Classifications

• • 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
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/19—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C313/02—Sulfinic acids; Derivatives thereof
  • C07C313/04—Sulfinic acids; Esters thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
  • C07C381/12—Sulfonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • 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
  • C07D295/14—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 carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D295/145—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 carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
  • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
  • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/76—Dibenzothiophenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
  • C07D493/18—Bridged systems
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
  • C07C2603/74—Adamantanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/86—Ring systems containing bridged rings containing four rings

Definitions

• the present invention relates to an actinic ray- or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in an ultra-microlithography process that can be applied to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the mold creation process for nanoimprinting, and the manufacturing process of high-density information recording media, as well as other photofabrication processes.
• ultra-microlithography process that can be applied to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the mold creation process for nanoimprinting, and the manufacturing process of high-density information recording media, as well as other photofabrication processes.
• Patent Document 1 describes an actinic ray-sensitive or radiation-sensitive resin composition containing an onium salt having a specific structure and a resin whose solubility in an alkaline developer increases under the action of an acid.
• Patent Document 2 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid having a specific structure upon irradiation with actinic rays or radiation.
• LWR performance refers to the ability to reduce the LWR of a pattern.
• resist compositions may be stored for a certain period of time after preparation, and it is desirable for them to have excellent LWR performance even when pattern formation is performed after the certain period of storage.
• the LWR performance of a resist composition immediately after production is also called “initial LWR performance,” and the LWR performance of a resist composition after a certain period of time has passed since preparation is also called “LWR performance after aging.”
• a resin whose polarity increases under the action of an acid; an onium salt (A) containing a sulfonate anion and not containing a fluorine atom or a structure represented by the following formula (Am-1); an onium salt (B) represented by the following formula (b-1), which contains a structure represented by the following formula (Am-1) and does not contain a fluorine atom;
• An actinic ray-sensitive or radiation-sensitive resin composition comprising:
• M B + represents an organic cation
• Z B - represents an organic anion, provided that at least one of M B + and Z B - contains the structure represented by formula (Am-1).
• Q 1 to Q 3 each independently represent a hydrogen atom or an organic group, and at least two of Q 1 to Q 3 may be bonded to each other to form a ring.
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by the following formula (y-1) or a substituent represented by the following formula (y - 2), and at least one of R 1a and R 2a represents a cyano group, a nitro group, a substituent represented by the following formula (y-1) or a substituent represented by the following formula (y-2).
• R 1b and R 2b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• L represents a single bond or a divalent linking group.
• X 1 represents a hydrogen atom or an organic group. At least two of R 1a , R 1b , R 2a , R 2b , L and X 1 may be bonded to each other to form a ring.
• M + represents an organic cation.
• Y1 and Y3 each independently represent -O- or -NR3- , where R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group or an aryl group.
• q and r each independently represent 0 or 1. * represents a bonding position.
• R 21a represents a hydrogen atom, a cyano group, a nitro group, or a substituent represented by the following formula (y-1).
• R 1b and R 2b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• R 22a represents a cyano group, a nitro group, a substituent represented by the following formula (y-1), or a substituent represented by the following formula (y-21).
• X 1 represents a hydrogen atom or an organic group.
• M + represents an organic cation. At least two of R 21a , R 1b , R 22a , R 2b , and X 1 may be bonded to each other to form a ring.
• Y1 and Y3 each independently represent -O- or -NR3- , where R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group or an aryl group.
• q and r each independently represent 0 or 1. * represents a bonding position.
• R 1 Y represents a cyano group, a nitro group or a substituent represented by formula (y-1), and * represents a bonding position.
• Z B - in formula (b-1) contains a structure represented by formula (Am-1).
• B onium salt
• R 31a , R 31b , R 32a and R 32b each independently represent a substituent not having a fluorine atom or a hydrogen atom. However, at least one of R 31a , R 31b , R 32a and R 32b represents a cyano group, a nitro group, a substituent represented by the following formula (yb-1) or a substituent represented by the following formula (yb-2).
• X 31 represents a hydrogen atom or an organic group. At least two of R 31a , R 31b , R 32a , R 32b and X 31 may be bonded to each other to form a ring. At least one of R 31a , R 31b , R 32a , R 32b and X 31 includes a structure represented by the above formula (Am-1).
• M B + represents an organic cation.
• Y 31 and Y 33 each independently represent -O- or -NR 33 -, where R 33 represents a hydrogen atom or an alkyl group.
• R represents an alkyl group, a cycloalkyl group or an aryl group.
• t and s each independently represent 0 or 1. * represents a bonding position.
• g represents an integer of 1 or 2.
• R YB represents a cyano group, a nitro group or a substituent represented by formula (yb-1) above. * represents a bonding position.
• R 41 represents R 42 -O- or R 43 -NR 44 -.
• R 42 and R 43 each independently represent an alkyl group, a cycloalkyl group, or an aryl group.
• R 44 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
• R 31c represents a cyano group or R 51 -SO 2 -.
• R 51 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R 31b and R 32b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• X 31 represents a hydrogen atom or an organic group. At least two of R 31b , R 32b , R 51 , and X 31 may be bonded to each other to form a ring. q1 represents 0 or 1. At least one of R 31b , R 32b , R 41 , R 51 and X 31 contains the structure represented by formula (Am-1) above. M B + represents an organic cation.
• R 21a in the formula (a-2) represents a cyano group, a nitro group, or a substituent represented by the formula (y-1).
• R 6 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p1 represents 0 or 1.
• R 31d represents a cyano group or R 7 -SO 2 -.
• R 7 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R 1b , R 2b , X 1 , and M + each have the same meaning as R 1b , R 2b , X 1 , and M + in formula (a-2) above. At least two of R 1b , R 2b , R 7 , and X 1 may be bonded to each other to form a ring.
• the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein (A)/(B), which is a mass ratio of the content of the onium salt (A) to the content of the onium salt (B) contained in the actinic ray-sensitive or radiation-sensitive resin composition, is 1 to 20.
• a pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10]; exposing the resist film; and developing the exposed resist film using a developer.
• a method for manufacturing an electronic device comprising the pattern formation method according to [12].
• the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in initial LWR performance and LWR performance after aging. Furthermore, the present invention can provide a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam).
• light means actinic rays or radiation.
• exposure includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV, and the like, but also drawing with particle beams such as electron beams and ion beams.
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• (meth)acrylate refers to at least one of acrylate and methacrylate.
• (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also called molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene equivalent values measured using a Gel Permeation Chromatography (GPC) device (Tosoh Corporation HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: refractive index detector).
• GPC Gel Permeation Chromatography
• the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes groups that have a substituent as well as groups that have no substituent.
• alkyl group includes not only alkyl groups that have no substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups).
• organic group in the present specification refers to a group that contains at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include a monovalent nonmetallic atomic group other than a hydrogen atom, and can be selected from the following substituents T.
• substituent T examples include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups
• examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).
• substituent T in the onium salt (A) and the onium salt (B) does not contain a fluorine atom.
• the bonding direction of the divalent groups is not limited unless otherwise specified.
• Y when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-.
• the above compound may be "X-CO-O-Z" or "X-O-CO-Z”.
• the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value calculated based on a database of Hammett's substituent constants and known literature values using the following software package 1. All pKa values described in this specification are values calculated using this software package.
• Software package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
• pKa can also be obtained by molecular orbital calculation.
• a specific example of this method is a method of calculating H + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
• the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in literature and are not limited to this.
• DFT density functional theory
• Gaussian16 is an example.
• pKa refers to a value calculated based on a database of Hammett's substituent constants and known literature values using the software package 1, as described above. However, when pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted. In this specification, pKa refers to "pKa in an aqueous solution” as described above, but when the pKa in an aqueous solution cannot be calculated, “pKa in a dimethyl sulfoxide (DMSO) solution” will be adopted.
• DMSO dimethyl sulfoxide
• solid content refers to components that form a film (preferably a resist film) formed using an actinic ray-sensitive or radiation-sensitive resin composition, and does not include solvents.
• any component that forms a film (preferably a resist film) formed using an actinic ray-sensitive or radiation-sensitive resin composition is considered to be a solid content even if it is in a liquid state.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin whose polarity increases under the action of an acid, a sulfonate anion, and a fluorine atom and a compound represented by the following formula:
• M B + represents an organic cation
• Z B - represents an organic anion, provided that at least one of M B + and Z B - contains the structure represented by formula (Am-1).
• Q 1 to Q 3 each independently represent a hydrogen atom or an organic group, and at least two of Q 1 to Q 3 may be bonded to each other to form a ring.
• the present inventors presume as follows, although the present invention is not limited in any way by the presumed mechanism below.
• the onium salt (A) does not contain fluorine atoms, it has high compatibility with resins whose polarity increases under the action of acid, and is uniformly dispersed. This is believed to suppress the variation in acid generated from the onium salt (A), thereby obtaining excellent LWR performance.
• the onium salt (B) also does not contain fluorine atoms, the compatibility between the onium salt (A) and the onium salt (B) is high. This is believed to suppress the variation in acid, thereby further improving the LWR performance, since the onium salt (B) is also uniformly dispersed.
• the composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition.
• the composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.
• the composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition.
• the composition of the present invention is preferably a chemically amplified resist composition.
• the composition of the present invention can be used to form an actinic ray- or radiation-sensitive film.
• the actinic ray- or radiation-sensitive film formed using the composition of the present invention is typically a resist film.
• the onium salt (A) contained in the composition of the present invention will now be described.
• the onium salt (A) is a compound that contains a sulfonate anion and does not contain a fluorine atom or a structure represented by the above formula (Am-1).
• the structure represented by the formula (Am-1) will be described in the explanation of the onium salt (B).
• the onium salt (A) is preferably a compound that generates an acid when irradiated with actinic rays or radiation (a photoacid generator).
