム塩化合物が好ましい。アンモニウム塩化合物は、少なくとも１つのアルキル基（好ましくは炭素数１～２０）が窒素原子に結合していれば、アルキル基の他に、シクロアルキル基（好ましくは炭素数３～２０）又はアリール基（好ましくは炭素数６～１２）が窒素原子に結合していてもよい。
　アンモニウム塩化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に１つ以上、好ましくは３～９個、更に好ましくは４～６個である。オキシアルキレン基の中でもオキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）若しくはオキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくは－ＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、更に好ましくはオキシエチレン基である。
　アンモニウム塩化合物のアニオンとしては、ハロゲン原子、スルホネート、ボレート、フォスフェート等が挙げられるが、中でもハロゲン原子、スルホネートが好ましい。ハロゲン原子としてはクロライド、ブロマイド、アイオダイドが特に好ましく、スルホネートとしては、炭素数１～２０の有機スルホネートが特に好ましい。有機スルホネートとしては、炭素数１～２０のアルキルスルホネート、アリールスルホネートが挙げられる。アルキルスルホネートのアルキル基は置換基を有していてもよく、置換基としては例えばフッ素、塩素、臭素、アルコキシ基、アシル基、アリール基等が挙げられる。アルキルスルホネートとして、具体的にはメタンスルホネート、エタンスルホネート、ブタンスルホネート、ヘキサンスルホネート、オクタンスルホネート、ベンジルスルホネート、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ノナフルオロブタンスルホネート等が挙げられる。アリールスルホネートのアリール基としてはベンゼン環、ナフタレン環、アントラセン環が挙げられる。ベンゼン環、ナフタレン環、アントラセン環は置換基を有していてもよく、置換基としては炭素数１～６の直鎖若しくは分岐アルキル基、炭素数３～６のシクロアルキル基が好ましい。直鎖若しくは分岐アルキル基、シクロアルキル基として、具体的には、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、ｉ－ブチル、ｔ－ブチル、ｎ－ヘキシル、シクロヘキシル等が挙げられる。他の置換基としては炭素数１～６のアルコキシ基、ハロゲン原子、シアノ、ニトロ、アシル基、アシルオキシ基等が挙げられる。 As the 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. In addition to the alkyl group, 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. Among the oxyalkylene groups, an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
Examples of 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, and the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of 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. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the 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. Specific examples of 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. Examples of 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.
　フェノキシ基を有するアミン化合物、フェノキシ基を有するアンモニウム塩化合物とは、アミン化合物又はアンモニウム塩化合物のアルキル基の窒素原子と反対側の末端にフェノキシ基を有するものである。フェノキシ基は、置換基を有していてもよい。フェノキシ基の置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、カルボン酸エステル基、スルホン酸エステル基、アリール基、アラルキル基、アシルオキシ基、アリールオキシ基等が挙げられる。置換基の置換位は、２～６位のいずれであってもよい。置換基の数は、１～５の範囲で何れであってもよい。 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. Examples of 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. Etc. 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.
　フェノキシ基と窒素原子との間に、少なくとも１つのオキシアルキレン基を有することが好ましい。オキシアルキレン基の数は、分子内に１つ以上、好ましくは３～９個、更に好ましくは４～６個である。オキシアルキレン基の中でもオキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）若しくはオキシプロピレン基（－ＣＨ（ＣＨ３）ＣＨ２Ｏ－若しくは－ＣＨ２ＣＨ２ＣＨ２Ｏ－）が好ましく、更に好ましくはオキシエチレン基である。 It is preferable to have at least one 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. Among the oxyalkylene groups, an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
　フェノキシ基を有するアミン化合物は、フェノキシ基を有する１又は２級アミンとハロアルキルエーテルを加熱して反応させた後、水酸化ナトリウム、水酸化カリウム、テトラアルキルアンモニウム等の強塩基の水溶液を添加した後、酢酸エチル、クロロホルム等の有機溶剤で抽出することにより得ることができる。又は、１又は２級アミンと末端にフェノキシ基を有するハロアルキルエーテルを加熱して反応させた後、水酸化ナトリウム、水酸化カリウム、テトラアルキルアンモニウム等の強塩基の水溶液を添加した後、酢酸エチル、クロロホルム等の有機溶剤で抽出することにより得ることができる。 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. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc. is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.
（プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する化合物（ＰＡ））
　本発明に係る組成物は、塩基性化合物として、プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する化合物〔以下、化合物（ＰＡ）ともいう〕を更に含んでいてもよい。 (A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from a proton acceptor property to an acidic property (PA) )
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).
　プロトンアクセプター性官能基とは、プロトンと静電的に相互作用し得る基或いは電子を有する官能基であって、例えば、環状ポリエーテル等のマクロサイクリック構造を有する官能基や、π共役に寄与しない非共有電子対をもった窒素原子を有する官能基を意味する。π共役に寄与しない非共有電子対を有する窒素原子とは、例えば、下記一般式に示す部分構造を有する窒素原子である。 The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-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 π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
　プロトンアクセプター性官能基の好ましい部分構造として、例えば、クラウンエーテル、アザクラウンエーテル、１～３級アミン、ピリジン、イミダゾール、ピラジン構造などを挙げることができる。 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.
　化合物（ＰＡ）は、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する。ここで、プロトンアクセプター性の低下、消失、又はプロトンアクセプター性から酸性への変化とは、プロトンアクセプター性官能基にプロトンが付加することに起因するプロトンアクセプター性の変化であり、具体的には、プロトンアクセプター性官能基を有する化合物（ＰＡ）とプロトンからプロトン付加体が生成する時、その化学平衡に於ける平衡定数が減少することを意味する。 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. Here, 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. Specifically, when 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.
　化合物（ＰＡ）の具体例としては、例えば、下記化合物を挙げることができる。更に、化合物（ＰＡ）の具体例としては、例えば、特開２０１４－４１３２８号公報の段落０４２１～０４２８、特開２０１４－１３４６８６号公報の段落０１０８～０１１６に記載されたものを援用することができ、これらの内容は本明細書に組み込まれる。 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.
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
　これらの塩基性化合物は、単独であるいは２種以上一緒に用いられる。 These basic compounds may be used alone or in combination of two or more.
　塩基性化合物の使用量は、感活性光線又は感放射線性組成物の固形分を基準として、通常、０．００１～１０質量％、好ましくは０．０１～５質量％である。 The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.
　光酸発生剤と塩基性化合物の組成物中の使用割合は、光酸発生剤／塩基性化合物（モル比）＝２．５～３００であることが好ましい。即ち、感度、解像度の点からモル比が２．５以上が好ましく、露光後加熱処理までの経時でのレジストパターンの太りによる解像度の低下抑制の点から３００以下が好ましい。光酸発生剤／塩基性化合物（モル比）は、より好ましくは５．０～２００、更に好ましくは７．０～１５０である。 The use ratio of the photoacid generator and the basic compound in the composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
　塩基性化合物としては、例えば、特開２０１３－１１８３３号公報の段落０１４０～０１４４に記載の化合物（アミン化合物、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等）を用いることができる。 As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.
＜（Ｄ）疎水性樹脂＞
　本発明の組成物は、疎水性樹脂（以下、「疎水性樹脂（Ｄ）」又は単に「樹脂（Ｄ）」ともいう）を含有してもよい。尚、疎水性樹脂（Ｄ）は樹脂（Ｂ）とは異なることが好ましい。
　疎水性樹脂（Ｄ）は、界面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性／非極性物質を均一に混合することに寄与しなくてもよい。
　疎水性樹脂を添加することの効果として、水に対するレジスト膜表面の静的／動的な接触角の制御、液浸液追随性の向上、アウトガスの抑制などを挙げることができる。 <(D) Hydrophobic resin>
The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”). The hydrophobic resin (D) is preferably different from the resin (B).
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to
Examples of the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.
　疎水性樹脂（Ｄ）は、膜表層への偏在化の観点から、“フッ素原子”、“珪素原子”、及び、“樹脂の側鎖部分に含有されたＣＨ３部分構造”のいずれか１種以上を有することが好ましく、２種以上を有することが更に好ましい。
　疎水性樹脂（Ｄ）が、フッ素原子及び／又は珪素原子を含む場合、疎水性樹脂（Ｄ）に於ける上記フッ素原子及び／又は珪素原子は、樹脂の主鎖中に含まれていてもよく、側鎖中に含まれていてもよい。 The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.
　疎水性樹脂（Ｄ）がフッ素原子を含んでいる場合、フッ素原子を有する部分構造として、フッ素原子を有するアルキル基、フッ素原子を有するシクロアルキル基、又は、フッ素原子を有するアリール基を有する樹脂であることが好ましい。
　フッ素原子を有するアルキル基（好ましくは炭素数１～１０、より好ましくは炭素数１～４）は、少なくとも１つの水素原子がフッ素原子で置換された直鎖又は分岐アルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
　フッ素原子を有するシクロアルキル基及びフッ素原子を有するアリール基は、それぞれ、１つの水素原子がフッ素原子で置換されたシクロアルキル基及びフッ素原子を有するアリール基であり、更にフッ素原子以外の置換基を有していてもよい。 When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have a substituent other than.
A cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.
　フッ素原子を有するアルキル基、フッ素原子を有するシクロアルキル基、及びフッ素原子を有するアリール基として、好ましくは、下記一般式（Ｆ２）～（Ｆ４）で表される基を挙げることができるが、本発明は、これに限定されるものではない。 Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
　一般式（Ｆ２）～（Ｆ４）中、
　Ｒ５７～Ｒ６８は、各々独立に、水素原子、フッ素原子又はアルキル基（直鎖若しくは分岐）を表す。但し、Ｒ５７～Ｒ６１の少なくとも１つ、Ｒ６２～Ｒ６４の少なくとも１つ、及びＲ６５～Ｒ６８の少なくとも１つは、各々独立に、フッ素原子又は少なくとも１つの水素原子がフッ素原子で置換されたアルキル基（好ましくは炭素数１～４）を表す。
　Ｒ５７～Ｒ６１及びＲ６５～Ｒ６７は、全てがフッ素原子であることが好ましい。Ｒ６２、Ｒ６３及びＲ６８は、少なくとも１つの水素原子がフッ素原子で置換されたアルキル基（好ましくは炭素数１～４）が好ましく、炭素数１～４のパーフルオロアルキル基であることが更に好ましい。Ｒ６２とＲ６３は、互いに連結して環を形成してもよい。 In general formulas (F2) to (F4),
R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that at least one of R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).
All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms. R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
　疎水性樹脂（Ｄ）は、珪素原子を含有してもよい。珪素原子を有する部分構造として、アルキルシリル構造（好ましくはトリアルキルシリル基）、又は環状シロキサン構造を有する樹脂であることが好ましい。
　フッ素原子又は珪素原子を有する繰り返し単位の例としては、ＵＳ２０１２／０２５１９４８Ａ１〔０５１９〕に例示されたものを挙げることが出来る。 The hydrophobic resin (D) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
　また、上記したように、疎水性樹脂（Ｄ）は、側鎖部分にＣＨ３部分構造を含むことも好ましい。
　ここで、疎水性樹脂（Ｄ）中の側鎖部分が有するＣＨ３部分構造（以下、単に「側鎖ＣＨ３部分構造」ともいう）には、エチル基、プロピル基等が有するＣＨ３部分構造を包含するものである。
　一方、疎水性樹脂（Ｄ）の主鎖に直接結合しているメチル基（例えば、メタクリル酸構造を有する繰り返し単位のα－メチル基）は、主鎖の影響により疎水性樹脂（Ｄ）の表面偏在化への寄与が小さいため、本発明におけるＣＨ３部分構造に包含されないものとする。 Further, as described above, the hydrophobic resin (D), it is also preferred to include CH 3 partial structure side chain moiety.
Here, CH 3 partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH 3 partial structure") The, CH 3 partial structure an ethyl group, and a propyl group having Is included.
On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH 3 partial structure in the present invention.
　より具体的には、疎水性樹脂（Ｄ）が、例えば、下記一般式（Ｍ）で表される繰り返し単位などの、炭素－炭素二重結合を有する重合性部位を有するモノマーに由来する繰り返し単位を含む場合であって、Ｒ１１～Ｒ１４がＣＨ３「そのもの」である場合、そのＣＨ３は、本発明における側鎖部分が有するＣＨ３部分構造には包含されない。
　一方、Ｃ－Ｃ主鎖から何らかの原子を介して存在するＣＨ３部分構造は、本発明におけるＣＨ３部分構造に該当するものとする。例えば、Ｒ１１がエチル基（ＣＨ２ＣＨ３）である場合、本発明におけるＣＨ３部分構造を「１つ」有するものとする。 More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
Meanwhile, CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention. For example, when R 11 is an ethyl group (CH 2 CH 3 ), it is assumed that it has “one” CH 3 partial structure in the present invention.
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
　上記一般式（Ｍ）中、
　Ｒ１１～Ｒ１４は、各々独立に、側鎖部分を表す。
　側鎖部分のＲ１１～Ｒ１４としては、水素原子、１価の有機基などが挙げられる。
　Ｒ１１～Ｒ１４についての１価の有機基としては、アルキル基、シクロアルキル基、アリール基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルアミノカルボニル基、シクロアルキルアミノカルボニル基、アリールアミノカルボニル基などが挙げられ、これらの基は、更に置換基を有していてもよい。 In the general formula (M),
R 11 to R 14 each independently represents a side chain portion.
Examples of R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
　疎水性樹脂（Ｄ）は、側鎖部分にＣＨ３部分構造を有する繰り返し単位を有する樹脂であることが好ましく、このような繰り返し単位として、下記一般式（ＩＩ）で表される繰り返し単位、及び、下記一般式（ＩＩＩ）で表される繰り返し単位のうち少なくとも一種の繰り返し単位（ｘ）を有していることがより好ましい。 The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).
　以下、一般式（ＩＩ）で表される繰り返し単位について詳細に説明する。 Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
　上記一般式（ＩＩ）中、Ｘｂ１は水素原子、アルキル基、シアノ基又はハロゲン原子を表し、Ｒ２は１つ以上のＣＨ３部分構造を有する、酸に対して安定な有機基を表す。ここで、酸に対して安定な有機基は、より具体的には、酸分解性基（酸の作用により分解してカルボキシ基などの極性基を生じる基）を有さない有機基であることが好ましい。 In the general formula (II), X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R 2 has one or more CH 3 partial structure represents a stable organic radical to acid. Here, the organic group that is stable to an acid is more specifically an organic group that does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferred.
　Ｘｂ１のアルキル基は、炭素数１～４のアルキル基が好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基又はトリフルオロメチル基等が挙げられるが、メチル基であることが好ましい。
　Ｘｂ１は、水素原子又はメチル基であることが好ましい。
　Ｒ２としては、１つ以上のＣＨ３部分構造を有する、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基が挙げられる。上記のシクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基は、更に、置換基としてアルキル基を有していてもよい。
　Ｒ２は、１つ以上のＣＨ３部分構造を有する、アルキル基又はアルキル置換シクロアルキル基が好ましい。
　Ｒ２としての１つ以上のＣＨ３部分構造を有する酸に安定な有機基は、ＣＨ３部分構造を２個以上１０個以下有することが好ましく、２個以上８個以下有することがより好ましい。
　一般式（ＩＩ）で表される繰り返し単位の好ましい具体例を以下に挙げる。尚、本発明はこれに限定されるものではない。 The alkyl group of Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X b1 is preferably a hydrogen atom or a methyl group.
Examples of R 2 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH 3 partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH 3 partial structures.
The acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
　一般式（ＩＩ）で表される繰り返し単位は、酸に安定な（非酸分解性の）繰り返し単位であることが好ましく、具体的には、酸の作用により分解して極性基を生じる基を有さない繰り返し単位であることが好ましい。
　以下、一般式（ＩＩＩ）で表される繰り返し単位について詳細に説明する。 The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
Hereinafter, the repeating unit represented by formula (III) will be described in detail.
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
　上記一般式（ＩＩＩ）中、Ｘｂ２は水素原子、アルキル基、シアノ基又はハロゲン原子を表し、Ｒ３は１つ以上のＣＨ３部分構造を有する、酸に対して安定な有機基を表し、ｎは１から５の整数を表す。
　Ｘｂ２のアルキル基は、炭素数１～４のものが好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基又はトリフルオロメチル基等が挙げられるが、水素原子である事が好ましい。
　Ｘｂ２は、水素原子であることが好ましい。
　Ｒ３は、酸に対して安定な有機基であるため、より具体的には、酸分解性基を有さない有機基であることが好ましい。 In the above general formula (III), X b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R 3 represents an acid-stable organic group having one or more CH 3 partial structures, n represents an integer of 1 to 5.
