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
• • 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
• • 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
  • G03F7/039—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
  • G03F7/004—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
• • 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
  • G03F7/20—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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers

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, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in ultra-microlithography processes applicable 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 processes applicable 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 a resist composition that contains a resin whose solubility in an organic solvent-containing developer changes under the action of acid, a photoacid generator, and a hydrophobic resin that has fluorine atoms.
• Patent Document 2 describes a resist composition that contains a first polymer that is acid-sensitive, a second polymer that has a specific structure and a surface energy lower than that of the first polymer, a photoacid generator, and a solvent.
• LWR performance refers to the ability to reduce the LWR of a pattern.
• the actinic ray-sensitive or radiation-sensitive resin composition comprises a resin (A) whose polarity increases under the action of an acid, an onium salt (B) represented by the following formula (1), and a resin (C) which satisfies all of the following (i) to (iii): (i) It does not contain fluorine atoms. (ii) The SP value [SP C ] of the resin (C) is smaller than the SP value [SP A ] of the resin (A) and is 17.00 or less. (iii) The content is 0.01 to 10% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.
• R 11 represents a hydrogen atom, a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• R 12 represents a substituent having no hydrogen atom or a fluorine atom.
• n represents an integer of 1 to 4. When n is an integer of 2 to 4, a plurality of R 11 and R 12 may be the same or different, and at least one R 11 represents a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• L represents a single bond or a divalent linking group.
• X1 represents a hydrogen atom or an organic group.
• M + represents an organic cation. At least two of R 11 , R 12 , L and X 1 may be bonded to each other to form a ring.
• Y1 and Y3 each independently represent -O- or -NR3- , and R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p represents an integer of 0 to 2
• q and r each independently represent 0 or 1.
• * represents a bonding position.
• R 1 X represents a cyano group or a nitro group. * represents the bonding position.
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B), and at least one of R 1a and R 2a represents a cyano group, a nitro group, or a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B).
• R 1b and R 2b each independently represent a substituent not having a hydrogen atom or a fluorine atom.
• L, X1 and M + respectively have the same meanings as L, X1 and M + in the above formula (1). 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.
• R 1a represents a hydrogen atom, a cyano group, a nitro group, or a substituent represented by the following formula (2A)
• R 2a represents a cyano group, a nitro group, a substituent represented by the following formula (2A), or a substituent represented by the following formula (2B).
• 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 and Y each represent a cyano group, a nitro group, or a substituent represented by formula (2A). * represents a bonding position.
• R 1Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
• R 2Z and R 3Z each independently represent a hydrogen atom or an alkyl group.
• a 1 represents a divalent linking group.
• R 2A represents an organic group containing two or more CH 3 partial structures. At least two of R 1Z to R 3Z and A 1 may be bonded to each other to form a ring.
• X represents an alicyclic group.
• A2 represents a divalent linking group.
• R2B represents an organic group containing two or more CH3 partial structures.
• R31 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
• A3 represents a divalent linking group.
• R2C represents an organic group containing two or more CH3 partial structures.
• R 1a represents a cyano group, a nitro group, or a substituent represented by the above formula (2A).
• R5 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p1 represents 0 or 1.
• R6 represents a cyano group or a group represented by -SO2 - R7 .
• R7 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R1b , R2b , X1 , and M + respectively have the same meanings as R1b , R2b , X1 , and M + in formula (2) above.
• 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 items [1] to [10]; exposing the resist film to light; 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 LWR performance and capable of reducing residues after development. Furthermore, the present invention can provide a resist film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.
• 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.).
• substituents for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.
• R 1b and R 2b in formula (N1) do not have a fluorine atom, such as in the case of a "substituent having no fluorine atom"
• the above-mentioned substituent T does not include 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
• solids refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents.
• any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid even if it is in liquid form.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") comprises a resin (A) whose polarity increases under the action of an acid, and a compound represented by the following formula (1):
• the actinic ray-sensitive or radiation-sensitive resin composition contains an onium salt (B) and a resin (C) that satisfies all of the following (i) to (iii): (i) It does not contain fluorine atoms.
• the SP value [SP C ] of the resin (C) is smaller than the SP value [SP A ] of the resin (A) and is 17.00 or less.
• the content is 0.01 to 10% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.
• R 11 represents a hydrogen atom, a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• R 12 represents a substituent having no hydrogen atom or a fluorine atom.
• n represents an integer of 1 to 4. When n is an integer of 2 to 4, a plurality of R 11 and R 12 may be the same or different, and at least one R 11 represents a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• L represents a single bond or a divalent linking group.
• X1 represents a hydrogen atom or an organic group.
• M + represents an organic cation. At least two of R 11 , R 12 , L and X 1 may be bonded to each other to form a ring.
• Y1 and Y3 each independently represent -O- or -NR3- , and R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p represents an integer of 0 to 2
• q and r each independently represent 0 or 1.
• * represents a bonding position.
• R 1 X represents a cyano group or a nitro group. * represents the bonding position.
• the mechanism by which the composition of the present invention has excellent LWR performance and reduces residue after development is not clear, but the present inventors presume as follows, although the present invention is not limited in any way by the presumed mechanism below.
• the onium salt (B) represented by formula (1) contained in the composition of the present invention has at least one cyano group, nitro group, substituent represented by formula (1A), or substituent represented by formula (1B) as R 11 in formula (1).