• the onium salt (A) is preferably represented by the following formula (a-1):
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by the following formula (y-1) or a substituent represented by the following formula (y - 2), and at least one of R 1a and R 2a represents a cyano group, a nitro group, a substituent represented by the following formula (y-1) or a substituent represented by the following formula (y-2).
• R 1b and R 2b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• L represents a single bond or a divalent linking group.
• X 1 represents a hydrogen atom or an organic group. At least two of R 1a , R 1b , R 2a , R 2b , L and X 1 may be bonded to each other to form a ring.
• M + represents an organic cation.
• Y1 and Y3 each independently represent -O- or -NR3- , where R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group or an aryl group.
• q and r each independently represent 0 or 1. * represents a bonding position.
• R Y represents a cyano group, a nitro group or a substituent represented by formula (y-1). * represents a bonding position.
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by formula (y-1), or a substituent represented by formula (y-2), and at least one of R 1a and R 2a represents a cyano group, a nitro group, a substituent represented by formula (y-1), or a substituent represented by formula (y-2).
• Y1 and Y3 each independently represent -O- or -NR3- , and R3 represents a hydrogen atom or an alkyl group.
• the alkyl group represented by R3 may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. It is preferred that Y1 and Y3 represent --O--.
• q represents 0 or 1, and preferably represents 0.
• r represents 0 or 1, and preferably represents 1.
• Y 2 in formula (y-1) represents —C( ⁇ O)— or —SO 2 —, and preferably represents —C( ⁇ O)—.
• R 4 represents an alkyl group, a cycloalkyl group or an aryl group, and preferably represents an alkyl group or a cycloalkyl group.
• the alkyl group represented by R 4 may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms.
• Examples of the alkyl group represented by R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
• the alkyl group represented by R 4 may have a substituent other than a fluorine atom.
• the substituent that the alkyl group represented by R 4 may have is not particularly limited except that it does not contain a fluorine atom, and examples thereof include a cycloalkyl group and an aryl group.
• the cycloalkyl group represented by R 4 may be a single ring or a polycyclic ring, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms.
• Examples of the cycloalkyl group represented by R 4 include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group.
• the cycloalkyl group represented by R 4 may have a substituent other than a fluorine atom.
• the substituent that the cycloalkyl group represented by R 4 may have is not particularly limited except that it does not contain a fluorine atom, and examples thereof include an alkyl group and an aryl group.
• the explanation, specific examples, and preferred ranges of the alkyl group and the aryl group as the substituent that the cycloalkyl group represented by R 4 may have are the same as those in the alkyl group represented by R 4 described above and the aryl group represented by R 4 described below.
• One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by a vinylene group.
• the aryl group represented by R 4 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or naphthyl group, and most preferably a phenyl group.
• the aryl group represented by R 4 may have a substituent other than a fluorine atom.
• the substituent that the aryl group represented by R 4 may have is not particularly limited except that it does not contain a fluorine atom, and examples thereof include an alkyl group and a cycloalkyl group.
• R 1 Y in formula (y-2) represents a cyano group, a nitro group, or a substituent represented by formula (y-1).
• R 1 Y is a substituent represented by formula (y-1)
• the explanation, specific examples, and preferred ranges of the substituent represented by formula (y-1) are as described above.
• R Y preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -OCOR 4 or -SO 2 R 4 , more preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 or -SO 2 R 4 , and even more preferably represents a cyano group, -COOR 4 , -OCOOR 4 or -SO 2 R 4.
• the definition, explanation, specific examples and preferred range of R 4 are as described above.
• p represents 1 or 2, and preferably represents 1.
• R 1a and R 2a preferably represent a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -OCOR 4 , -SO 2 R 4 , -SO 3 R 4 , -CH 2 CN, -CH 2 COOR 4 , -CH 2 OCOOR 4 , -CH 2 OCOR 4 , -CH 2 SO 2 R 4 or -CH 2 SO 3 R 4 , more preferably a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -SO 2 R 4 , -CH 2 CN, -CH 2 COOR 4 , -CH 2 OCOOR 4 or -CH 2 SO 2 R 4 , and more preferably a cyano group, -COOR 4 , -OCOOR 4 , and more preferably represents —SO 2 R 4 , —CH 2 COOR 4 , —CH 2 OCOOR 4 or ——
• R 1b and R 2b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• the fluorine atom as a substituent is a substituent having a fluorine atom, and is not a substituent not having a fluorine atom.
• the substituents not having a fluorine atom represented by R 1b and R 2b are not particularly limited except that they do not have a fluorine atom, and examples thereof include organic groups and nitro groups.
• the organic group represented by R 1b and R 2b is not particularly limited except that it does not have a fluorine atom.
• a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (y-1), or a substituent represented by formula (y-2) is preferable.
• the explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group represented by R 1b and R 2b are the same as those for R 4 in the above formula (y-1).
• R 1b and R 2b are the substituent represented by formula (y-1) and the substituent represented by formula (y-2), the explanations, specific examples and preferred ranges of the substituent represented by formula (y-1) (each symbol in formula (y-1)) and the substituent represented by formula (y-2) (each symbol in formula (y-2)) are as described above.
• X1 represents a hydrogen atom or an organic group.
• the organic group represented by X1 is not particularly limited except that it does not have a fluorine atom.
• a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (y-1), or a substituent represented by formula (y-2) is preferable.
• the explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group represented by X 1 are the same as those for R 4 in the above formula (y-1).
• L represents a single bond or a divalent linking group.
• the divalent linking group represented by L is not particularly limited, and examples thereof include -O-, -CO-, -COO-, -OCOO-, -NR 1 -, -CONR 1 -, -S-, -SO-, -SO 2 -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a group formed by combining two or more of these groups.
• R 1 represents a hydrogen atom or an alkyl group.
• the alkylene group represented by L is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.
• the number of carbon atoms of the cycloalkylene group represented by L is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15.
• the cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group.
• One of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group.
• the alkenylene group represented by L is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms.
• the arylene group represented by L is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms.
• the arylene group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.
• examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a 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, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
• M + represents an organic cation.
• M + is preferably a sulfonium or iodonium cation.
• the cation represented by M + is not particularly limited.
• the cation may have a valence of one or more than two.
• a cation represented by the following formula (ZaI) hereinafter also referred to as "cation (ZaI)" or a cation represented by the following formula (ZaII) (hereinafter also referred to as “cation (ZaII)"
• ZaI cation represented by the following formula (ZaI)
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group represented by R 201 , R 202 and R 203 is preferably 1 to 30, and more preferably 1 to 20.
• Any two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group.
• Examples of the group formed by bonding any two of R 201 to R 203 include an alkylene group (e.g., a butylene group and a pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
• the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
• the arylsulfonium cation all of R 201 to R 203 may be aryl groups, or some of R 201 to R 203 may be aryl groups, with the remainder being alkyl groups or cycloalkyl groups.
• R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring.
• Examples of the group formed by bonding two of R 201 to R 203 include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene group, pentylene group, and -CH 2 -CH 2 -O-CH 2 -CH 2 -).
• Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group which the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
• Preferred substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have are alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 14 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms other than fluorine atoms (e.g., chlorine atoms, bromine atoms, iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups.
• the above-mentioned substituents may further have a substituent, if possible. It is also preferred that the above
• the cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represent an organic group not having an aromatic ring.
• the aromatic ring also includes an aromatic ring containing a heteroatom.
• the organic group not having an aromatic ring represented by R 201 to R 203 preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.
• Examples of the alkyl group and cycloalkyl group of R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
• R 201 to R 203 may be further substituted with a halogen atom other than a fluorine atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group through any combination of the substituents.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom other than a fluorine atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, a t-butyl group), a cycloalkyl group, a halogen atom other than a fluorine atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c and R x and R y each independently form an acid-decomposable group through any combination of the substituents.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
• the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
• the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y includes alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom.
• the groups formed by combining R5c and R6c , and R5c and Rx are preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may each have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R 13 represents a hydrogen atom, a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group other than a fluorine atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part).
• a fluorine atom e.g., a chlorine atom, a bromine atom, an iodine atom
• R 13 represents a hydrogen atom, a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group
• R 14 represents a hydroxyl group, a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, an iodine atom), an alkyl group, a halogenated alkyl group other than a fluorine atom, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part).
• a halogen atom other than a fluorine atom e.g., a chlorine atom, a bromine atom, an iodine atom
• an alkyl group e.g., a halogenated alkyl group other than a fluor
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be bonded to each other to form a ring. When two R 15 are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferable that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
• the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by bonding two R 15 to each other may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like. It is also preferred that each of the substituents R 13 to R 15 and R x and R y independently form an acid-decomposable group through any combination of the substituents.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group of R 204 and R 205 may be an aryl group having a heterocycle with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group of R 204 and R 205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
• a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group
• a cycloalkyl group having 3 to 10 carbon atoms e.g
• the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include, for example, an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom other than a fluorine atom, a hydroxyl group, and a phenylthio group. It is also preferable that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of the substituents.
• the onium salt (A) is preferably represented by the following formula (a-2):
• R 21a represents a hydrogen atom, a cyano group, a nitro group, or a substituent represented by the following formula (y-1).
• R 1b and R 2b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• R 22a represents a cyano group, a nitro group, a substituent represented by the following formula (y-1), or a substituent represented by the following formula (y-21).
• X 1 represents a hydrogen atom or an organic group.
• M + represents an organic cation. At least two of R 21a , R 1b , R 22a , R 2b , and X 1 may be bonded to each other to form a ring.
• Y1 and Y3 each independently represent -O- or -NR3- , where R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group or an aryl group.
• q and r each independently represent 0 or 1. * represents a bonding position.