The alkyl group of Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X b2 is preferably a hydrogen atom.
Since R 3 is an organic group that is stable against acid, more specifically, R 3 is preferably an organic group having no acid-decomposable group.
　Ｒ３としては、１つ以上のＣＨ３部分構造を有する、アルキル基が挙げられる。
　Ｒ３としての１つ以上のＣＨ３部分構造を有する酸に安定な有機基は、ＣＨ３部分構造を１個以上１０個以下有することが好ましく、１個以上８個以下有することがより好ましく、１個以上４個以下有することが更に好ましい。
　ｎは１から５の整数を表し、１～３の整数を表すことがより好ましく、１又は２を表すことが更に好ましい。 R 3 includes an alkyl group having one or more CH 3 partial structures.
The acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has 1 or more and 10 or less CH 3 partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
　一般式（ＩＩＩ）で表される繰り返し単位の好ましい具体例を以下に挙げる。尚、本発明はこれに限定されるものではない。 Preferred specific examples of the repeating unit represented by the general formula (III) are given below. Note that the present invention is not limited to this.
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
　一般式（ＩＩＩ）で表される繰り返し単位は、酸に安定な（非酸分解性の）繰り返し単位であることが好ましく、具体的には、酸の作用により分解して、極性基を生じる基を有さない繰り返し単位であることが好ましい。 The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
　疎水性樹脂（Ｄ）が、側鎖部分にＣＨ３部分構造を含む場合であり、更に、特にフッ素原子及び珪素原子を有さない場合、一般式（ＩＩ）で表される繰り返し単位、及び、一般式（ＩＩＩ）で表される繰り返し単位のうち少なくとも一種の繰り返し単位（ｘ）の含有量は、疎水性樹脂（Ｄ）の全繰り返し単位に対して、９０モル％以上であることが好ましく、９５モル％以上であることがより好ましい。含有量は、疎水性樹脂（Ｄ）の全繰り返し単位に対して、通常、１００モル％以下である。 In the case where the hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin (D).
　疎水性樹脂（Ｄ）が、一般式（ＩＩ）で表される繰り返し単位、及び、一般式（ＩＩＩ）で表される繰り返し単位のうち少なくとも一種の繰り返し単位（ｘ）を、疎水性樹脂（Ｄ）の全繰り返し単位に対し、９０モル％以上で含有することにより、疎水性樹脂（Ｄ）の表面自由エネルギーが増加する。その結果として、疎水性樹脂（Ｄ）がレジスト膜の表面に偏在しにくくなり、水に対するレジスト膜の静的／動的接触角を確実に向上させて、液浸液追随性を向上させることができる。 The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.
　また、疎水性樹脂（Ｄ）は、（ｉ）フッ素原子及び／又は珪素原子を含む場合においても、（ｉｉ）側鎖部分にＣＨ３部分構造を含む場合においても、下記（ｘ）～（ｚ）の群から選ばれる基を少なくとも１つを有していてもよい。
　（ｘ）酸基、
　（ｙ）アルカリ現像液の作用により分解してアルカリ現像液に対する溶解度が増大する基（以下、極性変換基ともいう）、
　（ｚ）酸の作用により分解する基 In addition, the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH 3 partial structure is included in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter also referred to as a polar conversion group);
(Z) a group decomposable by the action of an acid
　酸基（ｘ）としては、フェノール性水酸基、カルボン酸基、フッ素化アルコール基、スルホン酸基、スルホンアミド基、スルホニルイミド基、（アルキルスルホニル）（アルキルカルボニル）メチレン基、（アルキルスルホニル）（アルキルカルボニル）イミド基、ビス（アルキルカルボニル）メチレン基、ビス（アルキルカルボニル）イミド基、ビス（アルキルスルホニル）メチレン基、ビス（アルキルスルホニル）イミド基、トリス（アルキルカルボニル）メチレン基、トリス（アルキルスルホニル）メチレン基等が挙げられる。
　好ましい酸基としては、フッ素化アルコール基（好ましくはヘキサフルオロイソプロパノール）、スルホンイミド基、ビス（アルキルカルボニル）メチレン基が挙げられる。 Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.
　酸基（ｘ）を有する繰り返し単位としては、アクリル酸、メタクリル酸による繰り返し単位のような樹脂の主鎖に、直接、酸基が結合している繰り返し単位、或いは、連結基を介して樹脂の主鎖に酸基が結合している繰り返し単位などが挙げられ、更には酸基を有する重合開始剤や連鎖移動剤を重合時に用いてポリマー鎖の末端に導入することもでき、いずれの場合も好ましい。酸基（ｘ）を有する繰り返し単位が、フッ素原子及び珪素原子の少なくともいずれかを有していてもよい。
　酸基（ｘ）を有する繰り返し単位の含有量は、疎水性樹脂（Ｄ）中の全繰り返し単位に対し、１～５０モル％が好ましく、より好ましくは３～３５モル％、更に好ましくは５～２０モル％である。
　酸基（ｘ）を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。式中、Ｒｘは水素原子、ＣＨ３、ＣＦ３、又は、ＣＨ２ＯＨを表す。 The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.
Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
　アルカリ現像液の作用により分解してアルカリ現像液に対する溶解度が増大する基（ｙ）としては、ラクトン構造を有する基、酸無水物基、又は酸イミド基が好ましく、ラクトン構造を有する基が特に好ましい。
　これらの基を含んだ繰り返し単位は、例えば、アクリル酸エステル及びメタクリル酸エステルによる繰り返し単位等の、樹脂の主鎖に直接この基が結合している繰り返し単位である。或いは、この繰り返し単位は、この基が連結基を介して樹脂の主鎖に結合している繰り返し単位であってもよい。或いは、この繰り返し単位は、この基を有する重合開始剤又は連鎖移動剤を重合時に用いて、樹脂の末端に導入されていてもよい。
　ラクトン構造を有する基を有する繰り返し単位としては、例えば、先に樹脂Ｐの項で説明したラクトン構造を有する繰り返し単位と同様のものが挙げられる。 The group (y) that decomposes by the action of an alkali developer and increases the solubility in the alkali developer is preferably a group having a lactone structure, an acid anhydride group, or an acid imide group, and particularly preferably a group having a lactone structure. .
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.
Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin P.
　アルカリ現像液の作用により分解してアルカリ現像液に対する溶解度が増大する基（ｙ）を有する繰り返し単位の含有量は、疎水性樹脂（Ｄ）中の全繰り返し単位を基準として、１～１００モル％であることが好ましく、３～９８モル％であることがより好ましく、５～９５モル％であることが更に好ましい。 The content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is preferably 3 to 98 mol%, more preferably 5 to 95 mol%.
　疎水性樹脂（Ｄ）に於ける、酸の作用により分解する基（ｚ）を有する繰り返し単位は、樹脂Ｐで挙げた酸分解性基を有する繰り返し単位と同様のものが挙げられる。酸の作用により分解する基（ｚ）を有する繰り返し単位が、フッ素原子及び珪素原子の少なくともいずれかを有していてもよい。疎水性樹脂（Ｄ）に於ける、酸の作用により分解する基（ｚ）を有する繰り返し単位の含有量は、樹脂（Ｄ）中の全繰り返し単位に対し、１～８０モル％が好ましく、より好ましくは１０～８０モル％、更に好ましくは２０～６０モル％である。
　疎水性樹脂（Ｄ）は、更に、上述した繰り返し単位とは別の繰り返し単位を有していてもよい。 In the hydrophobic resin (D), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin P. The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
The hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
　フッ素原子を含む繰り返し単位は、疎水性樹脂（Ｄ）に含まれる全繰り返し単位中１０～１００モル％が好ましく、３０～１００モル％がより好ましい。また、珪素原子を含む繰り返し単位は、疎水性樹脂（Ｄ）に含まれる全繰り返し単位中、１０～１００モル％が好ましく、２０～１００モル％がより好ましい。 The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
　一方、特に疎水性樹脂（Ｄ）が側鎖部分にＣＨ３部分構造を含む場合においては、疎水性樹脂（Ｄ）が、フッ素原子及び珪素原子を実質的に含有しない形態も好ましい。また、疎水性樹脂（Ｄ）は、炭素原子、酸素原子、水素原子、窒素原子及び硫黄原子から選ばれる原子のみによって構成された繰り返し単位のみで実質的に構成されることが好ましい。 On the other hand, particularly when the hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion, a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable. Moreover, it is preferable that hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
　疎水性樹脂（Ｄ）の標準ポリスチレン換算の重量平均分子量は、好ましくは１，０００～１００，０００で、より好ましくは１，０００～５０，０００である。
　また、疎水性樹脂（Ｄ）は、１種で使用してもよいし、複数併用してもよい。
　疎水性樹脂（Ｄ）の組成物中の含有量は、本発明の組成物中の全固形分に対し、０．０１～１０質量％が好ましく、０．０５～８質量％がより好ましい。 The standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.
　疎水性樹脂（Ｄ）は、残留単量体やオリゴマー成分が０．０１～５質量％であることが好ましく、より好ましくは０．０１～３質量％である。また、分子量分布（Ｍｗ／Ｍｎ、分散度ともいう）は、１～５の範囲が好ましく、より好ましくは１～３の範囲である。 In the hydrophobic resin (D), the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
　疎水性樹脂（Ｄ）は、各種市販品を利用することもできるし、常法に従って（例えばラジカル重合）合成することができる。 As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
＜（Ｆ）界面活性剤＞
　本発明において用いられる感活性光線又は感放射線性組成物は、界面活性剤（Ｆ）を更に含んでいてもよい。界面活性剤を含有することにより、波長が２５０ｎｍ以下、特には２２０ｎｍ以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
　界面活性剤としては、フッ素系及び／又はシリコン系界面活性剤を用いることが特に好ましい。
　フッ素系及び／又はシリコン系界面活性剤としては、例えば、米国特許出願公開第２００８／０２４８４２５号明細書の［０２７６］に記載の界面活性剤が挙げられる。また、エフトップＥＦ３０１若しくはＥＦ３０３（新秋田化成（株）製）；フロラードＦＣ４３０、４３１若しくは４４３０（住友スリーエム（株）製）；メガファックＦ１７１、Ｆ１７３、Ｆ１７６、Ｆ１８９、Ｆ１１３、Ｆ１１０、Ｆ１７７、Ｆ１２０若しくはＲ０８（ＤＩＣ（株）製）；サーフロンＳ－３８２、ＳＣ１０１、１０２、１０３、１０４、１０５若しくは１０６（旭硝子（株）製）；トロイゾルＳ－３６６（トロイケミカル（株）製）；ＧＦ－３００若しくはＧＦ－１５０（東亜合成化学（株）製）、サーフロンＳ－３９３（セイミケミカル（株）製）；エフトップＥＦ１２１、ＥＦ１２２Ａ、ＥＦ１２２Ｂ、ＲＦ１２２Ｃ、ＥＦ１２５Ｍ、ＥＦ１３５Ｍ、ＥＦ３５１、ＥＦ３５２、ＥＦ８０１、ＥＦ８０２若しくはＥＦ６０１（（株）ジェムコ製）；ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０若しくはＰＦ６５２０（ＯＭＮＯＶＡ社製）；又は、ＦＴＸ－２０４Ｇ、２０８Ｇ、２１８Ｇ、２３０Ｇ、２０４Ｄ、２０８Ｄ、２１２Ｄ、２１８Ｄ若しくは２２２Ｄ（（株）ネオス製）を用いてもよい。尚、ポリシロキサンポリマーＫＰ－３４１（信越化学工業（株）製）も、シリコン系界面活性剤として用いることができる。 <(F) Surfactant>
The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a surfactant (F). 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.
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include 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 FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
　また、界面活性剤は、上記に示すような公知のものの他に、テロメリゼーション法（テロマー法ともいわれる）又はオリゴメリゼーション法（オリゴマー法ともいわれる）により製造されたフルオロ脂肪族化合物を用いて合成してもよい。具体的には、このフルオロ脂肪族化合物から導かれたフルオロ脂肪族基を備えた重合体を、界面活性剤として用いてもよい。このフルオロ脂肪族化合物は、例えば、特開２００２－９０９９１号公報に記載された方法によって合成することができる。
　また、米国特許出願公開第２００８／０２４８４２５号明細書の［０２８０］に記載されているフッ素系及び／又はシリコン系以外の界面活性剤を使用してもよい。 In addition to known surfactants as described above, 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.
　これら界面活性剤は、１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 These surfactants may be used alone or in combination of two or more.
　本発明において用いられる感活性光線又は感放射線性組成物が界面活性剤を含んでいる場合、その含有量は、組成物の全固形分を基準として、好ましくは０～２質量％、より好ましくは０．０００１～２質量％、更に好ましくは０．０００５～１質量％である。 When the actinic ray-sensitive or radiation-sensitive composition used in the present invention contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably based on the total solid content of the composition. The content is 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.
＜その他の添加剤＞
　本発明において用いられる感活性光線又は感放射線性組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び／又は現像液に対する溶解性を促進させる化合物（例えば、分子量１０００以下のフェノール化合物、又はカルボキシ基を含んだ脂環族若しくは脂肪族化合物）を更に含んでいてもよい。 <Other additives>
The actinic ray- or radiation-sensitive composition used in the present invention is a compound (for example, molecular weight) that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer. 1000 or less phenol compounds, or alicyclic or aliphatic compounds containing a carboxy group) may further be included.
　本発明において用いられる感活性光線又は感放射線性組成物は、溶解阻止化合物を更に含んでいてもよい。ここで「溶解阻止化合物」とは、酸の作用により分解して有機系現像液中での溶解度が減少する、分子量３０００以下の化合物である。 The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a dissolution inhibiting compound. Here, 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.
　本発明において用いられる感活性光線又は感放射線性組成物は、有機酸を含有することも好ましい。この場合、有機酸の量は、経時安定性の観点から多い方が好ましく、本発明の感活性光線性又は感放射線性組成物中における有機酸の含有率が、全固形分に対し５質量％超となるよう添加されることが好ましい。本発明の一形態において、本発明の組成物における有機酸の含有率は、組成物中の全固形分を基準として５質量％より多く１５質量％未満あることがより好ましく、５質量％より多く１０質量％未満であることが更に好ましい。 The actinic ray-sensitive or radiation-sensitive composition used in the present invention preferably contains an organic acid. In this case, the amount of the organic acid is preferably larger from the viewpoint of stability over time, and the content of the organic acid in the actinic ray-sensitive or radiation-sensitive composition of the present invention is 5% by mass with respect to the total solid content. It is preferable to add so that it may become super. In one embodiment of the present invention, the organic acid content in the composition of the present invention is more preferably more than 5% by weight and less than 15% by weight based on the total solid content in the composition, more than 5% by weight. More preferably, it is less than 10 mass%.
　有機酸は、経時安定性の観点からは、ｐＫａが０～１０の範囲であることが好ましく、２～８の範囲であることがより好ましく、３～７の範囲が更に好ましい。ここでｐＫａとは、水溶液中でのｐＫａのことを表し、例えば、化学便覧（ＩＩ）（改訂４版、１９９３年、日本化学会編、丸善株式会社）に記載のものであり、この値が低いほど酸強度が大きいことを示している。水溶液中でのｐＫａは、具体的には、無限希釈水溶液を用い、２５℃での酸解離定数を測定することにより実測することができ、また、下記ソフトウェアパッケージ１を用いて、ハメットの置換基定数及び公知文献値のデータベースに基づいた値を、計算により求めることもできる。本明細書におけるｐＫａの値は、全て、このソフトウェアパッケージを用いて計算により求めた値を示している。ソフトウェアパッケージ１：　Ａｄｖａｎｃｅｄ　Ｃｈｅｍｉｓｔｒｙ　Ｄｅｖｅｌｏｐｍｅｎｔ　（ＡＣＤ／Ｌａｂｓ）　Ｓｏｆｔｗａｒｅ　Ｖ８．１４　ｆｏｒ　Ｓｏｌａｒｉｓ　（１９９４－２００７　ＡＣＤ／Ｌａｂｓ）。 The organic acid preferably has a pKa in the range of 0 to 10, more preferably in the range of 2 to 8, and still more preferably in the range of 3 to 7, from the viewpoint of stability over time. Here, pKa represents pKa in an aqueous solution. For example, it is described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). A lower value indicates a higher acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa in this specification all indicate values obtained by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).