• These groups having electron-withdrawing properties are hydrophilic and have high compatibility with the resin (A) whose polarity increases under the action of an acid, so that the onium salt (B) is uniformly dispersed, and it is considered that the onium salt (B) exhibits excellent LWR performance by suppressing the variation in the acid generated from the onium salt (B).
• the onium salt represented by formula (1) is uniformly dispersed, it is considered that ionic aggregates that cause residues are unlikely to be generated, and the residues after development can be reduced.
• a cyano group, a nitro group, a substituent represented by formula (1A), or a substituent represented by formula (1B), which have electron-withdrawing properties are bonded to the carbon atom to which -SO 3 - is bonded and the carbon atom bonded to the carbon atom, and the acid strength of the acid generated from the onium salt can be ensured.
• the hydrophobic resin is unevenly distributed on the surface opposite the substrate, and the highly hydrophilic photoacid generator is somewhat unevenly distributed on the substrate side.
• the resin (C) contained in the composition of the present invention is more hydrophobic than the resin (A), and is presumed to be unevenly distributed on the surface opposite the substrate in the thickness direction of the resist film, but since it does not contain fluorine atoms, it is not as hydrophobic as the fluorine-containing hydrophobic resins commonly used in resist compositions, and is considered to be unevenly distributed on the surface opposite the substrate.
• the dispersibility of the onium salt (B) in the thickness direction is improved, and further the LWR performance is improved.
• 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 a chemically amplified resist composition or a non-chemically amplified resist composition.
• the composition of the present invention is typically 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 composition of the present invention contains a resin (A) (also referred to as "resin (A)”) whose polarity increases under the action of an acid.
• Resin (A) 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.
• resin (A) has an acid-decomposable group, typically, in the pattern forming method of this specification, 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 a polar group is protected by a group (leaving group) that is eliminated under the action of an acid. That is, the resin (A) has a repeating unit that has a group that is eliminated 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.
• L1 is preferably -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom-.
• the arylene group is preferably a phenylene group.
• the alkylene group may be linear or branched. The number of carbon atoms in the alkylene 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 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 (A) 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 (A), 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 (A).
• 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 resin (A).
• 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 resin (A).
• Resin (A) 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 (A) 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 (A) may have at least one repeating unit selected from the group consisting of Group A.
• resin (A) preferably has at least one repeating unit selected from the group consisting of Group A.
• the resin (A) may contain at least one of a fluorine atom and an iodine atom.
• the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or the resin (A) may contain two types of repeating units, a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
• Resin (A) 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 (A) has a repeating unit having an aromatic group.
• Resin (A) may have at least one repeating unit selected from the group consisting of Group B.
• resin (A) preferably has at least one repeating unit selected from the group consisting of Group B.
• the resin (A) contains neither a fluorine atom nor a silicon atom.
• the resin (A) does not have an aromatic group.
• the resin (A) 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 (A) 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 join together 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 (A).
• 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 (A).
• the resin (A) 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 (A).
• 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 (A).
• 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 (A) 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 (A).
• the upper limit is not particularly limited, but is, for example, 100 mol% or less based on the total repeating units of the resin (A).
• 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 (A) 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 (A) 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 one of the following formulae (LC1-1) to (LC1-21), or a sultone structure represented by any one of the following formulae (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 (A).
• 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 (A).
• 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 (A).
• the resin (A) may contain, as a repeating unit other than those described 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 resin (A).
• 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 resin (A).
• the above-mentioned onium salt (N1) can also be used as the photoacid generating portion of a repeating unit having a photoacid generating group.
• the resin (A) 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.
• Resin (A) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of 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.
• Tg is preferably 400° C. or lower, more preferably 350° C. or lower.
• 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 (A) 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 (A) 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.
• resin (A) 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 (A).
• 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.
• 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.
• 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.
• each Re independently represents a hydrogen atom or an organic group.
• the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, each of which may have a substituent.
• Cyclic refers to a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO 2018/193954.
• the resin (A) 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 (A) 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 (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves the adhesion to the substrate and the affinity for the developer.
• the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
• the repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP2014-098921A.
• the resin (A) 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) substituted at the ⁇ -position with an electron-withdrawing group, with the carboxyl group being preferred.
• the resin (A) contains a repeating unit having an alkali-soluble group, which increases 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 JP 2014-098921 A.
• Resin (A) 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 (A) 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 (A) may have other repeating units in addition to the repeating units described above.
• resin (A) 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.
• resin (A) 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 (A) 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.
• resin (A) may contain fluorine atoms, but it is preferable that the content of fluorine atoms relative to the total solid content of the composition of the present invention is adjusted to fall within the range described below, and it is also preferable that resin (A) does not contain fluorine atoms.
• the SP value [SP C ] of resin (C) is smaller than the SP value [SP A ] of resin (A) and is 17.00 or less.
• [SP A ] is preferably more than 17.00, more preferably 17.50 or more, and even more preferably 18.00 or more. There is no particular upper limit, but it is preferably, for example, 21.00 or less.
• the method for measuring the SP value of the resin will be explained in the section on Resin (C).
• the resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight (Mw) of the resin (A) 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 (A) 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 side walls of the resist pattern are, and the better the roughness.