• R 1 Y represents a cyano group, a nitro group or a substituent represented by formula (y-1), and * represents a bonding position.
• R 21a in formula (a-2) represents a hydrogen atom, a cyano group, a nitro group, or a substituent represented by formula (y-1), and preferably represents a cyano group, a nitro group, or a substituent represented by formula (y-1).
• R 21a is a substituent represented by formula (y-1)
• the explanation, specific examples and preferred ranges of the substituent represented by formula (y-1) are as described above.
• R 22a represents a cyano group, a nitro group, a substituent represented by formula (y-1) or a substituent represented by formula (y-21).
• R 22a is a substituent represented by formula (y-1)
• the explanation, specific examples and preferred ranges of the substituent (each symbol in y-1) represented by formula (y-1) are as described above.
• R 1 Y represents a cyano group, a nitro group, or a substituent represented by formula (y-1).
• R Y in formula (y-21) is a substituent represented by formula (y-1)
• the explanation, specific examples and preferred ranges of the substituent represented by formula (y-1) are as described above.
• onium salt (A) is one represented by the following formula (a-3):
• R 6 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p1 represents 0 or 1.
• R 31d represents a cyano group or R 7 -SO 2 -.
• R 7 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R 1b , R 2b , X 1 , and M + each have the same meaning as R 1b , R 2b , X 1 , and M + in formula (a-2) above. At least two of R 1b , R 2b , R 7 , and X 1 may be bonded to each other to form a ring.
• R 31d represents a cyano group or R 7 -SO 2 -.
• R 7 represents an alkyl group, a cycloalkyl group, or an aryl group.
• the explanation, specific examples, and preferred ranges of the alkyl group, cycloalkyl group, and aryl group represented by R 7 are the same as those for R 4 in formula (y-1) above.
• the onium salt (A) may be a compound represented by the following formula (a-4):
• R 6 represents an alkyl group, a cycloalkyl group, or an aryl group. Two R 6s may be the same or different.
• R 2a , R 2b , X 1 , and M + respectively represent the same as R 2a , R 2b , X 1 , and M + in formula (a-1). At least two of R 2a , R 2b , and X 1 may be bonded to each other to form a ring.
• the onium salt (A) may be a compound represented by the following formula (a-5):
• R 2b , X 1 and M + have the same meanings as R 2b , X 1 and M + in formula (a-2), respectively.
• R 2b and X 1 may be bonded to each other to form a ring.
• R 2b , X 1 and M + in formula (a-5) are the same as those for R 2b , X 1 and M + in formula (a-2) above, respectively.
• the onium salt (A) may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. In addition, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination.
• the molecular weight of the onium salt (A) is not particularly limited, but is, for example, preferably 5000 or less, more preferably 3000 or less, and particularly preferably 2000 or less.
• the molecular weight of the onium salt (A) is preferably 100 or more, and more preferably 200 or more.
• the onium salt (A) When the onium salt (A) is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of a resin whose polarity increases by the action of an acid, or it may be incorporated into a resin different from the resin whose polarity increases by the action of an acid.
• the onium salt (A) is preferably in the form of a low molecular weight compound.
• the content of the onium salt (A) in the composition of the present invention is not particularly limited, but is preferably from 1.0 to 50.0 mass%, more preferably from 5.0 to 45.0 mass%, and even more preferably from 10.0 to 40.0 mass%, based on the total solid content of the composition of the present invention.
• the onium salt (A) may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the method for producing the onium salt (A) is not particularly limited.
• the compound represented by formula (a-1) can be synthesized, for example, by the following method.
• intermediate (N1-1) is synthesized under strong basic conditions.
• R c represents an alkyl group, and is preferably an ethyl group, a propyl group, a butyl group, or an isobutyl group.
• Z c1 represents a halogen atom, and is preferably a chlorine atom, a bromine atom, or an iodine atom.
• the base used is preferably one that is strongly basic and has low nucleophilicity, and is preferably sodium hydride or potassium tert-butoxide.
• the reaction solvent is not particularly limited as long as it does not react with the base used, but is preferably an ether solvent such as tetrahydrofuran, an amide solvent such as N,N-dimethylformamide, or a mixed solvent thereof.
• the reaction temperature is preferably 0°C to 80°C.
• the reaction is preferably carried out in a nitrogen atmosphere.
• the raw material (N1-1A) can be produced by using a commercially available reagent and a general esterification or sulfonation method.
• the raw material (N1-1A) can also be produced by a method other than the above.
• sulfonic acid esters in which R 1a is CH 3 SO 2 - and R 1b is H can be synthesized with reference to the non-patent document "Journal of Medicinal Chemistry, Vol. 27 (1984), pp. 664-670".
• the raw material (N1-1B) can be produced using commercially available reagents and common esterification or halogenation techniques.
• intermediate (N1-2) is synthesized from intermediate (N1-1) obtained in the above (1).
• a c represents an alkali metal atom, preferably sodium or potassium.
• Z c2 represents a halogen atom, preferably an iodine atom.
• a c + Z c2 - is preferably sodium iodide.
• the reaction solvent is preferably a solvent that dissolves A c + Z c2 - , and is preferably a nitrile solvent such as acetonitrile or a ketone solvent such as acetone.
• the reaction temperature is preferably 20°C to 100°C.
• a compound represented by formula (a-1) is synthesized from the intermediate (N1-2) obtained in the above (2).
• Z c3 represents a halogen atom, preferably a chlorine atom or a bromine atom.
• the reaction solvent is preferably a halogen-based solvent such as methylene chloride and water, and the reaction is preferably carried out in a two-layer system.
• the reaction temperature is preferably 0°C to 50°C.
• the onium salt (A) can also be produced by a method other than the above.
• a compound in which R 1a is CN, R 1b is H, R 2a is -COOR 4 , R 2b is H, L is a single bond, and X 1 is H in the formula (a-1) can be synthesized with reference to the non-patent document "Journal of Medicinal Chemistry, Vol. 54 (2011), pp. 3606-3623.”
• onium salt (A) examples include, but are not limited to, PAG-1 to PAG-30 used in the examples described below and the following compounds.
• the onium salt (B) contained in the composition of the present invention will now be described.
• the onium salt (B) is a compound represented by the following formula (b-1):
• the onium salt (B) is a compound that includes a structure represented by the following formula (Am-1) and does not contain a fluorine atom.
• the onium salt (B) is a compound different from the above-mentioned onium salt (A). Since the onium salt (B) contains a structure represented by the following formula (Am-1), it can function as an acid diffusion controller.
• the acid diffusion controller traps the acid generated from the photoacid generator or the like upon exposure to light, and acts as a quencher that suppresses the reaction of the resin, the polarity of which increases due to the action of the acid in the unexposed area, caused by the excess acid generated.
• M B + represents an organic cation
• Z B - represents an organic anion, provided that at least one of M B + and Z B - contains the structure represented by formula (Am-1).
• Q 1 to Q 3 each independently represent a hydrogen atom or an organic group, and at least two of Q 1 to Q 3 may be bonded to each other to form a ring.
• Q 1 to Q 3 each independently represent a hydrogen atom or an organic group.
• the organic group represented by Q 1 to Q 3 is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a carboxy group, an acyl group, an acyloxy group, a formyloxy group, an alkoxycarbonyl group, an alkylsulfoxy group, an arylsulfoxy group, an alkylsulfonyl group, an arylsulfonyl group, -OCO(OR 8 ) or -OCO(NR 9 R 10 ).
• R 8 , R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group.
• the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group, carboxy group, acyloxy group, formyloxy group, alkoxycarbonyl group, alkylsulfoxy group and arylsulfoxy group represented by Q1 to Q3 may further have one or more substituents.
• the alkyl group may be substituted with a hydroxy group.
• the hydrogen atom of the carboxy group may be substituted with a substituent.
• the groups represented by Q 1 to Q 3 will be described below.
• the number of carbon atoms of the alkyl group is not particularly limited, and may be, for example, 1 to 20, 1 to 10, or 1 to 6.
• the alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group.
• alkyl group portion of an alkoxy group the alkyl group portion of an aralkyl group, the alkyl group portion of an alkoxycarbonyl group, the alkyl group portion of an alkylsulfonyl group, the alkyl group portion of an alkylsulfoxy group, the alkyl group portion when the acyl group is an alkylcarbonyl group, and the alkyl group portion when the acyloxy group is an alkylcarbonyloxy group.
• the cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, etc., or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc.
• the number of carbon atoms in the cycloalkyl group is not particularly limited, and may be, for example, 5 to 20 or 5 to 15.
• the alkenyl group may be either linear or branched.
• the number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6.
• the alkynyl group may be either linear or branched.
• the number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6.
• the aryl group may be either a monocyclic or polycyclic (e.g., 2 to 6 rings, etc.).
• the number of ring atoms of the aryl group is not particularly limited, and may be, for example, 6 to 20, 6 to 15, or 6 to 10.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group.
• the heteroaryl group may be either a monocyclic or polycyclic (e.g., 2 to 6 rings, etc.).
• the number of heteroatoms contained in the heteroaryl group as ring atoms is not particularly limited, but may be, for example, 1 to 10.
• Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
• the number of ring atoms in the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.
• R 8 , R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group.
• the explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aralkyl group represented by R 8 , R 9 and R 10 are the same as those in Q 1 to Q 3 above.
• Q 1 to Q 3 may contain a cation or an anion, that is, the atoms or atomic groups contained in Q 1 to Q 3 may release electrons to become cations, or may receive electrons to become anions.
• At least one of M B + and Z B - in formula (b-1) contains a structure represented by formula (Am-1). At least one of M B + and Z B - may be represented by formula (Am-1), or at least one of a portion of the atomic groups contained in M B + and a portion of the atomic groups contained in Z B - may be represented by formula (Am-1).