　樹脂と光酸発生剤との間で生じる付加反応を抑制する観点から、有機酸のｐＫａは、樹脂のｐＫａより低いことが好ましく、また、酸発生剤から発生する酸のｐＫａより高いことが好ましい。本発明の一形態において、有機酸のｐＫａは、樹脂（Ｂ）のｐＫａより３以上低いことが好ましく、５以上低いことがより好ましい。また、他の形態において、有機酸のｐＫａは、光酸発生剤から発生する酸のｐＫａより２以上高いことが好ましく、３以上高いことがより好ましい。 From the viewpoint of suppressing the addition reaction occurring between the resin and the photoacid generator, the pKa of the organic acid is preferably lower than the pKa of the resin, and preferably higher than the pKa of the acid generated from the acid generator. . In one embodiment of the present invention, the pKa of the organic acid is preferably 3 or more and more preferably 5 or more lower than the pKa of the resin (B). In another embodiment, the pKa of the organic acid is preferably 2 or more, and more preferably 3 or more, higher than the pKa of the acid generated from the photoacid generator.
　本発明において使用し得る有機酸としては、例えば、有機カルボン酸、有機スルホン酸等が挙げられ、中でも有機カルボン酸が好ましい。有機カルボン酸としては、例えば、芳香族有機カルボン酸、脂肪族カルボン酸、脂環式カルボン酸、不飽和脂肪族カルボン酸、オキシカルボン酸、アルコキシカルボン酸等が挙げられる。本発明の一形態において、有機酸は、有機カルボン酸であることが好ましく、芳香族有機カルボン酸であることがより好ましく、安息香酸、サリチル酸、２－ヒドロキシ－３－ナフトエ酸、２－ナフトエ酸等であることが更に好ましく、サリチル酸であることが最も好ましい。　 Examples of the organic acid that can be used in the present invention include organic carboxylic acids and organic sulfonic acids, among which organic carboxylic acids are preferable. Examples of the organic carboxylic acid include aromatic organic carboxylic acids, aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, and alkoxycarboxylic acids. In one embodiment of the present invention, the organic acid is preferably an organic carboxylic acid, more preferably an aromatic organic carboxylic acid, benzoic acid, salicylic acid, 2-hydroxy-3-naphthoic acid, 2-naphthoic acid. Are more preferable, and salicylic acid is most preferable. *
　有機カルボン酸のｐＫａは、３．３以上であることが好ましい。
　また、有機カルボン酸は、カルボキシル基以外の酸基を有さないものであることが好ましい。 The pKa of the organic carboxylic acid is preferably 3.3 or more.
The organic carboxylic acid preferably has no acid group other than the carboxyl group.
　感活性光線又は感放射線性組成物が、有機カルボン酸を含有することにより、有機カルボン酸が感活性光線又は感放射線性組成物中の塩基性化合物を中和することで、樹脂（Ｂ）、疎水性樹脂（Ｄ）、及び、重合体に組み込まれた形態の化合物（Ａ）の経時分解を防ぎ、感活性光線又は感放射線性組成物の経時安定性が向上する傾向となる。 When the actinic ray or radiation sensitive composition contains an organic carboxylic acid, the organic carboxylic acid neutralizes the basic compound in the actinic ray or radiation sensitive composition, whereby the resin (B), The time-dependent degradation of the hydrophobic resin (D) and the compound (A) in a form incorporated in the polymer is prevented, and the stability over time of the actinic ray-sensitive or radiation-sensitive composition tends to be improved.
　以下、有機カルボン酸の好適な具体例を示す。 Hereinafter, preferred specific examples of the organic carboxylic acid will be shown.
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
＜レジスト膜＞
　本発明は、本発明の感活性光線又は感放射線性組成物により形成されたレジスト膜にも関し、このような膜は、例えば、本発明の組成物が基板等の支持体上に塗布されることにより形成される。この膜の厚みは、０．０２～０．１μｍが好ましい。基板上に塗布する方法としては、スピンコート、ロールコート、フローコート、ディップコート、スプレーコート、ドクターコート等の適当な塗布方法により基板上に塗布されるが、スピン塗布が好ましく、その回転数は１０００～３０００ｒｐｍが好ましい。塗布膜は６０～１５０℃で１～２０分間、好ましくは８０～１２０℃で１～１０分間プリベークして薄膜を形成する。
　被加工基板及びその最表層を構成する材料は、例えば、半導体用ウエハの場合、シリコンウエハを用いることができ、最表層となる材料の例としては、Ｓｉ、ＳｉＯ２、ＳｉＮ、ＳｉＯＮ、ＴｉＮ、ＷＳｉ、ＢＰＳＧ、ＳＯＧ、有機反射防止膜等が挙げられる。 <Resist film>
The present invention also relates to a resist film formed with the actinic ray-sensitive or radiation-sensitive composition of the present invention. For example, the composition of the present invention is coated on a support such as a substrate. Is formed. The thickness of this film is preferably 0.02 to 0.1 μm. As a method for coating on the substrate, spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. are applied on the substrate, but spin coating is preferred, and the number of rotations is 1000 to 3000 rpm is preferred. The coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes to form a thin film.
For example, in the case of a semiconductor wafer, a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer. Examples of the material that becomes the outermost layer include Si, SiO 2 , SiN, SiON, TiN, Examples thereof include WSi, BPSG, SOG, and an organic antireflection film.
　レジスト膜を形成する前に、基板上に予め反射防止膜を塗設してもよい。
　反射防止膜としては、チタン、二酸化チタン、窒化チタン、酸化クロム、カーボン、アモルファスシリコン等の無機膜型と、吸光剤とポリマー材料からなる有機膜型のいずれも用いることができる。また、有機反射防止膜として、ブリューワーサイエンス社製のＤＵＶ３０シリーズや、ＤＵＶ－４０シリーズ、シプレー社製のＡＲ－２、ＡＲ－３、ＡＲ－５等の市販の有機反射防止膜を使用することもできる。 Before forming the resist film, an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.
　尚、本発明のパターン形成方法においては、レジスト膜の上層にトップコートを形成してもよい。トップコートは、レジスト膜と混合せず、更にレジスト膜上層に均一に塗布できることが好ましい。
　トップコートについては、特に限定されず、従来公知のトップコートを、従来公知の方法によって形成でき、例えば、特開２０１４－０５９５４３号公報の段落００７２～００８２の記載に基づいてトップコートを形成できる。
　例えば、特開２０１３－６１６４８号公報に記載されたような塩基性化合物を含有するトップコートをレジスト膜上に形成することが好ましい。トップコートが含み得る塩基性化合物の具体的な例は、上述の塩基性化合物（Ｅ）と同様である。
　また、トップコートは、エーテル結合、チオエーテル結合、ヒドロキシル基、チオール基、カルボニル結合及びエステル結合からなる群より選択される基又は結合を少なくとも一つ含む化合物を含むことが好ましい。 In the pattern forming method of the present invention, a top coat may be formed on the upper layer of the resist film. 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. For example, the topcoat can be formed based on the description in paragraphs 0072 to 0082 of JP-A No. 2014-059543.
For example, it is preferable to form a topcoat containing a basic compound as described in JP2013-61648A on the resist film. Specific examples of the basic compound that can be contained in the top coat are the same as those of the basic compound (E) described above.
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.
　また、トップコートは、樹脂を含有することが好ましい。トップコートが含有することができる樹脂としては、特に限定されないが、感活性光線性又は感放射線性組成物に含まれ得る疎水性樹脂と同様のものを使用することができ、上述の疎水性樹脂（Ｄ）を好適に挙げることができる。
　疎水性樹脂に関しては、特開２０１３－６１６４７号公報の［００１７］～［００２３］（対応する米国公開特許公報２０１３／２４４４３８号の［００１７］～［００２３］）、及び特開２０１４－５６１９４号公報の［００１６］～［０１６５］の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
　トップコートは、芳香環を有する繰り返し単位を含有する樹脂を含むことが好ましい。芳香環を有する繰り返し単位を含有することで、特に電子線又はＥＵＶ露光の際に、二次電子の発生効率、及び活性光線又は放射線により酸を発生する化合物からの酸発生効率が高くなり、パターン形成時に高感度化、高解像化の効果が期待できる The top coat preferably contains a resin. The resin that can be contained in the top coat is not particularly limited, and the same hydrophobic resin that can be contained in the actinic ray-sensitive or radiation-sensitive composition can be used. (D) can be mentioned suitably.
As for 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. 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, are increased. High sensitivity and high resolution can be expected when forming
　樹脂の重量平均分子量は好ましくは３０００～１０００００であり、更に好ましくは３０００～３００００であり、最も好ましくは５０００～２００００である。トップコート形成用組成物中の樹脂の配合量は、全固形分中、５０～９９．９質量％が好ましく、７０～９９．７質量％がより好ましく、８０～９９.５質量％が更に好ましい。 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 the 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. .
　トップコートが複数の樹脂を含む場合、フッ素原子及び／又は珪素原子を有する樹脂（ＸＡ）を少なくとも１種含むことが好ましい。フッ素原子及び／又は珪素原子を有する樹脂（ＸＡ）を少なくとも１種、及び、フッ素原子及び／又は珪素原子の含有率が樹脂（ＸＡ）より小さい樹脂（ＸＢ）をトップコート組成物が含むことがより好ましい。これにより、トップコート膜を形成した際に、樹脂（ＸＡ）がトップコート膜の表面に偏在するため、現像特性や液浸液追随性などの性能を改良させることができる。 When the top coat contains a plurality of resins, it is preferable to contain at least one resin (XA) having fluorine atoms and / or silicon atoms. 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.
　樹脂（ＸＡ）の含有量は、トップコート組成物に含まれる全固形分を基準として、０．０１～３０質量％が好ましく、０．１～１０質量％がより好ましく、０．１～８質量％が更に好ましく、０．１～５質量％が特に好ましい。樹脂（ＸＢ）の含有量は、トップコート組成物に含まれる全固形分を基準として、５０．０～９９．９質量％が好ましく、６０～９９．９質量％がより好ましく、７０～９９．９質量％が更に好ましく、８０～９９．９質量％が特に好ましい。 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.
　樹脂（ＸＡ）に含有されるフッ素原子の好ましい範囲は、樹脂（ＸＡ）の重量平均分子量に対して、５～８０質量％であることが好ましく、１０～８０質量％であることがより好ましい。
　樹脂（ＸＡ）に含有される珪素原子の好ましい範囲は、樹脂（ＸＡ）の重量平均分子量に対して、２～５０質量％であることが好ましく、２～３０質量％であることがより好ましい。 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).
　樹脂（ＸＢ）としては、フッ素原子及び珪素原子を実質的に含有しない形態が好ましく、この場合、具体的には、フッ素原子を有する繰り返し単位及び珪素原子を有する繰り返し単位の合計の含有量が、樹脂（ＸＢ）中の全繰り返し単位に対して０～２０モル％が好ましく、０～１０モル％がより好ましく、０～５モル％が更に好ましく、０～３モル％が特に好ましく、理想的には０モル％、すなわち、フッ素原子及び珪素原子を含有しない。 As the resin (XB), a form that substantially does not contain a fluorine atom and a silicon atom is preferable. In this case, specifically, 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.
　トップコート組成物全体中の樹脂の配合量は、全固形分中、５０～９９．９質量％が好ましく、６０～９９．０質量％がより好ましい。 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.
　また、トップコートは、酸発生剤、架橋剤、及び、上記化合物（Ａ）を含有しても良い。これらの各成分の具体例及び好ましい例は上述の通りである。 The top coat may contain an acid generator, a crosslinking agent, and the compound (A). Specific examples and preferred examples of these components are as described above.
　トップコートは、典型的には、トップコート形成用組成物から形成される。
　トップコート形成用組成物は、各成分を溶剤に溶解し、フィルター濾過することが好ましい。フィルターとしては、ポアサイズ０．１μｍ以下、より好ましくは０．０５μｍ以下、更に好ましくは０．０３μｍ以下のポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のものが好ましい。尚、フィルターは、複数種類を直列又は並列に接続して用いてもよい。また、組成物を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であっても良い。更に、フィルター濾過の前後で、組成物に対して脱気処理などを行ってもよい。本発明のトップコート形成用組成物は、金属等の不純物を含まないことが好ましい。これら材料に含まれる金属成分の含有量としては、１０ｐｐｍ以下が好ましく、５ｐｐｍ以下がより好ましく、１ｐｐｍ以下が更に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が特に好ましい。 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 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Note that a plurality of types of filters may be connected in series or in parallel. Moreover, 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 behind 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). .
　後述する露光を液浸露光とする場合、トップコートは、レジスト膜と液浸液との間に配置され、レジスト膜を直接、液浸液に接触させない層としても機能する。この場合、トップコート（トップコート形成用組成物）が有することが好ましい特性としては、レジスト膜への塗布適性、放射線、特に１９３ｎｍに対する透明性、液浸液（好ましくは水）に対する難溶性である。また、トップコートは、レジスト膜と混合せず、更にレジスト膜の表面に均一に塗布できることが好ましい。
　尚、トップコート形成用組成物を、レジスト膜の表面に、レジスト膜を溶解せずに均一に塗布するために、トップコート形成用組成物は、レジスト膜を溶解しない溶剤を含有することが好ましい。レジスト膜を溶解しない溶剤としては、後に詳述する有機溶剤を含有する現像液（有機系現像液）とは異なる成分の溶剤を用いることが更に好ましい。 When the exposure described later is immersion exposure, 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. In this case, preferable properties of the topcoat (topcoat-forming composition) include suitability for application to a resist film, transparency to radiation, particularly 193 nm, and poor solubility in an immersion liquid (preferably water). . Further, it is preferable that the top coat is not mixed with the resist film and can be applied uniformly to the surface of the resist film.
In order to uniformly apply the topcoat-forming composition to the surface of the resist film without dissolving the resist film, the topcoat-forming composition preferably contains a solvent that does not dissolve the resist film. . As the solvent that does not dissolve the resist film, it is more preferable to use a solvent having a component different from that of the developer (organic developer) containing an organic solvent, which will be described in detail later.
　トップコート形成用組成物の塗布方法は、特に限定されず、従来公知のスピンコート法、スプレー法、ローラーコート法、浸漬法などを用いることができる。 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.
　トップコートの膜厚は特に制限されないが、露光光源に対する透明性の観点から、通常５ｎｍ～３００ｎｍ、好ましくは１０ｎｍ～３００ｎｍ、より好ましくは２０ｎｍ～２００ｎｍ、更に好ましくは３０ｎｍ～１００ｎｍの厚みで形成される。
　トップコートを形成後、必要に応じて基板を加熱（ＰＢ）する。
　トップコートの屈折率は、解像性の観点から、レジスト膜の屈折率に近いことが好ましい。
　トップコートは液浸液に不溶であることが好ましく、水に不溶であることがより好ましい。
　トップコートの後退接触角は、液浸液追随性の観点から、トップコートに対する液浸液の後退接触角（２３℃）が５０～１００度であることが好ましく、８０～１００度であることがより好ましい。
　液浸露光においては、露光ヘッドが高速でウエハ上をスキャンし露光パターンを形成していく動きに追随して、液浸液がウエハ上を動く必要があることから、動的な状態におけるトップコートに対する液浸液の接触角が重要になり、より良好なレジスト性能を得るためには、上記範囲の後退接触角を有することが好ましい。 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. .
After forming the top coat, 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.
In immersion exposure, 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. In order to obtain better resist performance, it is preferable to have a receding contact angle in the above range.
　トップコートを剥離する際は、有機系現像液を使用してもよいし、別途剥離剤を使用してもよい。剥離剤としては、レジスト膜への浸透が小さい溶剤が好ましい。トップコートの剥離がレジスト膜の現像と同時にできるという点では、トップコートは、有機系現像液により剥離できることが好ましい。剥離に用いる有機系現像液としては、レジスト膜の低露光部を溶解除去できるものであれば特に制限されない。 When peeling the top coat, an organic developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable. From the viewpoint that the top coat can be peeled off simultaneously with the development of the resist film, 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.