• the content of the resin (A) 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 actinic ray-sensitive or radiation-sensitive resin composition.
• Resin (A) 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.
• the onium salt (B) represented by the following formula (1) contained in the composition of the present invention will be described below.
• the onium salt (B) is preferably a compound that generates an acid when irradiated with actinic rays or radiation (a photoacid generator).
• R 11 represents a hydrogen atom, a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• R 12 represents a substituent having no hydrogen atom or a fluorine atom.
• n represents an integer of 1 to 4. When n is an integer of 2 to 4, a plurality of R 11 and R 12 may be the same or different, and at least one R 11 represents a cyano group, a nitro group, a substituent represented by the following formula (1A), or a substituent represented by the following formula (1B).
• L represents a single bond or a divalent linking group.
• X1 represents a hydrogen atom or an organic group.
• M + represents an organic cation. At least two of R 11 , R 12 , L and X 1 may be bonded to each other to form a ring.
• Y1 and Y3 each independently represent -O- or -NR3- , and R3 represents a hydrogen atom or an alkyl group.
• R4 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p represents an integer of 0 to 2
• q and r each independently represent 0 or 1.
• * represents a bonding position.
• R 1 X represents a cyano group or a nitro group. * represents the bonding position.
• R 11 represents a hydrogen atom, a cyano group, a nitro group, a substituent represented by formula (1A) above, or a substituent represented by formula (1B) above.
• 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--.
• p represents 0 or 1.
• q represents 0.
• r represents 1.
• Y 2 represents —C( ⁇ O)— or —SO 2 —, and preferably represents —C( ⁇ O)—.
• R 4 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R4 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.
• the substituent that the alkyl group represented by R 4 may have is not particularly limited, and examples thereof include a cycloalkyl group and an aryl group.
• the cycloalkyl group represented by R 4 may be a monocyclic or polycyclic group, 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, and a 1-ethyladamantyl group.
• the cycloalkyl group represented by R 4 may have a substituent.
• the substituent that the cycloalkyl group represented by R 4 may have is not particularly limited, and examples thereof include an alkyl group and an aryl group.
• the explanation and preferred range 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 the explanation and preferred range of the alkyl group represented by R 4 above and the aryl group represented by R 4 below, respectively.
• one or more methylene groups in the cycloalkyl group represented by R 4 may be substituted with an oxygen atom, a carbonyl group, or an ester 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.
• the substituent that the aryl group represented by R 4 may have is not particularly limited, and examples thereof include an alkyl group and a cycloalkyl group.
• the description and preferred range of the alkyl group and the cycloalkyl group as the substituent that the aryl group represented by R 4 may have are the same as the description and preferred range of the alkyl group and the cycloalkyl group represented by R 4 above.
• the alkyl group represented by R3 and the alkyl group, cycloalkyl group, and aryl group represented by R4 preferably do not have a fluorine atom. That is, the substituent represented by formula (1A) preferably does not have a fluorine atom.
• R 12 in formula (1) represents a substituent not containing a hydrogen atom or a fluorine atom.
• the substituent not having a fluorine atom represented by R 12 is not particularly limited except that it does not have a fluorine atom, and examples thereof include an organic group and a nitro group.
• the organic group is not particularly limited, but is preferably, for example, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (1A) or a substituent represented by formula (1B).
• the alkyl group 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 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 cycloalkyl group may be monocyclic or polycyclic, 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 include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, and a 1-ethyladamantyl group.
• the aryl group 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 alkyl group, cycloalkyl group and aryl group may have a substituent other than a fluorine atom.
• R 12 is a substituent represented by formula (1A) and a substituent represented by formula (1B)
• the explanation and preferred range of the substituent represented by formula (1A) and the substituent represented by formula (1B) are the same as the explanation and preferred range of the substituent represented by formula (1A) and the substituent represented by formula (1B) in R 11 , respectively.
• n represents an integer from 1 to 4, preferably 1 or 2, and more preferably 2.
• 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-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these.
• the alkylene group, cycloalkylene group and alkenylene group may have a substituent, but preferably does not have a fluorine atom.
• X1 represents a hydrogen atom or an organic group.
• the organic group is not particularly limited, but is preferably, for example, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a substituent represented by formula (1A) or a substituent represented by formula (1B).
• the alkyl group 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.
• alkyl group examples 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 cycloalkyl group may be monocyclic or polycyclic, 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.
• cycloalkyl group examples include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, and a 1-ethyladamantyl group.
• the aryl group 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 alkyl group, cycloalkyl group and aryl group may have a substituent, and it is preferable that the substituent does not contain a fluorine atom.
• X1 is a substituent represented by formula (1A) and a substituent represented by formula (1B)
• the explanation and preferred range of the substituent represented by formula (1A) and the substituent represented by formula (1B) are the same as the explanation and preferred range of the substituent represented by formula (1A) and the substituent represented by formula (1B) in R11 , respectively.
• M + represents an organic cation.
• M + is preferably a sulfonium or iodonium cation.
• the cation represented by M + is not particularly limited. The valence of the cation may be monovalent or divalent or higher.
• a cation represented by formula (ZaI) hereinafter also referred to as "cation (ZaI)" or a cation represented by formula (ZaII) (hereinafter also referred to as “cation (ZaII)" is preferred.