• Q 1 to Q 4 each independently represent a hydrogen atom or an organic group, and at least two of Q 1 to Q 4 may be bonded to each other to form a ring.
• the organic groups represented by Q 1 to Q 3 are as described above.
• the organic group represented by Q 4 is the same as that described above for Q 1 to Q 3 .
• Z B - in formula (b-1) represents an organic anion, and preferably represents a sulfonate anion. It is preferable that Z B - contains a structure represented by formula (Am-1).
• the onium salt (B) is preferably represented by the following formula (b-2).
• the compound represented by the following formula (b-2) can function as an acid diffusion control agent whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation.
• R 31a , R 31b , R 32a and R 32b each independently represent a substituent not having a fluorine atom or a hydrogen atom. However, at least one of R 31a , R 31b , R 32a and R 32b represents a cyano group, a nitro group, a substituent represented by the following formula (yb-1) or a substituent represented by the following formula (yb-2).
• X 31 represents a hydrogen atom or an organic group. At least two of R 31a , R 31b , R 32a , R 32b and X 31 may be bonded to each other to form a ring. At least one of R 31a , R 31b , R 32a , R 32b and X 31 includes a structure represented by formula (Am-1).
• M B + represents an organic cation.
• Y 31 and Y 33 each independently represent -O- or -NR 33 -, where R 33 represents a hydrogen atom or an alkyl group.
• R represents an alkyl group, a cycloalkyl group or an aryl group.
• t and s each independently represent 0 or 1. * represents a bonding position.
• g 1 or 2.
• R YB represents a cyano group, a nitro group or a substituent represented by formula (yb-1). * represents a bonding position.
• R 31a , R 31b , R 32a and R 32b each independently represent a substituent not having a fluorine atom or a hydrogen atom, provided that at least one of R 31a , R 31b , R 32a and R 32b represents a cyano group, a nitro group, a substituent represented by formula (yb-1) or a substituent represented by formula (yb-2).
• the substituents not having a fluorine atom represented by R 31a , R 31b , R 32a and R 32b are not particularly limited except that they do not have a fluorine atom, and examples thereof include organic groups and nitro groups.
• the organic group represented by R 31a , R 31b , R 32a and R 32b is not particularly limited except that it does not have a fluorine atom, and is preferably, for example, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (yb-1) or a substituent represented by formula (yb-2).
• the explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group represented by R 31a , R 31b , R 32a and R 32b are the same as those for R 4 in formula (y-1) above.
• Y 31 and Y 33 each independently represent -O- or -NR 33 -, where R 33 represents a hydrogen atom or an alkyl group.
• the alkyl group represented by R 33 may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. It is preferable that Y 31 and Y 33 each represent —O—.
• t represents 0 or 1, and preferably represents 0.
• s represents 0 or 1, and preferably represents 1.
• Y 32 represents —C( ⁇ O)— or —SO 2 —, and preferably represents —C( ⁇ O)—.
• R 34 represents an alkyl group, a cycloalkyl group, or an aryl group. The explanation, specific examples, and preferred ranges of the alkyl group, cycloalkyl group, and aryl group represented by R 34 are the same as those for R 4 in formula (y-1) above.
• R YB represents a cyano group, a nitro group, or a substituent represented by formula (yb-1).
• R YB is a substituent represented by formula (yb-1)
• the explanation, specific examples, and preferred ranges of the substituent represented by formula (yb-1) are as described above.
• R YB preferably represents a cyano group, a nitro group, -COOR 34 , -OCOOR 34 , -OCOR 34 or -SO 2 R 34 , more preferably represents a cyano group, a nitro group, -COOR 34 , -OCOOR 34 or -SO 2 R 34 , and even more preferably represents a cyano group, -COOR 34 , -OCOOR 34 or -SO 2 R 34.
• the definition, explanation, specific examples and preferred range of R 34 are as described above.
• g represents 1 or 2, and preferably represents 1.
• X 31 represents a hydrogen atom or an organic group.
• the organic group represented by X31 is not particularly limited except that it does not have a fluorine atom, and is preferably, for example, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (yb-1), or a substituent represented by formula (yb-2).
• the explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group represented by X 31 are the same as those for R 4 in the above formula (y-1).
• M B + represents an organic cation.
• the explanation, specific examples and preferred ranges of the organic cation represented by M B + are the same as those for M + in the above formula (a-1).
• onium salt (B) is one represented by the following formula (b-3):
• R 41 represents R 42 -O- or R 43 -NR 44 -.
• R 42 and R 43 each independently represent an alkyl group, a cycloalkyl group, or an aryl group.
• R 44 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
• R 31c represents a cyano group or R 51 -SO 2 -.
• R 51 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R 31b and R 32b each independently represent a substituent not having a fluorine atom or a hydrogen atom.
• X 31 represents a hydrogen atom or an organic group. At least two of R 31b , R 32b , R 51 , and X 31 may be bonded to each other to form a ring. q1 represents 0 or 1. At least one of R 31b , R 32b , R 41 , R 51 and X 31 includes a structure represented by formula (Am-1). M B + represents an organic cation.
• R 41 represents R 42 -O- or R 43 -NR 44 -.
• R 42 and R 43 each independently represent an alkyl group, a cycloalkyl group or an aryl group.
• R 44 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
• R 31b , R 32b , X 31 and M B + in formula (b-3) are the same as those for R 31b , R 32b , X 31 and M B + in formula (b-2) above, respectively.
• q1 represents 0 or 1, and preferably represents 0.
• R 31c represents a cyano group or R 51 -SO 2 -.
• R 51 represents an alkyl group, a cycloalkyl group, or an aryl group.
• the explanation, specific examples, and preferred ranges of the alkyl group, cycloalkyl group, and aryl group represented by R 51 are the same as those for R 4 in the above formula (y-1).
• M B + in formula (b-1) may contain a structure represented by formula (Am-1).
• preferred embodiments include the following (1) to (4).
• Z B - in formula (b-1) preferably represents a sulfonate anion, and more preferably represents a sulfonate anion in the above-mentioned formulas (a-1) to (a-5).
• Z B - in formula (b-1) represents a sulfonate anion in formulas (a-1) to (a-5)
• the explanation, specific examples and preferred ranges of the sulfonate anion in formulas (a-1) to (a-5) (each symbol in formulas (a-1) to (a-5)) are as described above.
• the onium salt (B) may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. In addition, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination.
• the molecular weight of the onium salt (B) is not particularly limited, but is, for example, preferably 5000 or less, more preferably 3000 or less, and particularly preferably 2000 or less.
• the molecular weight of the onium salt (B) is preferably 100 or more, and more preferably 200 or more.
• the onium salt (B) When the onium salt (B) is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of a resin whose polarity increases by the action of an acid, or it may be incorporated into a resin different from the resin whose polarity increases by the action of an acid.
• the onium salt (B) is preferably in the form of a low molecular weight compound.
• the content of the onium salt (B) in the composition of the present invention is not particularly limited, but is preferably from 0.1 to 30.0 mass%, more preferably from 0.5 to 20.0 mass%, and even more preferably from 1.0 to 15.0 mass%, based on the total solid content of the composition of the present invention.
• the onium salt (B) may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• onium salt (B) examples include, but are not limited to, PAG-B1 to PAG-B13 used in the examples described below and the following compounds.
• the method for producing the onium salt (B) is not particularly limited.
• the onium salt (B) can be synthesized, for example, by the same method as the onium salt (A) described above.
• the mass ratio (A)/(B) of the content of onium salt (A) to the content of onium salt (B) contained in the composition of the present invention is preferably 0.5 to 20, more preferably 1 to 20, and even more preferably 1 to 15.
• the composition of the present invention contains a resin (also referred to as "resin (P)”) whose polarity increases under the action of an acid.
• the resin (P) usually contains a group that decomposes under the action of an acid to increase polarity (also referred to as an "acid-decomposable group”), and preferably contains a repeating unit having an acid-decomposable group.
• the resin (P) typically, in the pattern forming method using the composition of the present invention, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
• the repeating unit having an acid-decomposable group in addition to the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable.
• the acid decomposable group refers to a group that decomposes under the action of an acid to generate a polar group.
• the acid decomposable group preferably has a structure in which the polar group is protected by a group (leaving group) that is eliminated under the action of an acid. That is, the resin (P) has a repeating unit that decomposes under the action of an acid to generate a polar group.
• the resin having this repeating unit has an increased polarity under the action of an acid, and its solubility in an alkaline developer is increased, and its solubility in an organic solvent is decreased.
• the polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.
• the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
• Examples of the group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4).
• Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
• Formula (Y3) -C(R 36 )(R 37 )(OR 38 )
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic).
• Rx 1 to Rx 3 are alkyl groups (linear or branched)
• Rx 1 to Rx 3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx 1 to Rx 3 each independently represent a linear alkyl group.
• Rx 1 to Rx 3 may be bonded to form a monocycle or polycycle.
• the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
• the cycloalkyl groups of Rx 1 to Rx 3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• the alkenyl group of Rx 1 to Rx 3 is preferably a vinyl group.
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
• one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.
• the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure
• the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3 , and the ring formed by bonding two of Rx1 to Rx3 further have a fluorine atom or an iodine atom as a substituent.
• R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
• R 37 and R 38 may be 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 a hydrogen atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group containing a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.
• one or more methylene groups may be replaced with a group containing a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.
• R 38 may be bonded to another substituent in the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 to another substituent in the main chain of the repeating unit is preferably an alkylene group such as a methylene group.
• the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure
• the monovalent organic groups represented by R 36 to R 38 and the ring formed by bonding R 37 and R 38 to each other further have a fluorine atom or an iodine atom as a substituent.
• the formula (Y3) is preferably a group represented by the following formula (Y3-1):
• L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group with an aryl group).
• M represents a single bond or a divalent linking group.
• Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
• the alkyl and cycloalkyl groups may, for example, have one of the methylene groups replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group.
• L1 and L2 are a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring). From the viewpoint of miniaturization of the pattern, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group.
• Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and an adamantane group.
• Tg glass transition temperature
• activation energy are high, so that in addition to ensuring the film strength, fogging can be suppressed.
• the alkyl group, cycloalkyl group, aryl group, and a group combining these groups represented by L1 and L2 preferably further have a fluorine atom or an iodine atom as a substituent.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have, for example, one of the methylene groups replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group.
• the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, in the alkyl group which may contain a heteroatom, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group, the ammonium group, the mercapto group, the cyano group, the aldehyde group, and groups combining these, represented by Q, it is also preferable that the heteroatom is a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.
• 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 preferably an aryl group.
• the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.
• the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.
• Other groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.
• the repeating unit having an acid-decomposable group is preferably a repeating unit represented by formula (A).
• L1 represents a divalent linking group which may have a fluorine atom or an iodine atom
• R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom
• R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom, provided that at least one of L1 , R1 , and R2 has a fluorine atom or an iodine atom.
• Examples of the divalent linking group represented by L1 which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO 2 -, a hydrocarbon group which may have a fluorine atom or an iodine atom (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked together.
• the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
• the alkyl group represented by R1 may be linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.
• the total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group represented by R1 may contain a heteroatom other than a halogen atom, such as an oxygen atom.
• Examples of the leaving group represented by R2 which may have a fluorine atom or an iodine atom include leaving groups represented by the above formulas (Y1) to (Y4) and which have a fluorine atom or an iodine atom.
• the repeating unit having an acid-decomposable group is preferably a repeating unit represented by 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.
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic ring (eg, a monocyclic or polycyclic cycloalkyl group).
• Examples of the alkyl group represented by Xa 1 which may have a substituent 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.
• Examples of the monovalent organic group represented by R 11 include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred.
• Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group, in which Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - group.
• 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, and a t-butyl group.
• the cycloalkyl groups of Rx 1 to Rx 3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• the alkenyl group of Rx 1 to Rx 3 is preferably a vinyl group.
• a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferable.
• a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group is preferable.
• a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
• cycloalkyl group formed by combining two of Rx1 to Rx3 for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.
• examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).
• repeating units having an acid-decomposable group are shown below, but are not limited to these.
• Xa1 represents H, CH 3 , CF 3 , or CH 2 OH
• Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
• the resin (P) may have, as the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond.
• the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by formula (B).
• Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.
• L represents a single bond, or a divalent linking group which may have a substituent.
• Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).
• Examples of the alkyl group represented by Xb which may have a substituent 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 which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred.
• Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Examples of the divalent linking group for L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group, in which Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable.
• L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group, where Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.
• the alkyl group of Ry 1 to Ry 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, and a t-butyl group.
• the cycloalkyl groups of Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group of Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• the alkenyl group for Ry 1 to Ry 3 is preferably a vinyl group.
• the alkynyl group for Ry 1 to Ry 3 is preferably an ethynyl group.
• a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferable.
• the cycloalkyl group formed by combining two of Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
• a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• cycloalkyl group or cycloalkenyl group formed by combining two of Ry1 to Ry3 for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, a vinylidene group, or a combination thereof.
• a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, a vinylidene group, or a combination thereof.
• one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
• Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
• Ry2 and Ry3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.
• examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
• an acid-decomposable (meth)acrylic acid tertiary ester repeating unit a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents
• the content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (P), and the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (P).
• Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond include the repeating units described in paragraphs [0067] to [0071] of WO 2022/024928. The above descriptions are incorporated herein by reference.
• the content of the repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (P).
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units in the resin (P).
• Resin (P) may contain at least one type of repeating unit selected from the group consisting of Group A below and/or at least one type of repeating unit selected from the group consisting of Group B below.
• Group A A group consisting of the following repeating units (20) to (25).
• (20) A repeating unit having an acid group, as described later.
• (21) A repeating unit having neither an acid decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom, as described later.
• (22) A repeating unit having a lactone group, a sultone group, or a carbonate group, as described later.
• (23) A repeating unit having a photoacid generating group, as described later.
• Group B A group consisting of the following repeating units (30) to (32).
• (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below.
• (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described below.
• (32) A repeating unit represented by formula (III) which has neither a hydroxyl group nor a cyano group, as described below.
• the resin (P) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group.
• the definition of an acid group will be explained later together with a preferred embodiment of a repeating unit having an acid group.
• Resin (P) may have at least one repeating unit selected from the group consisting of Group A.
• resin (P) preferably has at least one repeating unit selected from the group consisting of Group A.
• the resin (P) may contain at least one of a fluorine atom and an iodine atom.
• the resin (P) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (P) may have one repeating unit containing both a fluorine atom and an iodine atom, or the resin (P) may contain two types of repeating units, a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
• Resin (P) may have a repeating unit having an aromatic group.
• the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that resin (P) has a repeating unit having an aromatic group.
• Resin (P) may have at least one repeating unit selected from the group consisting of Group B.
• resin (P) preferably has at least one repeating unit selected from the group consisting of Group B.
• the resin (P) contains neither a fluorine atom nor a silicon atom.
• the resin (P) does not have an aromatic group.
• the resin (P) may have a repeating unit having an acid group.
• the acid group preferably has a pKa of 13 or less.
• the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10.
• the content of the acid group in the resin (P) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
• the acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• a fluorinated alcohol group preferably a hexafluoroisopropanol group
• a sulfonic acid group preferably a sulfonamide group
• an isopropanol group preferably, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• one or more (preferably one or two) fluorine atoms may be substituted with a group other than a fluorine atom (such
• the repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected with a group that is cleaved by the action of an acid described above, and a repeating unit having a lactone group, a sultone group, or a carbonate group described below.
• the repeating unit having an acid group may have a fluorine atom or an iodine atom.
• Specific examples of the repeating unit having an acid group include the repeating units described in paragraphs [0088] to [0089] and [0103] to [0110] of WO 2022/024928. The above descriptions are incorporated herein by reference.
• the repeating unit having an acid group is preferably a repeating unit represented by the following formula (b1-1):
• a a1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R 21 represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are a plurality of R 21, they may be the same or different. When there are a plurality of R 21 , they may combine with each other to form a ring.
• R 21 is preferably a hydrogen atom.
• a represents an integer of 1 to 3.
• b represents an integer of 0 to (5-a).
• the content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total repeating units in resin (P).
• the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in resin (P).
• the resin (P) may have a repeating unit (hereinafter also referred to as unit X) that has neither an acid decomposable group nor an acid group and has a fluorine atom, a bromine atom or an iodine atom.
• the ⁇ repeating unit having neither an acid decomposable group nor an acid group and has a fluorine atom, a bromine atom or an iodine atom> referred to here is preferably different from other types of repeating units belonging to Group A, such as the ⁇ repeating unit having a lactone group, a sultone group or a carbonate group> and the ⁇ repeating unit having a photoacid generating group> described below.
• the repeating unit X is preferably a repeating unit represented by formula (C).
• L5 represents a single bond or an ester group.
• R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.
• R10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which combines these.
• Specific examples of the repeating unit having a fluorine atom or an iodine atom include the repeating units described in paragraphs [0116] to [0117] of WO 2022/024928. The above descriptions are incorporated herein by reference.
• the content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in resin (P).
• the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in resin (P).
• the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom in the repeating units of the resin (P) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the resin (P).
• the upper limit is not particularly limited, but is, for example, 100 mol% or less based on the total repeating units of the resin (P).
• Examples of the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-decomposable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.
• the resin (P) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferred that the unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure.
• a 5- to 7-membered lactone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure is more preferred.
• Resin (P) preferably has a repeating unit having a lactone group or sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), and the lactone group or sultone group may be directly bonded to the main chain.
• the ring member atom of the lactone group or sultone group may constitute the main chain of Resin (P).
• the lactone structure or sultone structure may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group.
• n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the multiple Rb 2s may be different from each other, or the multiple Rb 2s may be bonded to each other to form a ring.
• An example of a repeating unit having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) is the repeating unit represented by the following formula (AI-2).
• Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
• Preferred examples of the substituent that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
• Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab represents 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 linking group formed by combining these.
• Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
• Ab 1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
• V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3).
• optical isomers exist in the repeating unit having a lactone group or a sultone group
• any optical isomer may be used.
• one optical isomer may be used alone, or multiple optical isomers may be used in combination.
• the optical purity (ee) is preferably 90 or more, and more preferably 95 or more.
• the carbonate group is preferably a cyclic carbonate group.
• the repeating unit having a cyclic carbonate group for example, refer to the description in paragraphs [0127] to [0133] of WO 2022/024928. The above description is incorporated herein by reference.
• the content of unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in resin (P).
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in resin (P).
• the resin (P) may contain, as a repeating unit other than those mentioned above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group").
• a repeating unit having a photoacid generating group is a repeating unit represented by 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.
• R 40 represents a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid in a side chain.
• Specific examples of the repeating unit having a photoacid generating group include the repeating units described in [0094] to [0105] of JP 2014-041327 A, the repeating unit described in [0094] of WO 2018/193954 A, and the repeating unit described in [0138] of WO 2022/024928 A. The above descriptions are incorporated herein by reference.
• Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP 2014-041327 A and the repeating unit described in paragraph [0094] of WO 2018/193954 A.
• the content of the repeating units having a photoacid generating group is preferably 1 mol% or more, and more preferably 5 mol% or more, based on the total repeating units in the resin (P).
• the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total repeating units in the resin (P).
• At least one of the onium salt (A) and onium salt (B) described above can also be used as the photoacid generating portion of a repeating unit having a photoacid generating group.
• the resin (P) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• the repeating units represented by the following formulae (V-1) and (V-2) are preferably repeating units different from the repeating units described above.