　有機系現像液で剥離するという観点からは、トップコートは有機系現像液に対する溶解速度が１～３００ｎｍ／ｓｅｃが好ましく、１０～１００ｎｍ／ｓｅｃがより好ましい。
　ここで、トップコートの有機系現像液に対する溶解速度とは、トップコートを成膜した後に現像液に暴露した際の膜厚減少速度であり、本発明においては２３℃の酢酸ブチルに浸漬させた際の速度とする。
　トップコートの有機系現像液に対する溶解速度を１／ｓｅｃ秒以上、好ましくは１０ｎｍ／ｓｅｃ以上とすることによって、レジスト膜を現像した後の現像欠陥発生が低減する効果がある。また、３００ｎｍ／ｓｅｃ以下、好ましくは１００ｎｍ／ｓｅｃとすることによって、おそらくは、液浸露光時の露光ムラが低減した影響で、レジスト膜を現像した後のパターンのラインエッジラフネスがより良好になるという効果がある。
　トップコートはその他の公知の現像液、例えば、アルカリ水溶液などを用いて除去してもよい。使用できるアルカリ水溶液として具体的には、テトラメチルアンモニウムヒドロキシドの水溶液が挙げられる。 From the viewpoint of peeling with an organic developer, the topcoat preferably has a dissolution rate in the organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
Here, 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. In the present invention, the top coat was immersed in butyl acetate at 23 ° C. Speed.
By setting the dissolution rate of the top coat in the organic developer to 1 / sec or more, preferably 10 nm / sec or more, there is an effect of reducing development defects after developing the resist film. In addition, by setting it to 300 nm / sec or less, preferably 100 nm / sec, 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. Specific examples of the aqueous alkali solution that can be used include an aqueous solution of tetramethylammonium hydroxide.
＜パターン形成方法＞
　本発明は、上記レジスト膜に活性光線又は放射線を照射する（露光する）ことと、上記活性光線又は放射線を照射した膜を現像することとを含むパターン形成方法に関する。本発明において、上記露光は、ＡｒＦエキシマレーザー、電子線又は極紫外線を用いて行われることが好ましい。 <Pattern formation method>
The present invention relates to a pattern forming method including irradiating (exposing) actinic light or radiation to the resist film and developing the film irradiated with the actinic light or radiation. In the present invention, the exposure is preferably performed using an ArF excimer laser, an electron beam or extreme ultraviolet rays.
　精密集積回路素子の製造などにおいてレジスト膜上への露光（パターン形成工程）は、まず、本発明のレジスト膜にパターン状に、ＡｒＦエキシマレーザー、電子線又は極紫外線（ＥＵＶ）照射を行うことが好ましい。露光量は、ＡｒＦエキシマレーザーの場合、１～１００ｍＪ／ｃｍ２程度、好ましくは２０～６０ｍＪ／ｃｍ２程度、電子線の場合、０．１～２０μＣ／ｃｍ２程度、好ましくは３～１０μＣ／ｃｍ２程度、極紫外線の場合、０．１～２０ｍＪ／ｃｍ２程度、好ましくは３～１５ｍＪ／ｃｍ２程度となるように露光する。
　次いで、ホットプレート上で、好ましくは６０～１５０℃で５秒～２０分間、より好ましくは８０～１２０℃で１５秒～１０分間、更に好ましくは８０～１２０℃で１～１０分間、露光後加熱（ポストエクスポージャーベーク）を行い、次いで、現像、リンス、乾燥することによりパターンを形成する。ここで、露光後加熱は、樹脂（Ｂ）における酸分解性基を有する繰り返し単位（ｂ）の酸分解性によって、適宜調整される。酸分解性が低い場合、露光後加熱の温度は１１０℃以上、加熱時間は４５秒以上であることも好ましい。樹脂（Ｂ）における酸分解性基を有する繰り返し単位（ｂ）が、式（ＡＩＩ）で表される繰り返し単位である場合、露光後加熱の温度は１１０℃以上、加熱時間は４５秒以上であることも好ましい。
　現像液は適宜選択されるが、アルカリ現像液（代表的にはアルカリ水溶液）又は有機溶剤を含有する現像液（有機系現像液ともいう）を用いることが好ましい。現像液がアルカリ水溶液である場合には、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、テトラブチルアンモニウムヒドロキシド（ＴＢＡＨ）等の、０．１～５質量％、好ましくは２～３質量％アルカリ水溶液で、０．１～３分間、好ましくは０．５～２分間、浸漬（ｄｉｐ）法、パドル（ｐｕｄｄｌｅ）法、スプレー（ｓｐｒａｙ）法等の常法により現像する。アルカリ現像液には、アルコール類及び／又は界面活性剤を、適当量添加してもよい。こうして、ネガ型パターンの形成おいては、未露光部分の膜は溶解し、露光された部分は現像液に溶解し難いことにより、またポジ型パターンの形成おいては、露光された部分の膜は溶解し、未露光部の膜は現像液に溶解し難いことにより、基板上に目的のパターンが形成される。 In the manufacture of a precision integrated circuit element or the like, the exposure (pattern formation process) on the resist film is performed by first irradiating the resist film of the present invention with ArF excimer laser, electron beam or extreme ultraviolet (EUV). preferable. Exposure in the case of ArF excimer laser, 1 ~ 100mJ / cm 2, preferably about 20 ~ 60mJ / cm 2 or so, when the electron beam, 0.1 ~ 20μC / cm 2, preferably about 3 ~ 10 [mu] C / cm about 2, in the case of extreme ultraviolet, 0.1 ~ 20 mJ / cm 2, preferably about exposed so that the 3 ~ 15 mJ / cm 2 or so.
Subsequently, post-exposure heating on a hot plate, preferably at 60 to 150 ° C. for 5 seconds to 20 minutes, more preferably at 80 to 120 ° C. for 15 seconds to 10 minutes, and even more preferably at 80 to 120 ° C. for 1 to 10 minutes. (Post exposure baking) is performed, and then a pattern is formed by developing, rinsing and drying. Here, the post-exposure heating is appropriately adjusted depending on the acid decomposability of the repeating unit (b) having an acid decomposable group in the resin (B). When the acid decomposability is low, the post-exposure heating temperature is preferably 110 ° C. or higher and the heating time is preferably 45 seconds or longer. When the repeating unit (b) having an acid-decomposable group in the resin (B) is a repeating unit represented by the formula (AII), the post-exposure heating temperature is 110 ° C. or higher, and the heating time is 45 seconds or longer. It is also preferable.
The developer is appropriately selected, but it is preferable to use an alkali developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an alkaline aqueous solution, it is 0.1 to 5% by mass, preferably 2 to 3% by mass alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), The development is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a paddle method, or a spray method. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer. Thus, in the formation of the negative pattern, the film of the unexposed portion is dissolved, and the exposed portion is difficult to dissolve in the developer, and in the formation of the positive pattern, the film of the exposed portion is formed. Is dissolved, and the film in the unexposed area is difficult to dissolve in the developer, whereby a target pattern is formed on the substrate.
　中でも、本発明のパターン形成方法においては、活性光線又は放射線を照射した膜を、有機溶剤を含有する現像液により現像して、ネガ型パターンを形成することが好ましい。 In particular, in the pattern forming method of the present invention, it is preferable to form a negative pattern by developing a film irradiated with actinic rays or radiation with a developer containing an organic solvent.
　本発明のパターン形成方法が、アルカリ現像液を用いて現像する工程を有する場合、アルカリ現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ－プロピルアミン等の第一アミン類、ジエチルアミン、ジ－ｎ－ブチルアミン等の第二アミン類、トリエチルアミン、メチルジエチルアミン等の第三アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドドキシド、テトラブチルアンモニウムヒドロキシド、テトラペンチルアンモニウムヒドロキシド、テトラヘキシルアンモニウムヒドロキシド、テトラオクチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ブチルトリメチルアンモニウムヒドロキシド、メチルトリアミルアンモニウムヒドロキシド、ジブチルジペンチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリエチルベンジルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシテチル）アンモニウムヒドロキシド等の第四級アンモニウム塩、ピロール、ピヘリジン等の環状アミン類等のアルカリ性水溶液を使用することができる。
　更に、上記アルカリ性水溶液にアルコール類、界面活性剤を適当量添加して使用することもできる。
　アルカリ現像液のアルカリ濃度は、通常０．１～２０質量％である。
　アルカリ現像液のｐＨは、通常１０．０～１５．０である。
　特に、テトラメチルアンモニウムヒドロキシドの２．３８質量％の水溶液が望ましい。 When the pattern forming method of the present invention includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, and triethanol Alcohol amines such as amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyl Tetraalkylammonium hydroxide such as ammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzyl Alkaline aqueous solutions such as quaternary ammonium salts such as ammonium hydroxide, triethylbenzylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, 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.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
　アルカリ現像の後に行うリンス処理におけるリンス液としては、純水を使用し、界面活性剤を適当量添加して使用することもできる。
　また、現像処理又はリンス処理の後に、パターン上に付着している現像液又はリンス液を超臨界流体により除去する処理を行うことができる。 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.
　本発明のパターン形成方法が、有機溶剤を含有する現像液を用いて現像する工程を有する場合、該工程における当該現像液（以下、有機系現像液とも言う）としては、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤等の極性溶剤及び炭化水素系溶剤を用いることができる。 When the pattern forming method of the present invention includes a step of developing using a developer containing an organic solvent, the developer in the step (hereinafter also referred to as an organic developer) includes a ketone solvent and an ester solvent. Polar solvents such as solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
　本発明において、エステル系溶剤とは分子内にエステル基を有する溶剤のことであり、ケトン系溶剤とは分子内にケトン基を有する溶剤のことであり、アルコール系溶剤とは分子内にアルコール性水酸基を有する溶剤のことであり、アミド系溶剤とは分子内にアミド基を有する溶剤のことであり、エーテル系溶剤とは分子内にエーテル結合を有する溶剤のことである。これらの中には、１分子内に上記官能基を複数種有する溶剤も存在するが、その場合は、その溶剤の有する官能基を含むいずれの溶剤種にも該当するものとする。例えば、ジエチレングリコールモノメチルエーテルは、上記分類中の、アルコール系溶剤、エーテル系溶剤いずれにも該当するものとする。また、炭化水素系溶剤とは置換基を有さない炭化水素溶剤のことである。
　特に、ケトン系溶剤、エステル系溶剤、アルコール系溶剤及びエーテル系溶剤から選択される少なくとも１種類の溶剤を含有する現像液であることが好ましい。 In the present invention, the ester solvent is a solvent having an ester group in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, and the alcohol solvent is alcoholic in the molecule. It is a solvent having a hydroxyl group, an amide solvent is a solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
In particular, a developer containing at least one kind of solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.
　現像液は、レジスト膜の膨潤を抑制できるという点から、炭素原子数が７以上（７～１４が好ましく、７～１２がより好ましく、７～１０が更に好ましい）、かつヘテロ原子数が２以下のエステル系溶剤を用いることが好ましい。
　上記エステル系溶剤のヘテロ原子は、炭素原子及び水素原子以外の原子であって、例えば、酸素原子、窒素原子、硫黄原子等が挙げられる。ヘテロ原子数は、２以下が好ましい。
　炭素原子数が７以上かつヘテロ原子数が２以下のエステル系溶剤の好ましい例としては、酢酸アミル、酢酸イソアミル、酢酸２－メチルブチル、酢酸１-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ヘプチル、ブタン酸ブチル、イソブタン酸イソブチルなどが挙げられ、酢酸イソアミル、又はイソブタン酸イソブチルを用いることが特に好ましい。 The developer has 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10), and 2 or less heteroatoms from the viewpoint that the swelling of the resist film can be suppressed. It is preferable to use the ester solvent.
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.
Preferred examples of 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 include heptyl propionate, butyl butanoate, isobutyl isobutanoate and the like, and it is particularly preferable to use isoamyl acetate or isobutyl isobutanoate.
　現像液は、上述した炭素原子数が７以上かつヘテロ原子数が２以下のエステル系溶剤に代えて、下記エステル系溶剤及び下記炭化水素系溶剤の混合溶剤、又は、下記ケトン系溶剤及び下記炭化水素溶剤の混合溶剤を用いてもよい。この場合においても、レジスト膜の膨潤の抑制に効果的である。
　エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、エステル系溶剤として酢酸イソアミルを用いることが好ましい。また、炭化水素系溶剤としては、レジスト膜の溶解性を調製するという観点から、飽和炭化水素溶剤（例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカンなど）を用いることが好ましい。
　ケトン系溶剤としては、例えば、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、アセトン、２－ヘプタノン（メチルアミルケトン）、４－ヘプタノン、１－ヘキサノン、２－ヘキサノン、ジイソブチルケトン、２，５－ジメチル－４－ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、イソホロン、プロピレンカーボネート等を挙げることができ、ジイソブチルケトン、２，５－ジメチル－４－ヘキサノンを用いることが特に好ましい。
　エステル系溶剤としては、例えば、酢酸メチル、酢酸ブチル、酢酸エチル、酢酸イソプロピル、酢酸ペンチル、酢酸イソアミル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル－３－エトキシプロピオネート、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル、酪酸ブチル、２－ヒドロキシイソ酪酸メチル等を挙げることができる。
　アルコール系溶剤としては、例えば、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、４－メチル－２－ペンタノール、ｔｅｒｔ－ブチルアルコール、イソブチルアルコール、ｎ－ヘキシルアルコール、ｎ－ヘプチルアルコール、ｎ－オクチルアルコール、ｎ－デカノール等のアルコールや、エチレングリコール、ジエチレングリコール、トリエチレングリコール等のグリコール系溶剤や、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、メトキシメチルブタノール等のグリコールエーテル系溶剤等を挙げることができる。
　エーテル系溶剤としては、例えば、上記グリコールエーテル系溶剤の他、アニソール、ジオキサン、テトラヒドロフラン等が挙げられる。
　アミド系溶剤としては、例えば、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、１，３－ジメチル－２－イミダゾリジノン等が使用できる。
　炭化水素系溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、オクタン、デカン、ウンデカン等の脂肪族炭化水素系溶剤が挙げられる。
　尚、炭化水素系溶剤である脂肪族炭化水素系溶剤においては、同じ炭素数で異なる構造の化合物の混合物であってもよい。例えば、脂肪族炭化水素系溶媒としてデカンを使用した場合、同じ炭素数で異なる構造の化合物である２－メチルノナン、２，２－ジメチルオクタン、４－エチルオクタン、イソオクタンなどが脂肪族炭化水素系溶媒に含まれていてもよい。
　また、上記同じ炭素数で異なる構造の化合物は、１種のみが含まれていてもよいし、上記のように複数種含まれていてもよい。
　上記の溶剤は、複数混合してもよいし、上記以外の溶剤や水と混合し使用してもよい。但し、本発明の効果を十二分に奏するためには、現像液全体としての含水率が１０質量％未満であることが好ましく、実質的に水分を含有しないことがより好ましい。
　すなわち、有機系現像液に対する有機溶剤の使用量は、現像液の全量に対して、９０質量％以上１００質量％以下であることが好ましく、９５質量％以上１００質量％以下であることが好ましい。
　特に、有機系現像液は、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも１種類の有機溶剤を含有する現像液であるのが好ましい。 Instead of the above-mentioned ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, the developer is a mixed solvent of the following ester solvent and the following hydrocarbon solvent, or the following ketone solvent and the following carbonized solvent. A mixed solvent of hydrogen solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. As 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.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, Examples include isophorone and propylene carbonate, and diisobutyl ketone and 2,5-dimethyl-4-hexanone are particularly preferable.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyric acid Examples include butyl and methyl 2-hydroxyisobutyrate.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of 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.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
The aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
In addition, 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 the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
　有機系現像液の蒸気圧は、２０℃に於いて、５ｋＰａ以下が好ましく、３ｋＰａ以下が更に好ましく、２ｋＰａ以下が特に好ましい。有機系現像液の蒸気圧を５ｋＰａ以下にすることにより、現像液の基板上あるいは現像カップ内での蒸発が抑制され、ウェハ面内の温度均一性が向上し、結果としてウェハ面内の寸法均一性が良化する。
　５ｋＰａ以下の蒸気圧を有する具体的な例としては、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、２－ヘプタノン（メチルアミルケトン）、４－ヘプタノン、２－ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルイソブチルケトン等のケトン系溶剤、酢酸ブチル、酢酸ペンチル、酢酸イソアミル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル－３－エトキシプロピオネート、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、ｔｅｒｔ－ブチルアルコール、イソブチルアルコール、ｎ－ヘキシルアルコール、ｎ－ヘプチルアルコール、ｎ－オクチルアルコール、ｎ－デカノール等のアルコール系溶剤、エチレングリコール、ジエチレングリコール、トリエチレングリコール等のグリコール系溶剤や、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、メトキシメチルブタノール等のグリコールエーテル系溶剤、テトラヒドロフラン等のエーテル系溶剤、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミドのアミド系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
　特に好ましい範囲である２ｋＰａ以下の蒸気圧を有する具体的な例としては、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、２－ヘプタノン、４－ヘプタノン、２－ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン等のケトン系溶剤、酢酸ブチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル－３－エトキシプロピオネート、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、ｔｅｒｔ－ブチルアルコール、イソブチルアルコール、ｎ－ヘキシルアルコール、ｎ－ヘプチルアルコール、ｎ－オクチルアルコール、ｎ－デカノール等のアルコール系溶剤、エチレングリコール、ジエチレングリコール、トリエチレングリコール等のグリコール系溶剤や、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、メトキシメチルブタノール等のグリコールエーテル系溶剤、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミドのアミド系溶剤、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン、ウンデカン等の脂肪族炭化水素系溶剤が挙げられる。 The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyrate formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n -Alcohol solvents such as heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl Glycol ether solvents such as butanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and aromatic hydrocarbons such as toluene and xylene And aliphatic hydrocarbon solvents such as octane and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio , Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, n-butyl Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvents, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents, N- Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents, aromatic hydrocarbon solvents such as xylene, octane, decane, include aliphatic hydrocarbon solvents undecane.