• 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., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., iodine), 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-mentioned substituents are combined in any desired manner to form an
• 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, 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, 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, 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 (e.g., an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, 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). These groups may have a substituent.
• a halogen atom e.g., an iodine atom, etc.
• R 13 represents a hydrogen atom, a halogen atom (e.g., an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a
• R 14 represents a hydroxyl group, a halogen atom (e.g., an iodine atom, etc.), an alkyl group, a halogenated alkyl group, 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). These groups may have a substituent. When there are a plurality of R 14 , each independently represents the above group such as a hydroxyl group.
• a halogen atom e.g., an iodine atom, etc.
• 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 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, 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.
• M + does not contain a fluorine atom.
• the onium salt represented by the above formula (1) is preferably represented by the following formula (2).
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B), and at least one of R 1a and R 2a represents a cyano group, a nitro group, a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B).
• R 1b and R 2b each independently represent a substituent not having a hydrogen atom or a fluorine atom.
• L, X1 and M + respectively have the same meanings as L, X1 and M + in the above formula (1). 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.
• R 1a and R 2a each independently represent a hydrogen atom, a cyano group, a nitro group, a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B), and at least one of R 1a and R 2a represents a cyano group, a nitro group, a substituent represented by the above formula (1A), or a substituent represented by the above formula (1B).
• R 1a and R 2a are substituents represented by formula (1A)
• the description and preferred range of the substituent represented by formula (1A) are the same as the description and preferred range of the substituent represented by formula (1A) in R 11.
• R 1a and R 2a are substituents represented by formula (1B)
• the description of the substituent represented by formula (1B) is the same as the description of the substituent represented by formula (1B) in R 11 .
• R 1a represents a hydrogen atom, a cyano group, a nitro group, or a substituent represented by the following formula (2A)
• R 2a preferably represents a cyano group, a nitro group, a substituent represented by the following formula (2A), or a substituent represented by the following formula (2B).
• 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 and Y each represent a cyano group, a nitro group, or a substituent represented by formula (2A). * represents a bonding position.
• Y 1 to Y 3 , R 4 , q and r in formula (2A) are the same as the definitions, explanations and preferred ranges of Y 1 to Y 3 , R 4 , q and r in formula (1A), respectively.
• formula (2B) the definitions, explanations and preferred ranges of Y 1 to Y 3 , R 4 , q and r in the substituent represented by formula (2A) as R Y are the same as the definitions, explanations and preferred ranges of Y 1 to Y 3 , R 4 , q and r in formula (1A), respectively.
• R Y in formula (2B) 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 further preferably represents a cyano group, -COOR 4 , -OCOOR 4 , or -SO 2 R 4.
• the definition, explanation, and preferred range of R 4 are as described above.
• R 1a in formula (2) preferably represents a cyano group, a nitro group, or a substituent represented by the above formula (2A), more preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -OCOR 4 , or -SO 2 R 4 , further preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , or -SO 2 R 4 , and particularly preferably represents a cyano group, -COOR 4 , -OCOOR 4 , or -SO 2 R 4.
• the definition, explanation, and preferred range of R 4 are as described above.
• R 2a preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -OCOR 4 , -SO 2 R 4 , or a substituent represented by the following formula (2C), more preferably represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , -SO 2 R 4 , or a substituent represented by the following formula (2C), and even more preferably represents a cyano group, -COOR 4 , -OCOOR 4 , -SO 2 R 4 , or a substituent represented by the following formula (2C).
• the definition, explanation and preferred range of R 4 are as described above.
• R Y2 represents a cyano group, a nitro group, -COOR 4 , -OCOOR 4 , or -SO 2 R 4.
• R 4 has the same meaning as R 4 in formula (1A). * represents a bonding position. The description and preferred range of R 4 are as described above.
• R 1b and R 2b in formula (2) are the same as the definition, explanation and preferred range of R 11 in formula (1) above.
• the onium salt represented by formula (2) preferably does not contain a fluorine atom.
• R 1a , R 1b , R 2a , and R 2b in formula (2) fall under the following (i)
• R 2b represents a nitro group, a substituent represented by formula (2A) or a substituent represented by formula (2B):
• X 1 represents an organic group:
• R 1a , R 1b and R 2a in formula (2) correspond to the following (iii)
• X 1 preferably represents an organic group.
• R 1a nor R 1b is a substituent represented by formula (2A), and only one of R 1a and R 1b is a cyano group, R 2a is a cyano group, and R 2b is not a cyano group.
• R 1a and R 1b are a substituent represented by formula (2A)
• Y 2 in formula (2A) is —C( ⁇ O)—
• R 1b is a hydrogen atom
• R 2a is a substituent represented by (2A).
• cases not corresponding to any of the above (i) to (iii) are also included in preferred embodiments of the onium salt (B).
• the onium salt represented by formula (2) is preferably represented by the following formula (4):
• R5 represents an alkyl group, a cycloalkyl group, or an aryl group.
• p1 represents 0 or 1.
• R6 represents a cyano group or a group represented by -SO2 - R7 .
• R7 represents an alkyl group, a cycloalkyl group, or an aryl group.
• R1b , R2b , X1 , and M + respectively have the same meanings as R1b , R2b , X1 , and M + in formula (2) above.
• R 7 in -SO 2 -R 7 represented by R 6 represents an alkyl group, a cycloalkyl group, or an aryl group.