• R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group.
• R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms
• n3 represents an integer of 0 to 6.
• n4 represents an integer of 0 to 4.
• X4 is a methylene group, an oxygen atom, or a sulfur atom.
• Examples of the repeating unit represented by formula (V-1) or (V-2) are shown below.
• Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph [0100] of WO 2018/193954.
• the resin (P) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of the generated acid or pattern collapse during development.
• Tg is preferably higher than 90° C., more preferably higher than 100° C., even more preferably higher than 110° C., and particularly preferably higher than 125° C.
• the Tg is preferably 400° C. or lower, more preferably 350° C. or lower.
• the glass transition temperature (Tg) of a polymer such as resin (P) (hereinafter referred to as "Tg of a repeating unit") is calculated by the following method.
• the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated by the Bicerano method.
• the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated.
• the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the Tg (°C) of the polymer.
• the Bicerano method is described in Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of the resin (P) include the following methods (a) to (e). (a) Introduction of a bulky substituent into the main chain; (b) Introduction of a plurality of substituents into the main chain; (c) Introduction of a substituent inducing an interaction between resins (P) in the vicinity of the main chain; (d) Formation of a main chain with a cyclic structure; (e) Linking of a cyclic structure to the main chain.
• the resin (P) preferably has a repeating unit showing a homopolymer Tg of 130° C. or higher.
• the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited, and may be any repeating unit exhibiting a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
• the repeating unit may be one exhibiting a homopolymer Tg of 130° C. or higher.
• One example of a specific means for achieving the above (a) is to introduce a repeating unit represented by formula (A) into resin (P).
• R represents a group containing a polycyclic structure.
• Rx represents a hydrogen atom, a methyl group, or an ethyl group.
• the group containing a polycyclic structure is a group containing a plurality of ring structures, and the plurality of ring structures may be condensed or not condensed.
• Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO 2018/193954.
• One example of a specific means for achieving the above (b) is to introduce a repeating unit represented by formula (B) into resin (P).
• R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two of R b1 to R b4 represent an organic group.
• the type of the other organic groups is not particularly limited.
• at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.
• Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO 2018/193954.
• R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a group containing a hydrogen-bonding hydrogen atom within three atoms from a main chain carbon.
• R c1 to R c4 is a group containing a hydrogen-bonding hydrogen atom within three atoms from a main chain carbon.
• Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO 2018/193954.
• One example of a specific means for achieving the above (d) is to introduce a repeating unit represented by formula (D) into resin (P).
• Cyclic represents a group forming a main chain with a cyclic structure.
• the number of constituent atoms of the ring is not particularly limited.
• Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO 2018/193954.
• One example of a specific means for achieving the above (e) is to introduce a repeating unit represented by formula (E) into resin (P).
• the resin (P) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
• the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (P) include the repeating units described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the preferred content is also as described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the resin (P) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) in which the ⁇ -position is substituted with an electron-withdrawing group, and the carboxyl group is preferred.
• the resin (P) contains a repeating unit having an alkali-soluble group, thereby increasing the resolution in contact hole applications. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP2014-098921A.
• the resin (P) may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposability. This can reduce elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure.
• repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposability include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.
• the resin (P) may have a repeating unit represented by formula (III) which has neither a hydroxyl group nor a cyano group.
• R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
• Ra represents a hydrogen atom, an alkyl group or a -CH 2 -O-Ra 2 group, where Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
• Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs [0087] to [0094] of JP2014-098921A.
• the resin (P) may have repeating units other than the repeating units described above.
• the resin (P) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.
• the resin (P) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developing solutions, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.
• the resin (P) particularly when the composition of the present invention is used as an ArF actinic ray- or radiation-sensitive resin composition, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate-based repeating units.
• any of the repeating units in which all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, or all of the repeating units are a mixture of methacrylate-based repeating units and acrylate-based repeating units can be used, and it is preferable that the acrylate-based repeating units account for 50 mol % or less of the total repeating units.
• the resin (P) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight (Mw) of the resin (P) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, as determined by GPC in terms of polystyrene.
• the dispersity (molecular weight distribution, Mw/Mn) of the resin (P) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern are, and the better the roughness.
• the content of the resin (P) in the composition of the present invention is preferably 30.0 to 99.9 mass%, more preferably 40.0 to 99.9 mass%, and even more preferably 60.0 to 90.0 mass%, based on the total solid content of the composition of the present invention.
• Resin (P) may be used alone or in combination of two or more. When two or more resins are used, the total content is preferably within the above-mentioned preferred content range.
• composition of the present invention may further contain a compound (C) that generates an acid when irradiated with actinic rays or radiation, and that is different from the onium salt (A) and the onium salt (B).
• the compound (C) may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer.
• the compound (C) may be in the form of a low molecular weight compound and the form of a compound incorporated into a part of a polymer in combination.
• the molecular weight of the compound (C) is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferable.
• the compound (C) is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the resin (P) or into a resin different from the resin (P).
• the compound (C) is preferably in the form of a low molecular weight compound.
• Examples of the compound (C) include compounds (onium salts) represented by "M + X - ", and are preferably compounds that generate an organic acid upon exposure to light.
• Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.
• M + represents a cation, and preferably represents an organic cation.
• the description, specific examples and preferred ranges of M + are the same as those for M + in the above formula (a-1).
• X - represents an anion, and preferably represents an organic anion.
• the organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions.
• anions having a significantly low ability to cause a nucleophilic reaction are preferred, and non-nucleophilic anions are more preferred.
• non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
• the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.
• the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
• the aryl 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 listed above may have a substituent.
• the substituent is not particularly limited, but examples include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon
• the aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms.
• Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
• the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
• Substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and 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, which increases the acid strength.
• non-nucleophilic anions include, for example, phosphorus fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• the substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group.
• Examples of the group that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.
• Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethy
• L represents a divalent linking group.
• each L may be the same or different.
• the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these.
• the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 -, or -COO-alkylene group-.
• a group represented by the following formula (AN1-1) is preferable. * a -(CR 2a 2 ) X -Q-(CR 2b 2 ) Y -* b (AN1-1)
• * a represents the bonding position to R 3 in formula (AN1).
• * b represents the bonding position to --C(R 1 )(R 2 )-- in formula (AN1).
• X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3.
• R 2a and R 2b each independently represent a hydrogen atom or a substituent. When a plurality of R 2a and a plurality of R 2b are present, the plurality of R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 which is directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B .
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
• * A represents the bonding position on the R3 side in formula (AN1)
• * B represents the bonding position on the --SO 3 -- side in formula (AN1).
• R3 represents an organic group.
• the organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group.
• the organic group may or may not have a substituent.
• the organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom).
• R3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be a monocyclic or polycyclic ring and may have a substituent.
• the ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1).
• the organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom), for example.
• the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure.
• the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the cyclic hydrocarbon group is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent.
• the cycloalkyl group may be a monocyclic group (such as a cyclohexyl group) or a polycyclic group (such as an adamantyl group), and preferably has 5 to 12 carbon atoms.
• lactone group and sultone group for example, in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-21) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3), a group in which one hydrogen atom is removed from a ring member atom constituting the lactone structure or the sultone structure is preferable.
• the non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.
• an anion represented by the following formula (AN2) is also preferred.
• o represents an integer from 1 to 3.
• p represents an integer from 0 to 10.
• q represents an integer from 0 to 10.
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4.
• the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3 , and further preferably both Xf are fluorine atoms.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R4s and R5s are present, R4s and R5s may be the same or different.
• the alkyl group represented by R4 and R5 preferably has 1 to 4 carbon atoms.
• the alkyl group may have a substituent.
• R4 and R5 are preferably a hydrogen atom.
• L represents a divalent linking group.
• the definition of L is the same as that of L in formula (AN1).
• W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group.
• the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
• the alicyclic group may be a monocyclic or polycyclic.
• the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
• the heterocyclic group may be a single ring or a polycyclic ring. In particular, when the heterocyclic group is a polycyclic ring, the diffusion of the acid can be further suppressed.
• the heterocyclic group may have aromaticity or may not have aromaticity.
• heterocyclic rings having aromaticity examples include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
• heterocyclic rings not having aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group.
• the carbon that constitutes the cyclic organic group (the carbon that contributes to the ring formation) may be a carbonyl carbon.
• the anion represented by formula (AN2) is preferably SO 3 - -CF 2 -CH 2 -OCO-(L) q' -W, SO 3 - -CF 2 -CHF-CH 2 -OCO-(L) q' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - -CF 2 -CH(CF 3 )-OCO-(L) q' -W.
• L, q and W are the same as those in formula (AN2).
• q' represents an integer of 0 to 10.
• an aromatic sulfonate anion represented by the following formula (AN3) is also preferred.
• Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group.
• substituent that may further be had include a fluorine atom and a hydroxyl group.
• n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 or 3, and even more preferably 3.
• D represents a single bond or a divalent linking group.
• divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more of these.
• B represents a hydrocarbon group.
• B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).
• the non-nucleophilic anion is also preferably a disulfonamide anion.
• An example of a disulfonamide anion is an anion represented by N ⁇ (SO 2 —R q ) 2 .
• R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
• Two R q may be bonded to each other to form a ring.
• the group formed by bonding two R q to each other is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group.
• the number of carbon atoms of the alkylene group is preferably 2 to 4.
• compound (C) is at least one selected from the group consisting of compounds (I) to (II).
• Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation:
• Structural moiety X a structural moiety consisting of an anionic moiety A 1 - and a cationic moiety M 1 + , which forms a first acidic moiety represented by HA 1 when irradiated with actinic rays or radiation.
• Structural moiety Y a structural moiety consisting of an anionic moiety A 2 - and a cationic moiety M 2 + , which forms a second acidic moiety represented by HA 2 when irradiated with actinic rays or radiation.