　有機系現像液は、塩基性化合物を含んでいてもよい。本発明で用いられる現像液が含みうる塩基性化合物の具体例及び好ましい例としては、前述した感活性光線又は感放射線性組成物が含みうる塩基性化合物におけるものと同様である。 The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the aforementioned actinic ray-sensitive or radiation-sensitive composition.
　有機系現像液には、必要に応じて界面活性剤を適当量添加することができる。
　界面活性剤としては特に限定されないが、例えば、イオン性や非イオン性のフッ素系及び／又はシリコン系界面活性剤等を用いることができる。これらのフッ素及び／又はシリコン系界面活性剤として、例えば特開昭６２－３６６６３号公報、特開昭６１－２２６７４６号公報、特開昭６１－２２６７４５号公報、特開昭６２－１７０９５０号公報、特開昭６３－３４５４０号公報、特開平７－２３０１６５号公報、特開平８－６２８３４号公報、特開平９－５４４３２号公報、特開平９－５９８８号公報、米国特許第５４０５７２０号明細書、同５３６０６９２号明細書、同５５２９８８１号明細書、同５２９６３３０号明細書、同５４３６０９８号明細書、同５５７６１４３号明細書、同５２９４５１１号明細書、同５８２４４５１号明細書記載の界面活性剤を挙げることができ、好ましくは、非イオン性の界面活性剤である。非イオン性の界面活性剤としては特に限定されないが、フッ素系界面活性剤又はシリコン系界面活性剤を用いることが更に好ましい。
　界面活性剤の使用量は現像液の全量に対して、好ましくは０～２質量％、更に好ましくは０．０００１～２質量％、特に好ましくは０．０００５～１質量％である。 An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer.
　現像方法としては、たとえば、現像液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面に現像液を表面張力によって盛り上げて一定時間静止することで現像する方法（パドル法）、基板表面に現像液を噴霧する方法（スプレー法）、一定速度で回転している基板上に一定速度で現像液吐出ノズルをスキャンしながら現像液を吐出しつづける方法（ダイナミックディスペンス法）などを適用することができる。
　上記各種の現像方法が、現像装置の現像ノズルから現像液をレジスト膜に向けて吐出する工程を含む場合、吐出される現像液の吐出圧（吐出される現像液の単位面積あたりの流速）は好ましくは２ｍＬ／ｓｅｃ／ｍｍ２以下、より好ましくは１．５ｍＬ／ｓｅｃ／ｍｍ２以下、更に好ましくは１ｍＬ／ｓｅｃ／ｍｍ２以下である。流速の下限は特に無いが、スループットを考慮すると０．２ｍＬ／ｓｅｃ／ｍｍ２以上が好ましい。
　吐出される現像液の吐出圧を上記の範囲とすることにより、現像後のレジスト残渣に由来するパターンの欠陥を著しく低減することができる。
　このメカニズムの詳細は定かではないが、恐らくは、吐出圧を上記範囲とすることで、現像液がレジスト膜に与える圧力が小さくなり、レジスト膜・パターンが不用意に削られたり崩れたりすることが抑制されるためと考えられる。
　尚、現像液の吐出圧（ｍＬ／ｓｅｃ／ｍｍ２）は、現像装置中の現像ノズル出口における値である。 As 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. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer may be reduced, and the resist film / pattern may be cut or collapsed carelessly. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
　現像液の吐出圧を調整する方法としては、例えば、ポンプなどで吐出圧を調整する方法や、加圧タンクからの供給で圧力を調整することで変える方法などを挙げることができる。 Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
　また、有機溶剤を含む現像液を用いて現像する工程の後に、他の溶媒に置換しながら、現像を停止する工程を実施してもよい。 Further, after the step of developing using a developer containing an organic solvent, a step of stopping development may be performed while substituting with another solvent.
　有機溶剤を含む現像液を用いて現像する工程の後には、リンス液を用いて洗浄する工程を含んでいてもよいが、スループット（生産性）、リンス液使用量等の観点から、リンス液を用いて洗浄する工程を含まなくてもよい。 After the step of developing with a developer containing an organic solvent, a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to include the step of using and washing.
　有機溶剤を含む現像液を用いて現像する工程の後のリンス工程に用いるリンス液としては、レジストパターンを溶解しなければ特に制限はなく、一般的な有機溶剤を含む溶液を使用することができる。上記リンス液としては、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも１種類の有機溶剤を含有するリンス液を用いることが好ましい。
　炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤の具体例としては、有機溶剤を含む現像液において説明したものと同様のものを挙げることができ、特に、酢酸ブチル及びメチルイソブチルカルビノールを好適に挙げることができる。
　有機溶剤を含む現像液を用いて現像する工程の後に、より好ましくは、エステル系溶剤、アルコール系溶剤、炭化水素系溶剤からなる群より選択される少なくとも１種類の有機溶剤を含有するリンス液を用いて洗浄する工程を行い、更に好ましくは、アルコール系溶剤又は炭化水素系溶剤を含有するリンス液を用いて洗浄する工程を行うことが好ましい。 The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent can include the same as those described in the developer containing an organic solvent, Particularly preferred are butyl acetate and methyl isobutyl carbinol.
More preferably, after the step of developing using a developer containing an organic solvent, a rinse solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is used. It is preferable to perform a cleaning step using a rinsing liquid containing an alcohol solvent or a hydrocarbon solvent.
　リンス液に含まれる有機溶剤としては、有機溶剤の中でも炭化水素系溶剤を用いることも好ましく、脂肪族炭化水素系溶剤を用いることがより好ましい。リンス液に用いられる脂肪族炭化水素系溶剤としては、その効果がより向上するという観点から、炭素数５以上の脂肪族炭化水素系溶剤（例えば、ペンタン、ヘキサン、オクタン、デカン、ウンデカン、ドデカン、ヘキサデカン等）が好ましく、炭素原子数が８以上の脂肪族炭化水素系溶剤が好ましく、炭素原子数が１０以上の脂肪族炭化水素系溶剤がより好ましい。
　尚、上記脂肪族炭化水素系溶剤の炭素原子数の上限値は特に限定されないが、例えば、１６以下が挙げられ、１４以下が好ましく、１２以下がより好ましい。
　上記脂肪側炭化水素系溶剤の中でも、特に好ましくは、デカン、ウンデカン、ドデカンであり、最も好ましくはウンデカンである。
　このようにリンス液に含まれる有機溶剤として炭化水素系溶剤（特に脂肪族炭化水素系溶剤）を用いることで、現像後にわずかにレジスト膜に染み込んでいた現像液が洗い流されて、膨潤がより抑制され、パターン倒れが抑制されるという効果が一層発揮される。 As the organic solvent contained in the rinsing liquid, it is also preferable to use a hydrocarbon solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent. As the aliphatic hydrocarbon solvent used in the rinsing liquid, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
In addition, although 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.
Among the above fat-side hydrocarbon solvents, decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.
By using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinsing liquid, the developer slightly soaked into the resist film after development is washed away, and swelling is further suppressed. Thus, the effect of suppressing pattern collapse is further exhibited.
　上記各成分は、複数混合してもよいし、上記以外の有機溶剤と混合し使用してもよい。 A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
　リンス液中の含水率は、１０質量％以下が好ましく、より好ましくは５質量％以下、特に好ましくは３質量％以下である。含水率を１０質量％以下にすることで、良好な現像特性を得ることができる。 The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
　有機溶剤を含む現像液を用いて現像する工程の後に用いるリンス液の蒸気圧は、２０℃に於いて０．０５ｋＰａ以上、５ｋＰａ以下が好ましく、０．１ｋＰａ以上、５ｋＰａ以下が更に好ましく、０．１２ｋＰａ以上、３ｋＰａ以下が最も好ましい。リンス液の蒸気圧を０．０５ｋＰａ以上、５ｋＰａ以下にすることにより、ウェハ面内の温度均一性が向上し、更にはリンス液の浸透に起因した膨潤が抑制され、ウェハ面内の寸法均一性が良化する。 The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic 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 at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.
　リンス液には、界面活性剤を適当量添加して使用することもできる。 An appropriate amount of a surfactant can be added to the rinse solution.
　リンス工程においては、有機溶剤を含む現像液を用いる現像を行ったウェハを上記の有機溶剤を含むリンス液を用いて洗浄処理する。洗浄処理の方法は特に限定されないが、たとえば、一定速度で回転している基板上にリンス液を吐出しつづける方法（回転塗布法）、リンス液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面にリンス液を噴霧する方法（スプレー法）、などを適用することができ、この中でも回転塗布方法で洗浄処理を行い、洗浄後に基板を２０００ｒｐｍ～４０００ｒｐｍの回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程（ＰｏｓｔＢａｋｅ）を含むことも好ましい。ベークによりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。リンス工程の後の加熱工程は、通常４０～１６０℃、好ましくは７０～９５℃で、通常１０秒～３分、好ましくは３０秒から９０秒間行う。 In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method 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), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. Moreover, it is also preferable to include a heating process (PostBake) after the rinsing process. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
　リンス液を用いて洗浄する工程を有さない場合、例えば、特開２０１５－２１６４０３の段落〔００１４〕～〔００８６〕に記載の現像処理方法を採用できる。 In the case where there is no washing step using a rinsing solution, for example, the development processing methods described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be employed.
　また、本発明のパターン形成方法は、有機系現像液を用いた現像工程と、アルカリ現像液を用いた現像工程とを有していてもよい。有機系現像液を用いた現像によって露光強度の弱い部分が除去され、アルカリ現像液を用いた現像を行うことによって露光強度の強い部分も除去される。このように現像を複数回行う多重現像プロセスにより、中間的な露光強度の領域のみを溶解させずにパターン形成が行えるので、通常より微細なパターンを形成できる（特開２００８－２９２９７５号公報の段落［００７７］と同様のメカニズム）。 Further, the pattern forming method of the present invention may have a developing step using an organic developer and a developing step using an alkali developer. A portion with low exposure intensity is removed by development using an organic developer, and a portion with high exposure intensity is also removed by development using an alkali developer. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only an intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A). [Mechanism similar to [0077]).
　本発明における感活性光線又は感放射線性組成物、及び、本発明のパターン形成方法において使用される各種材料（例えば、レジスト溶剤、現像液、リンス液、反射防止膜形成用組成物、トップコート形成用組成物など）は、金属、ハロゲンを含む金属塩、酸、アルカリ、硫黄原子又はリン原子を含む成分等の不純物を含まないことが好ましい。ここで、金属原子を含む不純物としては、Ｎａ、Ｋ、Ｃａ、Ｆｅ、Ｃｕ、Ｍｎ、Ｍｇ、Ａｌ、Ｃｒ、Ｎｉ、Ｚｎ、Ａｇ、Ｓｎ、Ｐｂ、Ｌｉ、又はこれらの塩などを挙げることができる。
　これら材料に含まれる不純物の含有量としては、１ｐｐｍ以下が好ましく、１ｐｐｂ以下がより好ましく、１００ｐｐｔ以下が更に好ましく、１０ｐｐｔ以下が特に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が最も好ましい。
　各種材料から金属等の不純物を除去する方法としては、例えば、フィルターを用いた濾過を挙げることができる。フィルター孔径としては、ポアサイズ１０ｎｍ以下が好ましく、５ｎｍ以下がより好ましく、３ｎｍ以下が更に好ましい。フィルターの材質としては、ポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、これらの材質とイオン交換メディアを組み合わせた複合材料であってもよい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列又は並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径及び／又は材質が異なるフィルターを組み合わせて使用しても良い。また、各種材料を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であっても良い。
　また、各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン（登録商標）でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
　フィルター濾過の他、吸着材による不純物の除去を行っても良く、フィルター濾過と吸着材を組み合わせて使用しても良い。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。
　また、本発明の有機系処理液に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン（登録商標）でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
　フィルター濾過の他、吸着材による不純物の除去を行ってもよく、フィルター濾過と吸着材を組み合わせて使用してもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。 Actinic ray-sensitive or radiation-sensitive composition in the present invention, and various materials used in the pattern forming method of the present invention (for example, resist solvent, developer, rinse solution, antireflection film-forming composition, topcoat formation) It is preferable that the composition or the like does not contain impurities such as a metal, a metal salt containing a halogen, an acid, an alkali, a component containing a sulfur atom or a phosphorus atom. Here, examples of the impurity containing a metal atom include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. it can.
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 the method for removing impurities such as metals from various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, 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. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
In addition, as a method of reducing impurities such as metals contained in various materials, 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.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
Further, as a method for reducing impurities such as metals contained in the organic processing liquid of the present invention, a raw material having a low metal content is selected as a raw material constituting various materials, and a filter is provided for the raw materials constituting various materials. Examples thereof include a method of performing filtration and distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
＜収容容器＞
　現像液及びリンス液に使用し得る有機溶剤（「有機系処理液」ともいう）としては、収容部を有する、化学増幅型又は非化学増幅型レジスト膜のパターニング用有機系処理液の収容容器に保存されたものを使用することが好ましい。この収容容器としては、例えば、収容部の、有機系処理液に接触する内壁が、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン－ポリプロピレン樹脂のいずれとも異なる樹脂、又は、防錆・金属溶出防止処理が施された金属から形成された、レジスト膜のパターニング用有機系処理液の収容容器であることが好ましい。この収容容器の上記収容部に、レジスト膜のパターニング用有機系処理液として使用される予定の有機溶剤を収容し、レジスト膜のパターニング時において、上記収容部から排出したものを使用することができる。 <Container>
An organic solvent (also referred to as “organic processing solution”) that can be used for the developer and the rinsing solution is a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified resist film having a storing portion. It is preferable to use a stored one. As this container, for example, the inner wall of the container that comes into contact with the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention / metal elution prevention treatment is performed. It is preferably a container for an organic processing liquid for patterning a resist film, which is formed from applied metal. An organic solvent to be used as an organic processing liquid for patterning a resist film is accommodated in the accommodating portion of the accommodating container, and the one discharged from the accommodating portion at the time of patterning the resist film can be used. .
　上記の収容容器が、更に、上記の収容部を密閉するためのシール部を有している場合、このシール部も、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン－ポリプロピレン樹脂からなる群より選択される１種以上の樹脂とは異なる樹脂、又は、防錆・金属溶出防止処理が施された金属から形成されることが好ましい。 In the case where the storage container further includes a seal portion for sealing the storage portion, the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.
　ここで、シール部とは、収容部と外気とを遮断可能な部材を意味し、パッキンやＯリングなどを好適に挙げることができる。 Here, the seal part means a member capable of shutting off the accommodating part and the outside air, and can preferably include a packing, an O-ring and the like.
　ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン－ポリプロピレン樹脂からなる群より選択される１種以上の樹脂とは異なる樹脂は、パーフルオロ樹脂であることが好ましい。 The resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.