• the description and preferred ranges of the alkyl group, cycloalkyl group, and aryl group represented by R 7 are the same as those of the alkyl group, cycloalkyl group, and aryl group represented by R 4 above.
• R 1b , R 2b , X 1 and M + in formula (4) are the same as those of R 1b , R 2b , X 1 and M + in formula (2), respectively.
• the onium salt represented by formula (4) preferably does not contain a fluorine atom.
• onium salt (B) examples include PAG1 to PAG31 used in the examples described below, but the present invention is not limited to these.
• 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 the resin (A) or into a resin different from the resin (A).
• 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 1 mass % to 50 mass %, more preferably from 5 mass % to 45 mass %, and even more preferably from 10 mass % to 40 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.
• the method for producing the onium salt (B) is not particularly limited, and the onium salt (B) can be synthesized by a known method.
• the compound represented by the above formula (2) 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 can be synthesized with reference to the non-patent document "Journal of Medicinal Chemistry, No. 54 (2011), pp. 3606-3623.”
• composition of the present invention may further contain a compound (B2) that generates an acid when irradiated with actinic rays or radiation and is different from the onium salt (B) to the extent that the effect of the present invention is not impaired.
• compound (B2) include the compounds described in paragraphs [0320] to [0321] of WO 2022/172715. The above descriptions are incorporated herein by reference.
• the composition of the present invention contains a resin (C) that satisfies all of the following (i) to (iii): (i) It does not contain fluorine atoms. (ii) The SP value [SP C ] of resin (C) is smaller than the SP value [SP A ] of resin (A) and is 17.00 or less. (iii) The content is 0.01 to 10% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.
• Resin (C) is a hydrophobic resin that does not contain fluorine atoms. Hydrophobic resins that contain fluorine atoms are generally used in resist compositions, but by using a hydrophobic resin that does not contain fluorine atoms, the dispersibility of the onium salt (B) in the thickness direction of the resist film is improved, improving LWR performance.
• Resin (C) has an SP value [SP C ] calculated by the following calculation method, which is smaller than the SP value [SP A ] of resin (A) and is 17.00 or less.
• the SP value of a resin is calculated by the following calculation method. ⁇ Calculation method for SP value of resin> 1. Calculate the SP value of each repeating unit constituting the resin using "HSPiP 5th Edition 5.1.08". 2. The content ratio of each repeating unit in the resin on a mass basis is multiplied by the SP value of each repeating unit obtained in 1 above, and the sum of these is taken as the SP value of the resin. In this manner, the SP value [SP C ] of resin (C) and the SP value [SP A ] of resin (A) are calculated.
• the SP value of each repeating unit that constitutes the resin is a value calculated by the above software using the structure of the monomer that corresponds to the raw material monomer of each repeating unit.
• the SP value [SP C ] of resin (C) is smaller than the SP value [SP A ] of resin (A).
• the difference between [SP C ] and [SP A ] is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more.
• the difference is preferably 5.0 or less, and more preferably 4.0 or less.
• the SP value [SP C ] of the resin (C) is 17.00 or less, and from the viewpoint of uneven distribution of the resin (C) on the film surface layer, it is preferably 16.70 or less, and more preferably 16.50 or less. Also, from the viewpoint of improving the dispersibility of the onium salt (B) in the film thickness direction of the resist film, it is preferably 14.00 or more, and more preferably 15.00 or more.
• the resin (C) has at least one of a "silicon atom” and a " CH3 partial structure contained in a side chain portion of the resin".
• the silicon atom in the resin (C) may be contained in the main chain or in a side chain of the resin.
• the resin preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom. Examples of repeating units having a silicon atom include those exemplified in US 2012/0251948 A1 [0519].
• resin (C) when resin (C) contains silicon atoms, resin (C) preferably has a repeating unit containing a silicon atom.
• the repeating unit containing a silicon atom preferably accounts for 10 to 100 mol %, and more preferably 20 to 100 mol %, of all repeating units contained in resin (C).
• the resin (C) contains a CH3 partial structure in the side chain portion.
• the CH3 partial structure possessed by the side chain portion in the resin (C) includes the CH3 partial structure possessed by an ethyl group, a propyl group, etc.
• a methyl group directly bonded to the main chain of the resin (C) for example, an ⁇ -methyl group of a repeating unit having a methacrylic acid structure
• resin (C) contains a repeating unit derived from a monomer having a polymerizable moiety with a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M), and R 11 to R 14 are "CH 3 itself," that CH 3 is not included in the CH 3 partial structure possessed by the side chain portion in the present invention.
• a CH3 partial structure that exists via some atom from the C-C main chain corresponds to the CH3 partial structure in the present invention.
• R11 is an ethyl group ( CH2CH3 )
• it is considered to have "one" CH3 partial structure in the present invention.
• R 11 to R 14 each independently represent a side chain moiety.
• R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
• the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group, and these groups may further have a substituent. At least two of R 11 to R 14 may be bonded to each other to form a ring.
• Resin (C) is preferably a resin having a repeating unit having a CH3 partial structure in the side chain portion, and preferably contains at least one of the repeating units represented by the following formula (3A) and the repeating units represented by the following formula (3B).
• R 1Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
• R 2Z and R 3Z each independently represent a hydrogen atom or an alkyl group.