• the compound (I) satisfies the following condition I.
• Compound PI which is obtained by replacing the cationic moiety M 1 + in the structural moiety X and the cationic moiety M 2 + in the structural moiety Y in compound (I) with H + , has an acid dissociation constant a1 derived from the acidic moiety represented by HA 1 , which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H + , and an acid dissociation constant a2 derived from the acidic moiety represented by HA 2 , which is obtained by replacing the cationic moiety M 2 + in the structural moiety Y with H + , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• compound (I) is, for example, a compound that generates an acid having one of the first acidic site derived from the structural moiety X and one of the second acidic site derived from the structural moiety Y
• compound PI corresponds to a "compound having HA 1 and HA 2.
• the acid dissociation constant a1 and the acid dissociation constant a2 of compound PI are calculated as follows: when compound PI is a "compound having A 1 - and HA 2 ", the pKa is the acid dissociation constant a1; and when the "compound having A 1 - and HA 2 " is a "compound having A 1 - and A 2 - ", the pKa is the acid dissociation constant a2.
• compound (I) is a compound that generates an acid having two of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y
• compound PI corresponds to a "compound having two HA 1 's and one HA 2.
• the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " and the acid dissociation constant when the "compound having one A 1 - , one HA 1 and one HA 2 " becomes "a compound having two A 1 - and one HA 2 " correspond to the above-mentioned acid dissociation constant a1.
• the acid dissociation constant when the "compound having two A 1 - and one HA 2 " becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when the compound has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 obtained by replacing the cationic site M 1 + in the structural site X with H + , the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1.
• the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-mentioned method for measuring an acid dissociation constant.
• the compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different from each other.
• the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
• a 1 - and A 2 - , as well as M 1 + and M 2 + may be the same or different, but it is preferable that A 1 - and A 2 - are different.
• the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more.
• the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
• the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less.
• the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
• the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less.
• the lower limit of the acid dissociation constant a1 is preferably -20.0 or more.
• the anionic moiety A 1 - and the anionic moiety A 2 - are structural moieties containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of the structural moieties represented by the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6).
• the anionic moiety A 1 - is preferably one capable of forming an acidic moiety with a small acid dissociation constant, and among these, any one of formulas (AA-1) to (AA-3) is more preferable, and any one of formulas (AA-1) and (AA-3) is even more preferable.
• the anionic moiety A 2 - is preferably one capable of forming an acidic moiety having a larger acid dissociation constant than the anionic moiety A 1 - , more preferably one represented by formulas (BB-1) to (BB-6), and even more preferably one represented by formulas (BB-1) and (BB-4).
• * represents a bonding position.
• R A represents a monovalent organic group.
• the monovalent organic group represented by R A is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
• the cationic moiety M 1 + and the cationic moiety M 2 + are structural moieties containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge. Examples of the organic cation include the organic cation represented by M + described above.
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation.
• Structural moiety Z a non-ionic moiety capable of neutralizing an acid
• compound PII which is obtained by replacing the cationic moiety M 1 + in the structural moiety X in compound (II) with H +
• the preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA 1 which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H +
• compound PII corresponds to a "compound having two HA 1s ".
• the acid dissociation constant when compound PII becomes a "compound having one A 1 - and one HA 1 " and the acid dissociation constant when the "compound having one A 1 - and one HA 1 " becomes a "compound having two A 1 -s " correspond to the acid dissociation constant a1.
• the acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant.
• the compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural moieties X may be the same or different, and the two or more A 1 ⁇ and the two or more M 1 + may be the same or different.
• the nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton, or a functional group having an electron.
• Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation.
• the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:
• Examples of partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.
• compound (C) include the compounds described in paragraphs [0320] to [0321] of WO 2022/172715. The above descriptions are incorporated herein by reference.
• the content of the compound (C) is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, based on the total solid content of the composition of the present invention.
• the content of the compound (C) is preferably 60.0 mass% or less, more preferably 50.0 mass% or less, and even more preferably 40.0 mass% or less, based on the total solid content of the composition of the present invention.
• the compound (C) may be used alone or in combination of two or more. When two or more compounds are used, the total content is preferably within the above-mentioned preferred content range.
• composition of the present invention may further contain an acid diffusion controller (also referred to as "compound (D)").
• the compound (D) is a compound different from the onium salt (A) and the onium salt (B).
• the acid diffusion controller functions as a quencher that traps the acid generated from the photoacid generator or the like upon exposure to light and suppresses the reaction of the resin, the polarity of which increases due to the action of excess acid generated in the unexposed areas.
• the type of compound (D) is not particularly limited, and examples thereof include a basic compound (DA), a low molecular weight compound (DB) having a nitrogen atom and a group that is eliminated by the action of an acid, and a compound (DC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation.
• Examples of the compound (DC) include an onium salt compound (DD) which is a weak acid relative to a photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.
• Specific examples of the basic compound (DA) include those described in paragraphs [0132] to [0136] of WO 2020/066824.
• Specific examples of the basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs [0137] to [0155] of WO 2020/066824 and those described in paragraph [0164] of WO 2020/066824.
• Specific examples of the low molecular weight compound (DB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs [0156] to [0163] of WO 2020/066824.
• Specific examples of the onium salt compound (DD) that is a weak acid relative to the photoacid generator include those described in paragraphs [0305] to [0314] of WO 2020/158337.
• the content of the compound (D) is preferably 0.01 to 30.0 mass%, more preferably 0.05 to 20.0 mass%, and still more preferably 0.1 to 15.0 mass%, based on the total solid content of the composition of the present invention.
• the compound (D) may be used alone or in combination of two or more. When two or more compounds are used, the total content is preferably within the above-mentioned preferred content range.
• the composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (E)") different from the resin (P).
• the hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances.
• the effects of adding the hydrophobic resin (E) include control of the static and dynamic contact angles of water on the resist film surface, and suppression of outgassing.
• the hydrophobic resin (E) preferably has one or more of fluorine atoms, silicon atoms, and CH3 partial structures contained in the side chain portion of the resin, more preferably has two or more.
• the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Examples of the hydrophobic resin (E) include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
• the content of the hydrophobic resin (E) is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 15.0 mass%, based on the total solid content of the composition of the present invention.
• the hydrophobic resin (E) may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the composition of the present invention may contain a surfactant.
• a surfactant When the composition contains a surfactant, a pattern having better adhesion and fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Examples of fluorine-based and/or silicone-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of WO 2018/193954.
• Surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably from 0.0001 to 2.0 mass%, more preferably from 0.0005 to 1.0 mass%, and still more preferably from 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention.
• the surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above-mentioned preferred content range.
• the composition of the present invention preferably contains a solvent.
• the solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate.
• the solvent may further contain components other than the components (M1) and (M2).
• the combination of the above-mentioned solvent and the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern.
• the above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, so that it is possible to suppress unevenness in the thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (M1) and (M2) are described in paragraphs [0218] to [0226] of WO 2020/004306, the contents of which are incorporated herein by reference.
• the content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %. This further improves the applicability of the composition of the present invention.
• composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).
• a dissolution inhibiting compound for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group.
• dissolution-blocking compound is a compound with a molecular weight of 3000 or less that decomposes under the action of acid and reduces its solubility in an organic developer.
• the content of fluorine atoms in the total solid content of the composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.
• the content of fluorine atoms represents the mass ratio of fluorine atoms in the total solid content to the total atoms in the total solid content in the composition of the present invention.
• the content (mass%) of fluorine atoms can be calculated by the following formula (1a).
• [C] is the molar ratio of carbon atoms in the total solid content
• [H] is the molar ratio of hydrogen atoms in the total solid content
• [F] is the molar ratio of fluorine atoms in the total solid content
• [N] is the molar ratio of nitrogen atoms in the total solid content
• [O] is the molar ratio of oxygen atoms in the total solid content
• [S] is the molar ratio of sulfur atoms in the total solid content.
• the molar ratio of carbon atoms in the total solid content [C] can be calculated from the number of carbon atoms, molecular weight, and content of each component in the solid content.
• the molar ratio of carbon atoms in the onium salt (A) can be calculated by the following formula (1b).
• Aw represents the amount of the onium salt (A) in the total solid content (unit: "g” or "mass %)
• a M represents the molecular weight of the onium salt (A)
• a C represents the number of carbon atoms in the onium salt (A).
• the molar ratio of carbon atoms in the total solid content [C] can be calculated by similarly calculating the molar ratio of carbon atoms for other components and summing them. By replacing the carbon atom in the above formula with another atom, the molar ratio of other atoms can be calculated in the same manner.
• the total solid content in the composition of the present invention contains an atom other than the above, it can be calculated in the same manner using the atomic weight of that atom and the molar ratio in the total solid content.
• it can also be calculated by an analytical method such as elemental analysis for a resist film obtained by evaporating the solvent component of the composition of the present invention.
• composition of the present invention is also suitable for use as a photosensitive composition for EUV exposure.
• the present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention.
• the actinic ray- or radiation-sensitive film of the present invention is preferably a resist film.
• the procedure for the pattern formation method using the composition of the present invention is not particularly limited, but it is preferable that the method comprises the following steps. Step 1: Forming a resist film on a substrate using the composition of the present invention; Step 2: Exposing the resist film to light; Step 3: Developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.
• Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.
• An example of a method for forming a resist film on a substrate using the composition of the present invention is a method in which the composition of the present invention is applied onto a substrate.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the composition of the present invention can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by a suitable application method such as a spinner or coater.
• the application method is preferably spin coating using a spinner.
• the rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm (rotations per minute).
• the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed under the resist film.