　パーフルオロ樹脂としては、四フッ化エチレン樹脂（ＰＴＦＥ）、四フッ化エチレン・パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、四フッ化エチレン－六フッ化プロピレン共重合樹脂（ＦＥＰ）、四フッ化エチレン－エチレン共重合体樹脂（ＥＴＦＥ）、三フッ化塩化エチレン－エチレン共重合樹脂（ＥＣＴＦＥ）、フッ化ビニリデン樹脂（ＰＶＤＦ）、三フッ化塩化エチレン共重合樹脂（ＰＣＴＦＥ）、フッ化ビニル樹脂（ＰＶＦ）等を挙げることができる。 Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride. 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.
　特に好ましいパーフルオロ樹脂としては、四フッ化エチレン樹脂、四フッ化エチレン・パーフルオロアルキルビニルエーテル共重合体、四フッ化エチレン－六フッ化プロピレン共重合樹脂を挙げることができる。 Particularly preferable perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
　防錆・金属溶出防止処理が施された金属における金属としては、炭素鋼、合金鋼、ニッケルクロム鋼、ニッケルクロムモリブデン鋼、クロム鋼、クロムモリブデン鋼、マンガン鋼等を挙げることができる。 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.
　防錆・金属溶出防止処理としては、皮膜技術を適用することが好ましい。 It is preferable to apply film technology as rust prevention and metal elution prevention treatment.
　皮膜技術には、金属被覆（各種メッキ），無機被覆（各種化成処理，ガラス，コンクリート，セラミックスなど）及び有機被覆（さび止め油，塗料，ゴム，プラスチックス）の３種に大別されている。 There are three types of coating technology: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rust prevention oil, paint, rubber, plastics). .
　好ましい皮膜技術としては、錆止め油、錆止め剤、腐食抑制剤、キレート化合物、可剥性プラスチック、ライニング剤による表面処理が挙げられる。 Preferred film technology includes surface treatment with a rust inhibitor oil, a rust inhibitor, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
　中でも、各種のクロム酸塩、亜硝酸塩、ケイ酸塩、燐酸塩、オレイン酸、ダイマー酸、ナフテン酸等のカルボン酸、カルボン酸金属石鹸、スルホン酸塩、アミン塩、エステル（高級脂肪酸のグリセリンエステルや燐酸エステル）などの腐食抑制剤、エチレンジアンテトラ酢酸、グルコン酸、ニトリロトリ酢酸、ヒドロキシエチルエチオレンジアミン三作酸、ジエチレントリアミン五作酸などのキレート化合物及びフッ素樹脂ライニングが好ましい。特に好ましいのは、燐酸塩処理とフッ素樹脂ライニングである。 Among them, 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) And chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine trisuccinic acid, diethylene triamine pentic acid, and fluororesin lining. Particularly preferred are phosphating and fluororesin lining.
　また、直接的な被覆処理と比較して、直接、錆を防ぐわけではないが、被覆処理による防錆期間の延長につながる処理方法として、防錆処理にかかる前の段階である「前処理」を採用することも好ましい。 In addition, compared with direct coating treatment, it does not directly prevent rust, but as a treatment method that leads to the extension of the rust prevention period by coating treatment, "pretreatment" is a stage before rust prevention treatment. It is also preferable to adopt.
　このような前処理の具体例としては、金属表面に存在する塩化物や硫酸塩などの種々の腐食因子を、洗浄や研磨によって除去する処理を好適に挙げることができる。 As a specific example of such pretreatment, 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.
　収容容器としては具体的に以下を挙げることができる。 Specific examples of the storage container include the following.
　・Ｅｎｔｅｇｒｉｓ社製　ＦｌｕｏｒｏＰｕｒｅＰＦＡ複合ドラム（接液内面；ＰＦＡ樹脂ライニング）
　・ＪＦＥ社製　鋼製ドラム缶（接液内面；燐酸亜鉛皮膜） ・ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining)
・ JFE steel drums (wetted inner surface; zinc phosphate coating)
　また、本発明において用いることができる収容容器としては、特開平１１－０２１３９３号公報［００１３］～［００３０］、及び特開平１０－４５９６１号公報［００１２］～［００２４］に記載の容器も挙げることができる。 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.
　本発明の有機系処理液は、静電気の帯電、引き続き生じる静電気放電に伴う薬液配管や各種パーツ（フィルター、Ｏ－リング、チューブなど）の故障を防止する為、導電性の化合物を添加しても良い。導電性の化合物としては特に制限されないが、例えば、メタノールが挙げられる。添加良は特に制限されないが、好ましい現像特性を維持する観点で、１０質量％以下が好ましく、更に好ましくは、５質量％以下である。薬液配管の部材に関しては、ＳＵＳ（ステンレス鋼）、或いは帯電防止処理の施されたポリエチレン、ポリプロピレン、又はフッ素樹脂（ポリテトラフルオロエチレン、パーフロオロアルコキシ樹脂など）で被膜された各種配管を用いることができる。フィルターやＯ－リングに関しても同様に、帯電防止処理の施されたポリエチレン、ポリプロピレン、又はフッ素樹脂（ポリテトラフルオロエチレン、パーフロオロアルコキシ樹脂など）を用いることができる。 The organic processing solution of the present invention can be added with a conductive compound to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. good. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The good addition 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. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.
　尚、一般的に、現像液及びリンス液は、使用後に配管を通して廃液タンクに収容される。その際、リンス液として炭化水素系溶媒を使用すると、現像液中に溶解したレジストが析出し、ウエハ背面や、配管側面などに付着することを防ぐために、再度、レジストが溶解する溶媒を配管に通す方法がある。配管に通す方法としては、リンス液での洗浄後に基板の背面や側面などをレジストが溶解する溶媒で洗浄して流す方法や、レジストに接触させずにレジストが溶解する溶剤を配管を通るように流す方法が挙げられる。
　配管に通す溶剤としては、レジストを溶解し得るものであれば特に限定されず、例えば上述した有機溶媒が挙げられ、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２－ヘプタノン、乳酸エチル、１－プロパノール、アセトン、等を用いることができる。中でも好ましくは、ＰＧＭＥＡ，ＰＧＭＥ，シクロヘキサノンを用いることができる。 In general, the developer and the rinse liquid are stored in a waste liquid tank through a pipe after use. At that time, if a hydrocarbon-based solvent is used as the rinsing solution, the resist dissolved in the developer is deposited, and in order to prevent the resist from adhering to the back surface of the wafer or the side of the pipe, the solvent in which the resist dissolves is added to the pipe again. There is a way to pass. As a method of passing through the piping, after cleaning with a rinsing liquid, 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 is mentioned.
The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl. Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, or the like can be used. Among these, PGMEA, PGME, and cyclohexanone can be preferably used.
　本発明のパターン形成方法により得られるパターンをマスクとして用い、適宜エッチング処理及びイオン注入などを行い、半導体微細回路、インプリント用モールド構造体、フォトマスク等を製造することができる。 Using a pattern obtained by the pattern forming method of the present invention as a mask, a semiconductor fine circuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation.
　上記の方法によって形成されたパターンは、ＤＳＡ（Ｄｉｒｅｃｔｅｄ　Ｓｅｌｆ-Ａｓｓｅｍｂｌｙ）におけるガイドパターン形成（例えば、ＡＣＳ　Ｎａｎｏ　Ｖｏｌ．４　Ｎｏ．８　Ｐａｇｅ４８１５-４８２３参照）にも用いることができる。また、上記の方法によって形成されたパターンは、例えば特開平３－２７０２２７及び特開２０１３－１６４５０９号公報に開示されたスペーサープロセスの芯材（コア）として使用できる。 The pattern formed by the above method can also be used for guide pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano Vol. 4 No. 8 Page 4815-4823). Further, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
　尚、本発明の組成物を用いてインプリント用モールドを作成する場合のプロセスについては、例えば、特許第４１０９０８５号公報、特開２００８－１６２１０１号公報、及び「ナノインプリントの基礎と技術開発・応用展開―ナノインプリントの基板技術と最新の技術展開―編集：平井義彦（フロンティア出版）」に記載されている。 Regarding the process for producing an imprint mold using the composition of the present invention, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application Deployment” -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".
　本発明のパターン形成方法を用いて製造されるフォトマスクは、ＡｒＦエキシマレーザー等で用いられる光透過型マスクであっても、ＥＵＶ光を光源とする反射系リソグラフィーで用いられる光反射型マスクであってもよい。 The photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.
　また、本発明は、上記した本発明のパターン形成方法を含む、電子デバイスの製造方法にも関する。 The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention.
　本発明の電子デバイスの製造方法により製造される電子デバイスは、電気電子機器（家電、ＯＡ（Ｏｆｆｉｃｅ　Ａｐｐｌｉａｎｃｅ）・メディア関連機器、光学用機器及び通信機器等）に、好適に、搭載されるものである。 The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) / media-related device, optical device, communication device, etc.). is there.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。尚、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.
＜合成例１：化合物（Ｃ－１３）の合成＞
　窒素フローしている１Ｌの三口フラスコに、酢酸ブチル０．１Ｌ、フェノキシエタノール２５ｇ（０．１３ｍｏｌ）を加え、９０℃に加温した。ｍ－キシリレンジイソシアネート４０．３８ｇ（０．２９ｍｏｌ）を上記フラスコの内温が１１０℃を超えない温度で滴下し、更に１００℃で４時間熟成を行った。その後、６０℃まで冷却し、メタノール１０ｍＬを加え１５分間撹拌した。更に、酢酸エチル／メタノール／ヘキサン＝５０ｍＬ／５０ｍＬ／２００ｍＬの混合液を加え１５分間撹拌した。析出した白色結晶を濾別し、この結晶を酢酸エチル／メタノール／ヘキサン＝５０ｍＬ／５０ｍＬ／２００ｍＬの混合液で洗浄し、減圧乾燥することで目的の化合物を合成した。 <Synthesis Example 1: Synthesis of Compound (C-13)>
To a 1 L three-necked flask with nitrogen flow, 0.1 L of butyl acetate and 25 g (0.13 mol) of phenoxyethanol were added and heated to 90 ° C. 40.38 g (0.29 mol) of m-xylylene diisocyanate was added dropwise at a temperature at which the internal temperature of the flask did not exceed 110 ° C., and further aged at 100 ° C. for 4 hours. Then, it cooled to 60 degreeC, added methanol 10mL, and stirred for 15 minutes. Furthermore, a mixed solution of ethyl acetate / methanol / hexane = 50 mL / 50 mL / 200 mL was added and stirred for 15 minutes. The precipitated white crystals were separated by filtration, and the crystals were washed with a mixed solution of ethyl acetate / methanol / hexane = 50 mL / 50 mL / 200 mL, and dried under reduced pressure to synthesize the target compound.
　上記合成例１と同様、その他の化合物（Ａ）も、対応するイソシアネート化合物と、対応するアミン化合物又はアルコール化合物との反応等に基づいて合成した。 As in Synthesis Example 1, the other compound (A) was synthesized based on the reaction of the corresponding isocyanate compound and the corresponding amine compound or alcohol compound.
　以下の実施例において、化合物（Ａ）としては、先に挙げた化合物Ｃ－１～Ｃ－３６、Ｕ－１～Ｕ－１６、Ａ－１～Ａ－２２、ＢＡ－１～ＢＡ－１４、Ｉ－１～Ｉ－１４、及び、ＣＡ－１～ＣＡ－１０から適宜選択して用いた。
　重合体に組み込まれた形態の化合物（Ａ）に関しては、下表に示す繰り返し単位の組成比（モル比；左から順に対応）、重量平均分子量（Ｍｗ）、及び、分散度（Ｍｗ／Ｍｎ）を有する化合物を使用した。 In the following Examples, the compound (A) includes compounds C-1 to C-36, U-1 to U-16, A-1 to A-22, BA-1 to BA-14, I-1 to I-14 and CA-1 to CA-10 were appropriately selected and used.
Regarding the compound (A) in a form incorporated in the polymer, the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) shown in the table below. A compound having was used.
Figure JPOXMLDOC01-appb-T000084
Figure JPOXMLDOC01-appb-T000084
　以下、実施例及び比較例に用いた、樹脂、光酸発生剤、塩基性化合物、架橋剤、疎水性樹脂、界面活性剤、溶剤、現像液及びリンス液を示す。 Hereinafter, resins, photoacid generators, basic compounds, crosslinking agents, hydrophobic resins, surfactants, solvents, developers, and rinses used in Examples and Comparative Examples are shown.
〔樹脂〕
　樹脂の構造、組成比（モル比）、重量平均分子量（Ｍｗ）、分散度（Ｍｗ／Ｍｎ）を以下に示す。Ｅｔはエチル基を表す。 〔resin〕
The resin structure, composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown below. Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-T000086
Figure JPOXMLDOC01-appb-T000086
〔光酸発生剤〕 [Photoacid generator]
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
〔塩基性化合物〕 [Basic compounds]
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
〔架橋剤〕 [Crosslinking agent]
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
　〔疎水性樹脂〕
　疎水性樹脂の構造、組成比（モル比）、重量平均分子量（Ｍｗ）、分散度（Ｍｗ／Ｍｎ）を以下に示す。 [Hydrophobic resin]
The structure, composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the hydrophobic resin are shown below.
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-T000091
Figure JPOXMLDOC01-appb-T000091
　〔溶剤〕
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（別名１－メトキシ－２－アセトキシプロパン）
ＰＧＭＥ：プロピレングリコールモノメチルエーテル（別名１－メトキシ－２－プロパノール）
ＥＬ：乳酸エチル
ＣｙＨｘ：シクロヘキサノン 〔solvent〕
PGMEA: Propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-acetoxypropane)
PGME: Propylene glycol monomethyl ether (also known as 1-methoxy-2-propanol)
EL: ethyl lactate CyHx: cyclohexanone
〔実施例１－１～１－３０、比較例１－１～１－５（電子線（ＥＢ）露光；ポジ型パターン形成）〕
　（１）レジスト組成物の塗液調製及び塗設
　下記表１～３に示す成分を下記表１～３に示す溶剤に溶解させ、固形分濃度４．０質量％の溶液を調製し、これを０．０２μｍのポアサイズを有するポリエチレンフィルターでろ過して、実施例１－１～１－３０及び比較例１－１～１－５のレジスト組成物溶液を得た。ここで、下記表１～３の溶剤における数値は、溶剤の全量に対する含有量を質量％で示したものである。これらのレジスト組成物溶液を、予めヘキサメチルジシラザン（ＨＭＤＳ）処理を施した６インチＳｉウェハ上に東京エレクトロン製スピンコーターＭａｒｋ８を用いて塗布し、１００℃、６０秒間ホットプレート上で乾燥して、膜厚１５０ｎｍのレジスト膜を得た。
　ここで、１インチは、０．０２５４ｍである。
　尚、上記Ｓｉウエハをクロム基板に変更しても、後述の実施例と同様の効果が得られるものである。 [Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-5 (electron beam (EB) exposure; positive pattern formation)]
(1) Coating composition preparation and coating of resist composition The components shown in Tables 1 to 3 below are dissolved in the solvents shown in Tables 1 to 3 to prepare a solution having a solid content concentration of 4.0% by mass. Filtration through a polyethylene filter having a pore size of 0.02 μm gave resist composition solutions of Examples 1-1 to 1-30 and Comparative Examples 1-1 to 1-5. Here, the numerical values for the solvents in Tables 1 to 3 below indicate the content of the solvent with respect to the total amount in terms of mass%. These resist composition solutions were 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 100 ° C. for 60 seconds. A resist film having a thickness of 150 nm was obtained.
Here, 1 inch is 0.0254 m.
Even if the Si wafer is changed to a chromium substrate, the same effects as those of the embodiments described later can be obtained.
　（２）ＥＢ露光及び現像
　上記（１）で得られたレジスト膜が塗布されたウェハを、電子線描画装置（（株）日立製作所製ＨＬ７５０、加速電圧５０ＫｅＶ）を用いて、パターン照射を行った。この際、１：１のラインアンドスペースが形成されるように描画を行った。電子線描画後、ホットプレート上で、１００℃で６０秒間加熱した後、２．３８質量％のテトラメチルアンモニウムハイドロオキサイド水溶液をパドルして３０秒間現像し、純水でリンスをした後、４０００ｒｐｍの回転数で３０秒間ウェハを回転させた後、９５℃で６０秒間加熱を行うことにより、線幅５０ｎｍの１：１ラインアンドスペースパターンのレジストパターンを得た。 (2) EB exposure and development The wafer coated with the resist film obtained in (1) above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). . At this time, drawing was performed so that a 1: 1 line and space was formed. After drawing the electron beam, it was heated on a hot plate at 100 ° C. for 60 seconds, then padded with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, developed for 30 seconds, rinsed with pure water, and then rotated at 4000 rpm. After rotating the wafer for 30 seconds at the number of rotations, heating was performed at 95 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.