• a 1 represents a divalent linking group.
• R 2A represents an organic group containing two or more CH 3 partial structures. At least two of R 1Z to R 3Z and A 1 may be bonded to each other to form a ring.
• X represents an alicyclic group.
• A2 represents a divalent linking group.
• R2B represents an organic group containing two or more CH3 partial structures.
• R 1Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
• the alkyl group represented by R 1Z preferably has 1 to 4 carbon atoms, and examples of such groups include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group, with a methyl group being preferred.
• the cycloalkyl group represented by R1Z may be monocyclic or polycyclic, 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 R1 include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, and a 1-ethyladamantyl group.
• R 1Z is preferably a hydrogen atom or a methyl group.
• R 2Z and R 3Z each independently represent a hydrogen atom or an alkyl group.
• alkyl group represented by R 2Z and R 3Z include the alkyl groups represented by R 1Z , and preferred examples are also the same.
• R2Z and R3Z are preferably hydrogen atoms.
• Examples of the divalent linking group represented by A1 in formula (3A) include -CO-, -O-, -S-, -SO-, -SO2- , hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, arylene groups, etc.), and linking groups in which multiple of these are linked together.
• hydrocarbon groups e.g., alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, arylene groups, etc.
• the alkylene group may be a straight-chain or branched-chain alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 3 carbon atoms is preferred.
• the cycloalkylene group includes monocyclic or polycyclic cycloalkylene groups having 3 to 15 carbon atoms.
• the alkenylene group includes linear or branched alkenylene groups having 2 to 10 carbon atoms.
• the cycloalkenylene group includes monocyclic or polycyclic cycloalkenylene groups having 3 to 15 carbon atoms.
• the arylene group includes an arylene group having 6 to 14 carbon atoms, and a phenylene group is preferable.
• the above-mentioned hydrocarbon group may further have a substituent.
• one or more methylene groups forming the above-mentioned alkylene group, cycloalkylene group, alkenylene group, and cycloalkenylene group may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group.
• A1 is preferably —CO—O— or a phenylene group.
• R 2A represents an organic group containing two or more CH 3 partial structures.
• the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group.
• the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the aryl group, and the aralkyl group preferably further have an alkyl group as a substituent.
• the alkyl group may be a branched alkyl group, preferably an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 3 to 10 carbon atoms.
• Examples of the alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 2-ethylhexyl group, a 2,4-dimethyl-3-pentyl group, and a 2,2-dimethyl-3-butyl group.
• the cycloalkyl group may be monocyclic or polycyclic, 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 include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, and an adamantyl group.
• the above alkenyl group is preferably a linear or branched alkenyl group, more preferably an alkenyl group having 2 to 20 carbon atoms, and even more preferably an alkenyl group having 2 to 10 carbon atoms.
• the cycloalkenyl group may be monocyclic or polycyclic, and is preferably a cycloalkenyl group having 3 to 20 carbon atoms, more preferably a cycloalkenyl group having 4 to 15 carbon atoms, and even more preferably a cycloalkenyl group having 5 to 10 carbon atoms.
• the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
• the aryl group in the aralkyl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
• the alkyl group in the aralkyl group includes linear or branched alkyl groups, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
• the alkyl group as a substituent of the above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group can be a linear or branched alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
• the number of alkyl groups as a substituent may be one or two or more.
• R 2A is preferably an alkyl group or an alkyl-substituted cycloalkyl group having two or more CH 3 moieties.
• the organic group having two or more CH3 partial structures as R2A preferably has 2 to 10 CH3 partial structures, more preferably 2 to 8 CH3 partial structures.
• X represents an alicyclic group.
• Examples of the alicyclic ring in the alicyclic group represented by X include monocyclic or polycyclic cycloalkane rings and cycloalkene rings having 3 to 20 carbon atoms, and monocyclic or polycyclic cycloalkane rings having 5 to 10 carbon atoms are preferred.
• Examples of the divalent linking group represented by A2 in formula (3B) include the divalent linking groups represented by A1 in formula (3A), and preferred examples are also the same.
• Examples of the organic group having two or more CH3 partial structures represented by R 2B in formula (3B) include organic groups having two or more CH3 partial structures represented by R 2A in formula (3A), and preferred examples are the same.
• the organic group having two or more CH3 partial structures as R2B preferably has 2 to 10 CH3 partial structures, more preferably 2 to 8 CH3 partial structures.
• the repeating units represented by the above formula (3A) and the repeating units represented by the above formula (3B) are preferably repeating units that are not acid decomposable.
• the repeating unit represented by the above formula (3A) is preferably a repeating unit represented by the following formula (3C) which is not acid decomposable. That is, the resin (C) is preferably represented by the following formula (3C) and contains a repeating unit that is not acid decomposable.
• R31 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a cyano group.
• A3 represents a divalent linking group.
• R2C represents an organic group containing two or more CH3 partial structures.
• R 31 , A 3 and R 2C in formula (3C) are respectively defined as R 1Z , A 1 and R 2A in formula (3A), and preferred examples are also the same.
• this does not include the case where any of R 31 and -A 3 -R 2C has a group that decomposes under the action of an acid to generate a polar group.
• the polar group has a structure protected by an acid-decomposable group described in resin (A), that is, a group that leaves under the action of an acid (leaving group).