• the drying method may be, for example, a method of drying by heating. Heating can be performed by a means provided in a normal exposure machine and/or a developing machine, and may also be performed using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
• the thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm, since it allows for the formation of fine patterns with higher accuracy.
• the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
• a top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film.
• the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs [0072] to [0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that the top coat may contain include the basic compounds that may be contained in the composition of the present invention.
• the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is a step of exposing the resist film to light.
• the exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask.
• the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably having a wavelength of 250 nm or less, more preferably having a wavelength of 220 nm or less, and particularly preferably having a wavelength of 1 to 200 nm.
• actinic ray or radiation examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called post-exposure bake.
• Step 3 is a step of developing the exposed resist film with a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).
• Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the substrate surface by surface tension and leaving it to stand for a certain period of time to develop (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
• a step of stopping the development while replacing the solvent with another solvent may be carried out.
• the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds.
• the temperature of the developer is preferably from 0 to 50°C, and more preferably from 15 to 35°C.
• the alkaline developer is preferably an aqueous alkaline solution containing an alkali.
• aqueous alkaline solution containing quaternary ammonium salts such as tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines.
• the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH).
• TMAH tetramethylammonium hydroxide
• Appropriate amounts of alcohols, surfactants, etc. may be added to the alkaline developer.
• the alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is usually preferably 10.0 to 15.0.
• 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, ether solvents, and hydrocarbon solvents.
• the above-mentioned solvents may be mixed in combination, or may be mixed with a solvent other than the above or with water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.
• the above pattern formation method preferably includes, after step 3, a step of washing with a rinsing liquid.
• the rinse liquid used in the rinse step following the step of developing with an alkaline developer is, for example, pure water, to which an appropriate amount of a surfactant may be added.
• a suitable amount of a surfactant may be added to the rinse solution.
• the rinse liquid used in the rinse step following the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. It is preferable to use 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.
• the method of the rinsing step is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method).
• the pattern forming method may also include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between the patterns and inside the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern.
• the heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the formed pattern may be used as a mask to perform an etching process on the substrate. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form a pattern on the substrate.
• the method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, a method for forming a pattern on the substrate is preferred by performing dry etching on the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask.
• the dry etching is preferably oxygen plasma etching.
• the composition of the present invention and various materials used in the pattern formation method preferably do not contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
• Methods for reducing metal and other impurities contained in various materials include, for example, selecting raw materials with low metal content as the raw materials that make up the various materials, filtering the raw materials that make up the various materials, and performing distillation under conditions that minimize contamination as much as possible, such as lining the inside of the equipment with Teflon (registered trademark).
• impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used.
• adsorbent known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• inorganic adsorbents such as silica gel and zeolite
• organic adsorbents such as activated carbon.
• the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferable.
• An organic processing liquid such as a rinse liquid may contain a conductive compound to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge.
• the conductive compound is not particularly limited, but an example thereof is methanol.
• the amount added is not particularly limited, but from the viewpoint of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. There is no particular lower limit, and 0.01% by mass or more is preferable.
• the chemical liquid piping may be made of, for example, stainless steel (SUS), or various piping coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the filter and O-ring may be made of antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method.
• a preferred embodiment of the electronic device of the present invention is one in which it is mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
• a mixed solution of 6.9 g (0.060 mol) of maleic acid monoamide and 64 g of methylene chloride was cooled to 0° C. or less under a nitrogen atmosphere and stirred while dropping 12.4 g (0.122 mol) of triethylamine, and then 43.8 g (purity 68.5%, 0.131 mol) of intermediate 1-1, and stirred at room temperature overnight.
• 69 g of water was added to the reaction solution to extract the organic layer.
• the organic layer was further washed three times with 69 g of water and then concentrated under reduced pressure.
• a mixed solution of 13.4 g (0.054 mol) of intermediate 1-2 and 214 ml of tetrahydrofuran (THF) was cooled to ⁇ 20° C. or lower under a nitrogen atmosphere and stirred, while a mixed solution of 7.3 g (0.096 mol) of thioacetic acid, 16.2 g (0.125 mol) of diisopropylethylamine and 53 ml of THF was dropped into the above solution and stirred at room temperature overnight.
• the reaction solution was cooled to 0° C., and 178 g of methylene chloride and 668 g of water were added to extract the organic layer.
• PAG-B1 to PAG-B21 were used as the onium salt (B).
• PAG-B1 to PAG-B21 can function as an acid diffusion controller whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation.
• Z-2 and Z-3 were used as acid diffusion controllers that are not onium salts (B).
• Z-2 and Z-3 are also listed in the onium salt (B) column in Table 2 below.
• reaction solution A To a mixed solution of 20.0 g (0.087 mol) of intermediate B2-1, 200 ml of tetrahydrofuran (THF), and 100 ml of N,N-dimethylformamide (DMF), 10.2 g (0.091 mol) of tert-butoxy potassium (tBuOK) was slowly added at 0° C. under a nitrogen atmosphere, and the mixture was stirred at 0° C. for 10 minutes. This is reaction solution A. To a mixed solution of 37.7 g (0.096 mol) of intermediate B17-2 and 50 ml of tetrahydrofuran (THF), the reaction solution A was slowly added dropwise at 0° C.
• C-1 to C-2 were used as the basic compounds.
• C-1 to C-2 can function as an acid diffusion control agent.
• ⁇ Hydrophobic resin> As the hydrophobic resin, D-1 to D-11 were used.
• the structural formula and content (mol %) of each repeating unit contained in D-1 to D-11, and the weight average molecular weight (Mw) and dispersity (Mw/Mn) of D-1 to D-11 are shown below.
• the content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units contained in each resin.
• the weight average molecular weight (Mw) and dispersity (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (quantities calculated as polystyrene).
• the content of repeating units was measured by 13 C-NMR.
• E-1 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
• each component When two or more types of each component were used, the type and content of each component was expressed by separating them with a "/" symbol.
• "PAG-13/PAG-30” indicates that two types of onium salt (A), PAG-13 and PAG-30, were used, and "5.1/5.1” indicates that the content of PAG-13 was 5.1% by mass, and the content of PAG-30 was 5.1% by mass.
• the content (mass %) of fluorine atoms relative to the total solid content of each resist composition is shown in the column “F content” in Tables 1 to 3. The content of fluorine atoms was calculated by the method described above.
• ⁇ Pattern formation method (1) ArF exposure, alkali development (positive), Examples AP-1 to AP-60, Comparative Examples RAP-1 to RAP4>
• the resist compositions shown in Tables 4 and 5 were applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 100° C. for 60 seconds to obtain a resist film with a thickness of 90 nm.
• 1 inch is 0.0254 m.
• the wafer on which the resist film was formed was subjected to pattern exposure through an exposure mask using an ArF excimer laser scanner (manufactured by ASML, PAS5500/1500, wavelength 193 nm, NA 0.50). After that, it was baked at a temperature of 115° C. for 60 seconds, developed with a 2.38 mass % tetramethylammonium hydroxide aqueous solution (TMAHaq) for 30 seconds, rinsed with pure water, and then spin-dried. As a result, a resist pattern of a 1:1 line and space pattern with a line width of 50 nm was obtained.
• TMAHaq tetramethylammonium hydroxide aqueous solution
• ⁇ LWR is greater than ⁇ 0.5 nm and equal to or less than ⁇ 0.2 nm, or equal to or greater than 0.2 nm and less than 0.5 nm.
• ⁇ Pattern formation method (2) ArF exposure, organic solvent development (negative), Examples AN-1 to AN-48, Comparative Examples RAN-1 to RAN-4>
• the resist compositions shown in Tables 6 and 7 were applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 100° C. for 60 seconds to obtain a resist film with a thickness of 90 nm.
• 1 inch is 0.0254 m.
• the wafer on which the resist film was formed was subjected to pattern exposure through an exposure mask using an ArF excimer laser scanner (manufactured by ASML, PAS5500/1500, wavelength 193 nm, NA 0.50). After that, it was baked at a temperature of 115° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried. As a result, a resist pattern of a 1:1 line and space pattern with a line width of 50 nm was obtained.
• the “mass %” column indicates the content (mass %) of each component relative to the total solid content in the resist composition. Tables 1 to 3 also show the amount (mass ratio) of the solvent used. In Tables 1 to 3, the content (mass %) of fluorine atoms relative to the total solid content of each resist composition is shown in the column "F content.”
• ⁇ Pattern formation method (3) EUV exposure, alkaline development (positive), Examples EP-1 to EP-50, Comparative Examples REP-1 to REP4>
• An underlayer film-forming composition AL412 manufactured by Brewer Science was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm.
• a resist composition shown in Tables 8 and 9 was applied onto the underlayer film and baked at 100° C. for 60 seconds to form a resist film having a thickness of 30 nm.
• the silicon wafer having the resist film thus obtained was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech).
• EUV exposure apparatus Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech.
• a reticle a mask with a line size of 25 nm and a line:space ratio of 1:1 was used.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.
• ⁇ LWR is greater than ⁇ 0.5 nm and equal to or less than ⁇ 0.2 nm, or equal to or greater than 0.2 nm and less than 0.5 nm.
• ⁇ Pattern formation method (4) EUV exposure, organic solvent development (negative), Examples EN-1 to EN-44, Comparative Examples REN-1 to REN4>
• An underlayer film-forming composition AL412 manufactured by Brewer Science was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm.
• a resist composition shown in Tables 10 and 11 was applied onto the underlayer film and baked at 100° C. for 60 seconds to form a resist film having a thickness of 30 nm.
• the silicon wafer having the resist film thus obtained was subjected to pattern irradiation using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36).
• EUV exposure apparatus Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36.
• a reticle a mask with a line size of 25 nm and a line:space ratio of 1:1 was used.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.
• the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in initial LWR performance and LWR performance after aging. Furthermore, the present invention can provide a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

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