　（３）レジストパターンの評価
　走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、得られたレジストパターンの性能評価を下記の方法に基づき実施した。結果を下記表４に示す。 (3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), performance evaluation of the obtained resist pattern was performed based on the following method. The results are shown in Table 4 below.
〔感度〕
　得られたパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－４３００）を用いて観察した。線幅５０ｎｍの１：１ラインアンドスペースのレジストパターンを解像するときの露光量（電子線照射量）を感度（Ｅｏｐ）とした。
　ただし、比較例１－１～１－５については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例１－１においては線幅６７ｎｍの１：１ラインアンドスペースパターンを、比較例１－２においては線幅６８ｎｍの１：１ラインアンドスペースパターンを、比較例１－３～１－５においては線幅６６ｎｍの１：１ラインアンドスペースパターンを解像するときの露光量（電子線照射量）を感度（Ｅｏｐ）とした。 〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when resolving a 1: 1 line and space resist pattern with a line width of 50 nm was defined as sensitivity (Eop).
However, in Comparative Examples 1-1 to 1-5, since a 1: 1 line and space pattern with a line width of 50 nm could not be resolved, in Comparative Example 1-1, a 1: 1 line with a line width of 67 nm was used. In the comparative example 1-2, the 1: 1 line and space pattern having a line width of 68 nm was resolved, and in the comparative examples 1-3 to 1-5, the 1: 1 line and space pattern having a line width of 66 nm was resolved. The exposure amount (electron beam irradiation amount) at the time of performing was defined as sensitivity (Eop).
〔解像力〕
　上記の感度を示す露光量（電子線照射量）における限界解像力（ラインとスペースが分離解像する最小の線幅）を解像力（ｎｍ）とした。 [Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount (electron beam irradiation amount) showing the above sensitivity.
〔ラインウィズスラフネス（ＬＷＲ）性能〕
　線幅５０ｎｍの１：１ラインアンドスペースパターンの長手方向０．５μｍの任意の５０点について、走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、線幅を計測し、その標準偏差を求め、３σを算出した。値が小さいほど良好な性能であることを示す。
　ただし、比較例１－１～１－５については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例１－１においては線幅６７ｎｍの１：１ラインアンドスペースパターンについて、比較例１－２においては線幅６８ｎｍの１：１ラインアンドスペースパターンについて、比較例１－３～１－５においては線幅６６ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記の距離の標準偏差を求め、３σを算出した。 [Line width roughness (LWR) performance]
Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the line width was measured at an arbitrary 50 points of 0.5 μm in the longitudinal direction of a 1: 1 line and space pattern with a line width of 50 nm. The standard deviation was calculated and 3σ was calculated. A smaller value indicates better performance.
However, in Comparative Examples 1-1 to 1-5, since a 1: 1 line and space pattern with a line width of 50 nm could not be resolved, in Comparative Example 1-1, a 1: 1 line with a line width of 67 nm was used. With respect to the and space pattern, in Comparative Example 1-2, the 1: 1 line and space pattern with a line width of 68 nm, and in Comparative Examples 1-3 to 1-5, the 1: 1 line and space pattern with a line width of 66 nm, respectively. The standard deviation of the above distance was obtained and 3σ was calculated.
〔パターン断面形状〕
　線幅５０ｎｍの１：１ラインアンドスペースのレジストパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて観察し、「矩形」、「ラウンドトップ形状（パターン断面の上部が丸みを帯びている形状）」等の評価を行った。
　ただし、比較例１－１～１－５については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例１－１においては線幅６７ｎｍの１：１ラインアンドスペースパターンについて、比較例１－２においては線幅６８ｎｍの１：１ラインアンドスペースパターンについて、比較例１－３～１－５においては線幅６６ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記評価を行った。
　パターン断面形状は、「矩形」であることが好ましい。 [Pattern cross-sectional shape]
The cross-sectional shape of a 1: 1 line and space resist pattern having a line width of 50 nm was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). The shape of the upper part is rounded) ”was evaluated.
However, in Comparative Examples 1-1 to 1-5, since a 1: 1 line and space pattern with a line width of 50 nm could not be resolved, in Comparative Example 1-1, a 1: 1 line with a line width of 67 nm was used. With respect to the and space pattern, in Comparative Example 1-2, the 1: 1 line and space pattern with a line width of 68 nm, and in Comparative Examples 1-3 to 1-5, the 1: 1 line and space pattern with a line width of 66 nm, respectively. The above evaluation was performed.
The pattern cross-sectional shape is preferably “rectangular”.
Figure JPOXMLDOC01-appb-T000092
Figure JPOXMLDOC01-appb-T000092
Figure JPOXMLDOC01-appb-T000093
Figure JPOXMLDOC01-appb-T000093
Figure JPOXMLDOC01-appb-T000094
 
Figure JPOXMLDOC01-appb-T000094
 
　上表において、化合物Ｈ－１～Ｈ－４は、以下に示す通りである。尚、化合物Ｈ－４は、酸架橋性基を有する化合物（架橋剤）に相当する。 In the above table, compounds H-1 to H-4 are as shown below. Compound H-4 corresponds to a compound having an acid crosslinkable group (crosslinking agent).
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-T000096
Figure JPOXMLDOC01-appb-T000096
　上表により、化合物（Ａ）に適合する化合物を含有するレジスト組成物を用いた実施例１－１～１－３０は、該化合物を含有しないレジスト組成物を用いた比較例１－１～１－５と比較して、超微細のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できることが分かった。 According to the above table, Examples 1-1 to 1-30 using a resist composition containing a compound compatible with the compound (A) are Comparative Examples 1-1 to 1 using a resist composition not containing the compound. Compared to -5, it was found that in the formation of an ultrafine pattern, a pattern excellent in all of sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
〔実施例２－１～２－１３、比較例２－１～２－３（電子線（ＥＢ）露光；ネガ型パターン形成）〕
　下記表５に示す成分を下記表５に示す溶剤に溶解させ、固形分濃度２．７質量％の溶液を調製し、これを０．０２μｍのポアサイズを有するポリエチレンフィルターでろ過して、実施例２－１～２－１３及び比較例２－１～２－３のレジスト組成物溶液を得た。ここで、下記表５の溶剤における数値は、溶剤の全量に対する含有量を質量％で示したものである。これらのレジスト組成物を用いた以外は、実施例１－１と同様に、レジスト組成物の塗設、ＥＢ露光及び現像、及び、レジストパターンの評価を実施した。結果を下記表６に示す。 [Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-3 (electron beam (EB) exposure; negative pattern formation)]
The components shown in Table 5 below were dissolved in the solvent shown in Table 5 below to prepare a solution having a solid content concentration of 2.7% by mass, and this was filtered through a polyethylene filter having a pore size of 0.02 μm. Resist composition solutions of -1 to 2-13 and Comparative Examples 2-1 to 2-3 were obtained. Here, the numerical value in the solvent of the following Table 5 shows content with respect to the whole quantity of a solvent with the mass%. Except for using these resist compositions, coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1. The results are shown in Table 6 below.
Figure JPOXMLDOC01-appb-T000097
Figure JPOXMLDOC01-appb-T000097
Figure JPOXMLDOC01-appb-T000098
Figure JPOXMLDOC01-appb-T000098
　上表により、化合物（Ａ）に適合する化合物を含有するレジスト組成物を用いた実施例２－１～２－１３は、該化合物を含有しないレジスト組成物を用いた比較例２－１～２－３と比較して、超微細のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できることが分かった。 According to the above table, Examples 2-1 to 2-13 using a resist composition containing a compound compatible with compound (A) are comparative examples 2-1 to 2-2 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
　尚、上記実施例において、現像液、リンス液を前述の有機溶剤に変更して、ネガ型パターンを形成しても同様の効果が得られる。 In the above embodiment, the same effect can be obtained by forming a negative pattern by changing the developing solution and the rinsing solution to the organic solvent described above.
〔実施例３－１～３－８、比較例３－１～３－３（ＡｒＦエキシマレーザー露光；ネガ型パターン形成）〕
　（１）レジスト組成物の塗液調製及び塗設
　下記表７に示す成分を下記表７に示す溶剤に溶解させ、固形分濃度３．５質量％の溶液を調製し、これを０．０４μｍのポアサイズを有するポリエチレンフィルターでろ過して、実施例３－１～３－８及び比較例３－１～３－３のレジスト組成物溶液を得た。ここで、下記表７の溶剤における数値は、溶剤の全量に対する含有量を質量％で示したものである。これらのレジスト組成物溶液を、予めヘキサメチルジシラザン（ＨＭＤＳ）処理を施した６インチＳｉウェハ上に東京エレクトロン製スピンコーターＭａｒｋ８を用いて塗布し、１００℃、６０秒間ホットプレート上で乾燥して、膜厚１２０ｎｍのレジスト膜を得た。 [Examples 3-1 to 3-8, Comparative Examples 3-1 to 3-3 (ArF excimer laser exposure; negative pattern formation)]
(1) Coating composition preparation and coating of resist composition The components shown in Table 7 below are dissolved in the solvent shown in Table 7 below to prepare a solution having a solid content concentration of 3.5% by mass. Filtration through a polyethylene filter having a pore size gave resist composition solutions of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-3. Here, the numerical value in the solvent of the following Table 7 shows content with respect to the whole quantity of a solvent with the mass%. These resist composition solutions were 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 100 ° C. for 60 seconds. A resist film having a thickness of 120 nm was obtained.
　（２）ＡｒＦ露光及び現像
　上記（１）で得られたレジスト膜が塗布されたウェハを、ＡｒＦエキシマレーザー液浸スキャナー（ＡＳＭＬ社製；ＸＴ１７００ｉ、ＮＡ１．２０、Ｃ－Ｑｕａｄ、アウターシグマ０．９００、インナーシグマ０．７９０、Ｙ偏向）を用い、線幅５０ｎｍの１：１ラインアンドスペースパターンのハーフトーンマスクを介して、パターン露光を行った。液浸液としては超純水を用いた。その後、９０℃で６０秒間加熱（ＰＥＢ：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ）した。次いで、酢酸ブチルで３０秒間パドルして現像し、４－メチル－２－ペンタノールで３０秒間パドルしてリンスした。続いて、２０００ｒｐｍの回転数で３０秒間ウエハを回転させることにより、線幅５０ｎｍの１：１ラインアンドスペースパターンのレジストパターンを得た。 (2) ArF exposure and development A wafer coated with the resist film obtained in (1) above was used as an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900). , Inner sigma 0.790, Y deflection), and pattern exposure was performed through a half-tone mask of a 1: 1 line and space pattern having a line width of 50 nm. Ultra pure water was used as the immersion liquid. Then, it heated at 90 degreeC for 60 second (PEB: Post Exposure Bake). Then, it was developed by paddle with butyl acetate for 30 seconds, and rinsed by paddle with 4-methyl-2-pentanol for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 2000 rpm for 30 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.
　（３）レジストパターンの評価
　走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、得られたレジストパターンの性能評価を下記の方法に基づき実施した。結果を下記表８に示す。 (3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), performance evaluation of the obtained resist pattern was performed based on the following method. The results are shown in Table 8 below.
〔感度〕
　得られたパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－４３００）を用いて観察した。線幅５０ｎｍの１：１ラインアンドスペースのレジストパターンを解像するときの露光量を感度（Ｅｏｐ）とした。
　ただし、比較例３－２～３－３については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例３－２においては線幅５２ｎｍの１：１ラインアンドスペースパターンを、比較例３－３においては線幅５５ｎｍの１：１ラインアンドスペースパターンを解像するときの露光量を感度（Ｅｏｐ）とした。 〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when resolving a 1: 1 line and space resist pattern with a line width of 50 nm was defined as sensitivity (Eop).
However, in Comparative Examples 3-2 to 3-3, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, in Comparative Example 3-2, a 1: 1 line with a line width of 52 nm was used. In the comparative example 3-3, the exposure amount when resolving the 1: 1 line and space pattern having a line width of 55 nm was defined as sensitivity (Eop).
〔解像力〕
　上記の感度を示す露光量における限界解像力（ラインとスペースが分離解像する最小の線幅）を解像力（ｎｍ）とした。 [Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount showing the above sensitivity.
〔ラインウィズスラフネス（ＬＷＲ）性能〕
　線幅５０ｎｍの１：１ラインアンドスペースパターンの長手方向０．５μｍの任意の５０点について、走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、線幅を計測し、その標準偏差を求め、３σを算出した。値が小さいほど良好な性能であることを示す。
　ただし、比較例３－２～３－３については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例３－２においては線幅５２ｎｍの１：１ラインアンドスペースパターンについて、比較例３－３においては線幅５５ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記の距離の標準偏差を求め、３σを算出した。 [Line width roughness (LWR) performance]
Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the line width was measured at an arbitrary 50 points of 0.5 μm in the longitudinal direction of a 1: 1 line and space pattern with a line width of 50 nm. The standard deviation was calculated and 3σ was calculated. A smaller value indicates better performance.
However, in Comparative Examples 3-2 to 3-3, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, in Comparative Example 3-2, a 1: 1 line with a line width of 52 nm was used. With respect to the and space pattern, in Comparative Example 3-3, the standard deviation of the distance was obtained for the 1: 1 line and space pattern having a line width of 55 nm, and 3σ was calculated.
〔パターン断面形状〕
　線幅５０ｎｍの１：１ラインアンドスペースのレジストパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて観察し、「矩形」、「ラウンドトップ形状」等の評価を行った。
　ただし、比較例３－２～３－３については、線幅５０ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例３－２においては線幅５２ｎｍの１：１ラインアンドスペースパターンについて、比較例３－３においては線幅５５ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記評価を行った。
　パターン断面形状は、「矩形」であることが好ましい。 [Pattern cross-sectional shape]
The cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 50 nm was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) and evaluated as “rectangular”, “round-top shape”, etc. Went.
However, in Comparative Examples 3-2 to 3-3, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, in Comparative Example 3-2, a 1: 1 line with a line width of 52 nm was used. With regard to the and space pattern, in Comparative Example 3-3, the above-described evaluation was performed on the 1: 1 line and space pattern having a line width of 55 nm.
The pattern cross-sectional shape is preferably “rectangular”.
Figure JPOXMLDOC01-appb-T000099
Figure JPOXMLDOC01-appb-T000099
Figure JPOXMLDOC01-appb-T000100
Figure JPOXMLDOC01-appb-T000100
　上表により、化合物（Ａ）に適合する化合物を含有するレジスト組成物を用いた実施例３－１～３－８は、該化合物を含有しないレジスト組成物を用いた比較例３－１～３－３と比較して、超微細のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できることが分かった。 According to the above table, Examples 3-1 to 3-8 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 3-1 to 3-3 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
〔実施例４－１～４－１３、比較例４－１～４－３（ＥＵＶ露光；ネガ型パターン形成）〕
　（１）レジスト組成物の塗液調製及び塗設
　下記表９に示す成分を下記表９に示す溶剤に溶解させ、固形分濃度１．３質量％の溶液を調製し、これを０．０３μｍのポアサイズを有するポリエチレンフィルターでろ過して、実施例４－１～４－１３及び比較例４－１～４－３のレジスト組成物溶液を得た。ここで、下記表９の溶剤における数値は、溶剤の全量に対する含有量を質量％で示したものである。これらのレジスト組成物溶液を、予めヘキサメチルジシラザン（ＨＭＤＳ）処理を施した６インチＳｉウェハ上に東京エレクトロン製スピンコーターＭａｒｋ８を用いて塗布し、１００℃、６０秒間ホットプレート上で乾燥して、膜厚４０ｎｍのレジスト膜を得た。 [Examples 4-1 to 4-13, Comparative Examples 4-1 to 4-3 (EUV exposure; negative pattern formation)]
(1) Coating composition preparation and coating of resist composition The components shown in Table 9 below are dissolved in the solvent shown in Table 9 below to prepare a solution having a solid content concentration of 1.3% by mass. Filtration through a polyethylene filter having a pore size gave resist composition solutions of Examples 4-1 to 4-13 and Comparative Examples 4-1 to 4-3. Here, the numerical value in the solvent of the following Table 9 shows content with respect to the whole quantity of a solvent with the mass%. These resist composition solutions were 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 100 ° C. for 60 seconds. A resist film having a thickness of 40 nm was obtained.