• the content of at least one repeating unit (x) selected from the repeating units represented by formula (3A) and the repeating units represented by formula (3B) is preferably 70 mol % or more, and more preferably 80 mol % or more, based on the total repeating units of resin (C).
• the content is usually 100 mol % or less, based on the total repeating units of resin (C).
• the resin (C), whether (i) containing a silicon atom or (ii) containing a CH3 partial structure in the side chain portion, may have at least one group selected from the group consisting of (x) to (z) below.
• Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid 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.
• Preferred acid groups include a sulfonimide group and a bis(alkylcarbonyl)methylene group.
• the repeating unit having an acid group (x) examples include a repeating unit in which an acid group is directly bonded to the main chain of a resin, such as a repeating unit of acrylic acid or methacrylic acid, or a repeating unit in which an acid group is bonded to the main chain of a resin via a linking group, and further, a polymerization initiator or a chain transfer agent having an acid group can be used during polymerization to introduce the acid group into the end of the polymer chain, either of which is preferable.
• the repeating unit having an acid group (x) may have a silicon atom.
• the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol %, more preferably from 3 to 35 mol %, and even more preferably from 5 to 20 mol %, based on the total repeating units in the resin (C).
• the acid anhydride group or the acid imide group (y), a group having a lactone structure is particularly preferred.
• the repeating units containing these groups are, for example, repeating units of acrylic acid ester and methacrylic acid ester, in which the group is directly bonded to the main chain of the resin.
• the repeating units may be repeating units in which the group is bonded to the main chain of the resin via a linking group.
• the repeating units may be introduced to the end of the resin by using a polymerization initiator or chain transfer agent having the group during polymerization.
• repeating unit having a group having a lactone structure examples include the same repeating units having a lactone structure as those described above in the section on Resin (A) (excluding those having a fluorine atom as a substituent).
• the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group (y) may contain a CH3 partial structure in the side chain portion.
• the content of repeating units having a group with a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and even more preferably 5 to 95 mol %, based on the total repeating units in resin (C).
• the repeating unit having a group (z) decomposed by the action of an acid may be the same as the repeating unit having an acid decomposable group listed in the resin (A).
• the repeating unit having a group (z) decomposed by the action of an acid may have a silicon atom, and may contain a CH3 partial structure in the side chain portion.
• the content of the repeating unit having a group (z) decomposed by the action of an acid in the resin (C) is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and even more preferably 20 to 60 mol% based on the total repeating units in the resin (C).
• the resin (C) may or may not have a group (z) which is decomposed by the action of an acid, but it is preferable that it does not have such a group. In other words, it is preferable that the resin (C) does not have acid decomposability.
• Resin (C) may further have repeating units other than the repeating units described above.
• the weight average molecular weight of resin (C) in terms of standard polystyrene is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.
• the content of resin (C) in the composition is 0.01 to 10 mass % relative to the total solid content in the composition of the present invention, more preferably 0.05 to 8 mass %, and even more preferably 0.1 to 7 mass %.
• the resin (C) may be used alone or in combination with two or more kinds. When two or more kinds are used, it is preferable that the total content is within the range of the preferred content described above.
• the mass ratio ((C)/(B)) of the resin (C) to the content of the onium salt (B) contained in the composition of the present invention is preferably 0.05 to 3.0 from the viewpoint of improving LWR performance.
• the mass ratio is more preferably 0.1 to 3.0, and even more preferably 0.15 to 2.8.
• Resin (C) preferably has a residual monomer or oligomer content of 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
• the molecular weight distribution (Mw/Mn, also called the degree of dispersion) is preferably in the range of 1 to 5, more preferably 1 to 3.
• Resin (C) can be any commercially available product, or can be synthesized according to conventional methods (e.g., radical polymerization).
• compositions of the present invention may also include an acid diffusion control agent.
• 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 inhibits the reaction of the acid-decomposable resin in the unexposed areas caused by excess acid generated.
• the type of acid diffusion controller 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.
• DB low molecular weight compound having a nitrogen atom and a group that is eliminated by the action of an acid
• DD onium salt compound that is a weak acid relative to the photoacid generator
• the content of the acid diffusion controller (the total content when a plurality of types are present) is preferably 0.1 to 30.0 mass %, more preferably 0.1 to 15.0 mass %, and even more preferably 1.0 to 15.0 mass %, based on the total solid content of the composition of the present invention.
• the acid diffusion controller 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.
• a fluorosurfactant may be used as the surfactant, but it is preferable that the content of fluorine atoms relative to the total solid content of the composition of the present invention is adjusted to fall within the range described below.
• 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 solvent further contains components other than components (M1) and (M2)
• the content of the components other than components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.
• 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 composition of the present invention is 1.00 mass% or less relative to the total solid content of the composition.
• the content of fluorine atoms in the composition of the total solid content is more preferably 0.50 mass% or less, and even more preferably 0.10 mass% or less.
• the composition does not contain fluorine atoms.
• 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.
• the content of fluorine atoms (mass%) is calculated by the following formula: 100 ⁇ 19 ⁇ [F]/(12 ⁇ [C]+1 ⁇ [H]+19 ⁇ [F]+14 ⁇ [N]+16 ⁇ [O]+32 ⁇ [S])
• [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 oxygen 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 onium salt B can be calculated by the following formula Bw / BM x Bc It can be calculated by the formula.