　（２）ＥＵＶ露光及び現像
　上記（１）で得られたレジスト膜の塗布されたウェハを、ＥＵＶ露光装置（Ｅｘｉｔｅｃｈ社製　Ｍｉｃｒｏ　Ｅｘｐｏｓｕｒｅ　Ｔｏｏｌ、ＮＡ０．３、Ｑｕａｄｒｕｐｏｌｅ、アウターシグマ０．６８、インナーシグマ０．３６）を用い、露光マスク（ライン／スペース＝１／１）を使用して、パターン露光を行った。露光後、ホットプレート上で、１００℃で９０秒間加熱した後、酢酸イソアミルをパドルして３０秒間現像し、ウンデカンを用いてリンスした後、４０００ｒｐｍの回転数で３０秒間ウェハを回転させた後、９５℃で６０秒間ベークを行なうことにより、線幅３２ｎｍの１：１ラインアンドスペースパターンのレジストパターンを得た。 (2) EUV exposure and development The wafer coated with the resist film obtained in the above (1) is subjected to an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0, manufactured by Exitech) .36) and pattern exposure was performed using an exposure mask (line / space = 1/1). After exposure, after heating at 100 ° C. for 90 seconds on a hot plate, paddle with isoamyl acetate, develop for 30 seconds, rinse with undecane, rotate the wafer for 30 seconds at 4000 rpm, By baking at 95 ° C. for 60 seconds, a 1: 1 line and space resist pattern having a line width of 32 nm was obtained.
　（３）レジストパターンの評価
　走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、得られたレジストパターンの性能評価を下記の方法に基づき実施した。結果を下記表１０に示す。 (3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), performance evaluation of the obtained resist pattern was performed based on the following method. The results are shown in Table 10 below.
〔感度〕
　得られたパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－４３００）を用いて観察した。線幅３２ｎｍの１：１ラインアンドスペースのレジストパターンを解像するときの露光量を感度（Ｅｏｐ）とした。
　ただし、比較例４－１～４－３については、線幅３２ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例４－１及び４－３においては線幅３５ｎｍの１：１ラインアンドスペースパターンを、比較例４－２においては線幅３６ｎｍの１：１ラインアンドスペースパターンを解像するときの露光量を感度（Ｅｏｐ）とした。 〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when resolving a 1: 1 line and space resist pattern having a line width of 32 nm was defined as sensitivity (Eop).
However, in Comparative Examples 4-1 to 4-3, a 1: 1 line and space pattern having a line width of 32 nm could not be resolved. Therefore, in Comparative Examples 4-1 and 4-3, a line width of 35 nm was obtained. The exposure amount when resolving the 1: 1 line and space pattern and the 1: 1 line and space pattern having a line width of 36 nm in Comparative Example 4-2 was defined as sensitivity (Eop).
〔解像力〕
　上記の感度を示す露光量における限界解像力（ラインとスペースが分離解像する最小の線幅）を解像力（ｎｍ）とした。 [Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount showing the above sensitivity.
〔ラインウィズスラフネス（ＬＷＲ）性能〕
　線幅３２ｎｍの１：１ラインアンドスペースパターンの長手方向０．５μｍの任意の５０点について、走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて、線幅を計測し、その標準偏差を求め、３σを算出した。値が小さいほど良好な性能であることを示す。
　ただし、比較例４－１～４－３については、線幅３２ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例４－１及び４－３においては線幅３５ｎｍの１：１ラインアンドスペースパターンについて、比較例４－２においては線幅３６ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記の距離の標準偏差を求め、３σを算出した。 [Line width roughness (LWR) performance]
Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the line width was measured at an arbitrary 50 points of 0.5 μm in the longitudinal direction of a 1: 1 line and space pattern with a line width of 32 nm. The standard deviation was calculated and 3σ was calculated. A smaller value indicates better performance.
However, in Comparative Examples 4-1 to 4-3, a 1: 1 line and space pattern having a line width of 32 nm could not be resolved. Therefore, in Comparative Examples 4-1 and 4-3, a line width of 35 nm was obtained. With respect to the 1: 1 line and space pattern, in Comparative Example 4-2, the standard deviation of the above distance was obtained for the 1: 1 line and space pattern with a line width of 36 nm, and 3σ was calculated.
〔パターン断面形状〕
　線幅３２ｎｍの１：１ラインアンドスペースのレジストパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－９２２０）を用いて観察し、「矩形」、「ラウンドトップ形状」等の評価を行った。
　ただし、比較例４－１～４－３については、線幅３２ｎｍの１：１ラインアンドスペースパターンを解像することができなかったため、比較例４－１及び４－３においては線幅３５ｎｍの１：１ラインアンドスペースパターンについて、比較例４－２においては線幅３６ｎｍの１：１ラインアンドスペースパターンについて、それぞれ、上記評価を行った。
　パターン断面形状は、「矩形」であることが好ましい。 [Pattern cross-sectional shape]
The cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 32 nm was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) and evaluated as “rectangular”, “round top shape”, etc. Went.
However, in Comparative Examples 4-1 to 4-3, a 1: 1 line and space pattern having a line width of 32 nm could not be resolved. Therefore, in Comparative Examples 4-1 and 4-3, a line width of 35 nm was obtained. With respect to the 1: 1 line and space pattern, in Comparative Example 4-2, the above evaluation was performed on the 1: 1 line and space pattern having a line width of 36 nm.
The pattern cross-sectional shape is preferably “rectangular”.
Figure JPOXMLDOC01-appb-T000101
Figure JPOXMLDOC01-appb-T000101
Figure JPOXMLDOC01-appb-T000102
Figure JPOXMLDOC01-appb-T000102
　上表により、化合物（Ａ）に適合する化合物を含有するレジスト組成物を用いた実施例４－１～４－１３は、該化合物を含有しないレジスト組成物を用いた比較例４－１～４－３と比較して、超微細のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できることが分かった。 According to the above table, Examples 4-1 to 4-13 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 4-1 to 4-4 using a resist composition not containing the compound. Compared to -3, it was found that in the formation of an ultrafine pattern, a pattern excellent in sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
　表９の実施例の組成物をＥＵＶ露光した際、酢酸イソアミルをジイソブチルケトンと酢酸イソアミルの５０：５０質量部の混合としても同様の効果が得られる。
　表９の実施例の組成物をＥＵＶ露光した際、リンス液をウンデカンとジイソブチルケトンの４０：６０質量部の混合としても同様の効果が得られる。 When the compositions of the examples in Table 9 are exposed to EUV, the same effect can be obtained by mixing isoamyl acetate with 50:50 parts by mass of diisobutyl ketone and isoamyl acetate.
When the compositions of the examples in Table 9 are exposed to EUV, the same effect can be obtained even if the rinsing liquid is a mixture of 40:60 parts by mass of undecane and diisobutyl ketone.
〔実施例５－１～５－１３、比較例５－１～５－２（電子線（ＥＢ）露光；ポジ型パターン形成）〕
　下記表１１に示す成分を下記表１１に示す溶剤に溶解させ、固形分濃度４．０質量％の溶液を調製し、これを０．０２μｍのポアサイズを有するポリエチレンフィルターでろ過して、実施例５－１～５－１３及び比較例５－１～５－２のレジスト組成物溶液を得た。ここで、下記表１１の溶剤における数値は、溶剤の全量に対する含有量を質量％で示したものである。これらのレジスト組成物を用いた以外は、実施例１－１と同様に、レジスト組成物の塗設、ＥＢ露光及び現像、及び、レジストパターンの評価を実施した。結果を下記表１２に示す。 [Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-2 (electron beam (EB) exposure; positive pattern formation)]
The components shown in Table 11 below were dissolved in the solvent shown in Table 11 below to prepare a solution having a solid content concentration of 4.0% by mass, and this was filtered through a polyethylene filter having a pore size of 0.02 μm. Example 5 Resist composition solutions of -1 to 5-13 and Comparative Examples 5-1 to 5-2 were obtained. Here, the numerical values for the solvents in Table 11 below indicate the content of the solvent with respect to the total amount in mass%. Except for using these resist compositions, coating of the resist composition, EB exposure and development, and evaluation of the resist pattern were carried out in the same manner as in Example 1-1. The results are shown in Table 12 below.
Figure JPOXMLDOC01-appb-T000103
Figure JPOXMLDOC01-appb-T000103
Figure JPOXMLDOC01-appb-T000104
Figure JPOXMLDOC01-appb-T000104
　上表により、化合物（Ａ）に適合する化合物を含有するレジスト組成物を用いた実施例５－１～５－１３は、該化合物を含有しないレジスト組成物を用いた比較例５－１～５－２と比較して、超微細のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成できることが分かった。 According to the above table, Examples 5-1 to 5-13 using a resist composition containing a compound compatible with compound (A) are Comparative Examples 5-1 to 5-5 using a resist composition not containing the compound. Compared to -2, it was found that in the formation of an ultrafine pattern, a pattern excellent in all of sensitivity, resolution, roughness performance and pattern cross-sectional shape can be formed.
　尚、上記実施例において、現像液、リンス液を前述の好ましい範囲内で変更しても、同様の性能を示す。また現像液を２種以上、リンス液を２種以上、混合して使用しても同様の性能を示す。
　また、上記実施例において、レジスト膜の上に、発明を実施するための形態において説明したトップコートを設けても、同様の効果が得られる。 In the above-described embodiment, the same performance is exhibited even when the developer and the rinsing liquid are changed within the above-described preferable range. The same performance is exhibited even when two or more types of developer and two or more types of rinse solutions are mixed and used.
Moreover, in the said Example, the same effect is acquired even if it provides the topcoat demonstrated in the form for inventing on a resist film.
　本発明によれば、特に、超微細（例えば、線幅５０ｎｍ以下）のパターンの形成において、感度、解像性、ラフネス性能及びパターン断面形状の全てに優れたパターンを形成することができる、感活性光線又は感放射線性組成物、並びに、これを用いたレジスト膜、パターン形成方法及び電子デバイスの製造方法を提供することができる。 According to the present invention, it is possible to form a pattern that is excellent in sensitivity, resolution, roughness performance, and pattern cross-sectional shape, particularly in the formation of an ultrafine pattern (for example, a line width of 50 nm or less). An actinic ray or radiation sensitive composition, and a resist film, a pattern formation method, and an electronic device manufacturing method using the same can be provided.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１５年９月３０日出願の日本特許出願（特願２０１５－１９４４４６）、及び２０１６年２月１８日出願の日本特許出願（特願２０１６－０２９１９７）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 30, 2015 (Japanese Patent Application No. 2015-194446) and a Japanese patent application filed on February 18, 2016 (Japanese Patent Application No. 2016-029197). Is incorporated herein by reference.

Claims (18)

  1. 　（Ａ）下記一般式（１）で表される構造を２個以上有し、酸架橋性基を有さない化合物、及び、活性光線又は放射線により酸を発生する化合物を含有する、感活性光線又は感放射線性組成物。
    Figure JPOXMLDOC01-appb-C000001
     
    式中、Ｘは、酸素原子又は硫黄原子を表し、Ｒは、水素原子又は１価の有機基を表す。＊は、結合手を表す。     (A) An actinic ray containing a compound having two or more structures represented by the following general formula (1), having no acid crosslinkable group, and a compound capable of generating an acid by actinic rays or radiation. Or a radiation sensitive composition.
    Figure JPOXMLDOC01-appb-C000001

    In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  2. 　上記一般式（１）における複数個のＲの内の少なくとも１つが水素原子である、請求項１に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to claim 1, wherein at least one of the plurality of Rs in the general formula (1) is a hydrogen atom.
  3. 　前記化合物（Ａ）が、前記一般式（１）で表される構造として、下記一般式（２）で表される構造を有する、請求項１又は２に記載の感活性光線又は感放射線性組成物。
    Figure JPOXMLDOC01-appb-C000002
     
    式中、Ｘ及びＲは、それぞれ、上記一般式（１）におけるＸ及びＲと同義である。Ａは、－ＮＲ’－又は酸素原子を表す。Ｒ’は、水素原子又は１価の有機基を表す。＊は、結合手を表す。     The actinic ray-sensitive or radiation-sensitive composition according to claim 1 or 2, wherein the compound (A) has a structure represented by the following general formula (2) as the structure represented by the general formula (1). object.
    Figure JPOXMLDOC01-appb-C000002

    In formula, X and R are synonymous with X and R in the said General formula (1), respectively. A represents —NR′— or an oxygen atom. R ′ represents a hydrogen atom or a monovalent organic group. * Represents a bond.
  4. 　前記化合物（Ａ）の分子量が４５０以上である、請求項１～３のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 3, wherein the compound (A) has a molecular weight of 450 or more.
  5. 　前記化合物（Ａ）が、芳香族基を有する、請求項１～４のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 4, wherein the compound (A) has an aromatic group.
  6. 　前記化合物（Ａ）の共役酸のｐＫａが１以下である、請求項１～５のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 5, wherein the pKa of the conjugate acid of the compound (A) is 1 or less.
  7. 　前記化合物（Ａ）が、極性基が酸の作用により分解し脱離する脱離基で保護された構造を有さない、請求項１～６のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or sensitizing compound according to any one of claims 1 to 6, wherein the compound (A) does not have a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid. Radiation composition.
  8. 　前記化合物（Ａ）が、上記一般式（１）で表される構造を３個以上有する、請求項１～７のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 7, wherein the compound (A) has three or more structures represented by the general formula (1).
  9. 　前記化合物（Ａ）が、下記一般式（ａ）で表される化合物である、請求項８に記載の感活性光線又は感放射線性組成物。
    Figure JPOXMLDOC01-appb-C000003
     
    　Ｌは３価の連結基を表し、Ｙ１、Ｙ２及びＹ３は、それぞれ独立して、前記一般式（１）で表される構造を有する１価の有機基を表す。     The actinic ray-sensitive or radiation-sensitive composition according to claim 8, wherein the compound (A) is a compound represented by the following general formula (a).
    Figure JPOXMLDOC01-appb-C000003

    L represents a trivalent linking group, and Y 1 , Y 2 and Y 3 each independently represent a monovalent organic group having a structure represented by the general formula (1).
  10. 　前記化合物（Ａ）が、重合体である、請求項１～９のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 9, wherein the compound (A) is a polymer.
  11. 　樹脂（Ｂ）を更に含有し、前記化合物（Ａ）の含有量が、前記樹脂（Ｂ）の含有量に対して１～３０質量％である、請求項１～１０のいずれか１項に記載の感活性光線又は感放射線性組成物。 The resin (B) is further contained, and the content of the compound (A) is 1 to 30% by mass with respect to the content of the resin (B). An actinic ray-sensitive or radiation-sensitive composition.
  12. 　樹脂（Ｂ）を更に含有し、前記樹脂（Ｂ）が、芳香族基を有する、請求項１～１１のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 11, further comprising a resin (B), wherein the resin (B) has an aromatic group.
  13. 　架橋剤（Ｃ）を更に含有する、請求項１～１２のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 12, further comprising a crosslinking agent (C).
  14. 　疎水性樹脂（Ｄ）を更に含有する、請求項１～１３のいずれか１項に記載の感活性光線又は感放射線性組成物。 The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 13, further comprising a hydrophobic resin (D).
  15. 　請求項１～１４のいずれか１項に記載の感活性光線又は感放射線性組成物により形成されたレジスト膜。 A resist film formed from the actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 14.
  16. 　請求項１５に記載のレジスト膜に活性光線又は放射線を照射することと、前記活性光線又は放射線を照射した膜を現像することとを含むパターン形成方法。 A pattern forming method comprising irradiating the resist film according to claim 15 with actinic rays or radiation and developing the film irradiated with the actinic rays or radiation.
  17. 　前記活性光線又は放射線を照射した膜を、有機溶剤を含有する現像液により現像して、ネガ型パターンを形成する、請求項１６に記載のパターン形成方法。 The pattern forming method according to claim 16, wherein the film irradiated with actinic rays or radiation is developed with a developer containing an organic solvent to form a negative pattern.
  18. 　請求項１６又は１７に記載のパターン形成方法を含む、電子デバイスの製造方法。 An electronic device manufacturing method including the pattern forming method according to claim 16.
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