• Bw represents the amount (g or mass%) of onium salt B in the total solid content
• BM represents the molecular weight of onium salt B
• BC represents the number of carbon atoms in onium salt B.
• 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.
• the molar ratio of other atoms can be calculated in the same manner.
• the total solid content in the composition 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.
• 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).
• Resin (A) [Various components of actinic ray- or radiation-sensitive resin composition]
• the resins (A) (resins A-1 to A-20) shown in Tables 3 and 4 are shown below. Resins A-1 to A-20 were synthesized in accordance with the synthesis method of Resin A-1 (Synthesis Example 1) described later. Table 1 shows the composition ratio (molar ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw/Mn) of each repeating unit shown later.
• the weight average molecular weight (Mw) and dispersity (Mw/Mn) of Resins A-1 to A-20 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent).
• the composition ratio (mol % ratio) of the resins was measured by 13 C-NMR (nuclear magnetic resonance).
• Table 1 also shows the SP values [SP A ] of Resins A-1 to A-20.
• the SP value of a resin ([SP A ]) is calculated by the following calculation method. ⁇ Calculation method of SP value of resin> 1. Calculate the SP value of each repeating unit constituting the resin using "HSPiP 5th Edition 5.1.08". 2. The content ratio of each repeating unit in the resin on a mass basis is multiplied by the SP value of each repeating unit obtained in 1 above, and the sum of these is taken as the SP value of the resin. In this manner, the SP value [SP A ] of the resin (A) is calculated.
• the SP value of each repeating unit that constitutes the resin is a value calculated by the above software using the structure of the monomer that corresponds to the raw material monomer of each repeating unit.
• PAG1 to PAG31 were used as the onium salt (B).
• the structures of PAG1 to PAG31 shown in Tables 3 and 4 are shown below.
• PAG1 to PAG31 are photoacid generators.
• PAGR2 was used as a photoacid generator other than the onium salt (B).
• PAGR2 is also listed in the onium salt (B) column in Table 4 below.
• the weight average molecular weight (Mw) and dispersity (Mw/Mn) of hydrophobic resins C-1 to C-12 and CR-1 to CR-2 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent).
• the composition ratio (mol % ratio) of the resins was measured by 13C -NMR (nuclear magnetic resonance).
• Table 2 also shows the SP values [SPc] of hydrophobic resins C-1 to C-12 and CR-1 to CR-2.
• the SP value ([SPc]) of the resin is calculated by the following calculation method. ⁇ Calculation method of SP value of resin> 1. Calculate the SP value of each repeating unit constituting the resin using "HSPiP 5th Edition 5.1.08". 2. The content ratio of each repeating unit in the resin on a mass basis is multiplied by the SP value of each repeating unit obtained in 1 above, and the sum of these is taken as the SP value of the resin. In this manner, the SP value [SP C ] of the resin (C) is calculated.
• the SP value of each repeating unit that constitutes the resin is a value calculated by the above software using the structure of the monomer that corresponds to the raw material monomer of each repeating unit.
• E-1 As the surfactant, E-1 was used. E-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
• Tables 3 and 4 also show the SP value [SP A ] of resin (A) and the SP value [SPc] of resin (C).
• the SP values of resins A-6 and A-8 were multiplied by their respective content ratios on a mass basis, and the sum was taken as [SP A ].
• the SP values of resins C-2 and C-5 were multiplied by their respective content ratios on a mass basis, and the sum was taken as [SPc].
• the content of fluorine atoms relative to the total solid content of the resist composition is shown in Tables 3 and 4 as "F atom content” (mass%).
• ⁇ Pattern formation method (1) ArF exposure, alkaline development (positive)>
• the resist compositions shown in Tables 3 and 4 immediately after production 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).
• TMAHaq tetramethylammonium hydroxide aqueous solution
• ⁇ Pattern formation method (2) ArF exposure, organic solvent development (negative)>
• the resist compositions shown in Tables 3 and 4 immediately after production 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).
• ⁇ Pattern formation method (3) EUV exposure, alkaline development (positive)>
• An underlayer film-forming composition AL412 manufactured by Brewer Science
• An underlayer film-forming composition AL412 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 Table 7 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).
• a mask with a line size of 25 nm and a line:space ratio of 1:1 was used as a reticle.
• 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 performance A 25 nm (1:1) line and space pattern resolved with the optimum exposure dose for resolving a line pattern with an average line width of 25 nm was observed from above using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), and the line width was observed at 50 locations to determine the standard deviation ( ⁇ ). The measurement variation in line width was evaluated at 3 ⁇ , and the value of 3 ⁇ was taken as the LWR (nm). The smaller the LWR value, the better the LWR performance.
• the LWR is preferably 4.2 nm or less, more preferably 4.0 nm or less, and particularly preferably 3.7 nm or less.
• ⁇ Pattern formation method (4) EUV exposure, organic solvent development (negative)>
• An underlayer film-forming composition AL412 manufactured by Brewer Science
• An underlayer film-forming composition AL412 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 Table 8 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).
• a mask with a line size of 25 nm and a line:space ratio of 1:1 was used as a reticle.
• 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 LWR performance and capable of reducing residues after development. Furthermore, the present invention can provide a resist film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

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