Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/325—Non-aqueous compositions

Definitions

• the present invention relates to a method for producing a solution, a method for producing a resist composition, a pattern formation method, and a method for producing an electronic device. More specifically, the present invention relates to a method for producing a solution, a method for producing a resist composition, a pattern formation method, and a method for producing an electronic device that can be used to prepare a resist composition that can be suitably used in ultra-microlithography processes and other photofabrication processes that can be applied to the manufacturing process of VLSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, and the manufacturing process of high-density information recording media.
• VLSI Large Scale Integration
• immersion liquid a liquid having a high refractive index
• EB electron beams
• EUV extreme ultraviolet rays
• resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.
• Patent Document 1 describes a method for producing a polymer for semiconductor lithography, which includes a step of using a solvent contained in a container whose inner wall surface is made of electrolytically polished stainless steel.
• Patent Document 2 describes a method for producing a polymer for semiconductor lithography, which includes a step of delivering a liquid material through a liquid delivery pipe formed by connecting a plurality of piping members, and in which a connecting member made of a perfluoroelastomer or the like is disposed at a portion where the piping members are connected to each other in the liquid delivery pipe.
• a solid substance used as a component of a resist composition may be handled as a powder, but particularly those that are difficult to crystallize or have deliquescent properties may be dissolved in a solvent and handled as a solution.
• a solution by dissolving a solid substance to be used as a component of a resist composition in a solvent or when preparing a resist composition by dissolving a solid substance to be used as a component of a resist composition in a solvent, stainless steel containers or glass containers have been used.
• a resist composition prepared using a solution prepared by a conventional method and a resist composition prepared by a conventional method are prone to development defects when used in pattern formation.
• the present invention aims to provide a method for producing a solution that can be used to prepare a resist composition that can suppress the occurrence of development defects when used in pattern formation, a method for producing the resist composition, a method for forming a pattern using the resist composition produced by the method for producing the resist composition, and a method for producing an electronic device.
• [1] A method for producing a solution comprising dissolving one or more solid substances in a solvent, the method comprising the steps of: The one or more solid substances are used as components of a resist composition, A method for producing a solution, comprising the steps of placing the one or more solid substances and the solvent in a container containing a resin on at least a portion of an inner wall surface, and dissolving a part or all of the solid content consisting of the one or more solid substances. [2] The method for producing a solution according to [1], wherein the solvent contains at least one selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2):
• X 1 and X 2 each independently represent a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group.
• the two Rc's may be the same or different.
• C 1 and C 2 each independently represent sp 3 carbon or sp 2 carbon.
• L 1 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 1 to R 4 each independently represent a hydrogen atom or an organic group. At least two of X 1 , X 2 , R 1 to R 4 and L 1 may be bonded to each other to form a ring.
• n1 represents 0 or 1. However, when C 1 is an sp 2 carbon, n1 is 0, and when C 1 is an sp 3 carbon, n1 is 1.
• n2 represents 0 or 1.
• X 3 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• C 3 represents sp 3 carbon or sp 2 carbon.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• L 2 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 5 and R 6 each independently represent a hydrogen atom or an organic group.
• R 7 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 8.
• R 8 represents an organic group.
• n3 represents 0 or 1. However, when C3 is an sp2 carbon, n3 is 0, and when C3 is an sp3 carbon, n3 is 1.
• the method for producing a solution according to [3], wherein the compound having a salt structure includes at least one selected from the group consisting of a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3):
• M 1 + represents an organic cation.
• a 1 - represents a residue of an acid.
• X 4 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• C 4 and C 5 each independently represent sp 3 carbon or sp 2 carbon.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• L 3 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 9 to R 12 each independently represent a hydrogen atom or an organic group. At least two of X 4 , R 9 to R 12 and L 3 may be bonded to each other to form a ring.
• n4 represents 0 or 1, provided that when C 4 is an sp 2 carbon, n4 is 0, and when C 4 is an sp 3 carbon, n4 is 1.
• n5 represents 0 or 1, provided that when C 5 is an sp 2 carbon, n5 is 0, and when C 5 is an sp 3 carbon, n5 is 1.
• M 2 + represents an organic cation.
• a 2 - represents an acid residue.
• L 4 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• C 6 represents an sp 3 carbon or an sp 2 carbon.
• R 13 and R 14 each independently represent a hydrogen atom or an organic group.
• R 15 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 16.
• R 16 represents an organic group. At least two of R 13 to R 16 and L 4 may be bonded to each other to form a ring.
• n6 represents 0 or 1. However, when C 6 is an sp 2 carbon, n6 is 0, and when C 6 is an sp 3 carbon, n6 is 1.
• M 3 + represents an organic cation.
• a 3 - represents a residue of an acid.
• X 5 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. Two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. Two Rc's may be the same or different.
• C 7 represents sp 3 carbon or sp 2 carbon.
• R 17 and R 18 each independently represent a hydrogen atom or an organic group. At least two of X 5 , R 17 , and R 18 may be bonded to each other to form a ring.
• n7 represents 0 or 1. However, if C7 is an sp2 carbon, then n7 is 0, and if C7 is an sp3 carbon, then n7 is 1.
• a method for producing a resist composition comprising the steps of placing one or more solid substances to be used as components of the resist composition and a solvent in a container containing a resin on at least a portion of the inner wall surface, and dissolving a part or all of the solid content consisting of the one or more solid substances.
• a method for producing a resist composition comprising: preparing a resist composition using a solution produced by the method for producing a solution according to any one of [1] to [6].
• a pattern formation method comprising: a resist film formation step of forming a resist film using a resist composition produced by the method for producing a resist composition according to [7] or [8]; an exposure step of exposing the resist film to light; and a development step of developing the exposed resist film using a developer.
• a method for producing an electronic device comprising the pattern forming method according to [9].
• the present invention provides a method for producing a solution that can be used to prepare a resist composition that can suppress the occurrence of development defects when used in pattern formation, a method for producing the resist composition, a method for forming a pattern using the resist composition produced by the method for producing the resist composition, and a method for producing an electronic device.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam).
• light means actinic rays or radiation.
• exposure includes not only exposure to the emission 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, and an isobutyryl group.
• halogen atoms such as a fluorine atom,
• substituent T examples include acyl groups such as acryloyl, methacryloyl, and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; and the like.
• acyl groups such as acryloyl, methacryloyl, and methoxalyl groups
• sulfanyl groups alkyls
• 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.).
• 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, it 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 the calculation method is 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
• the solid content of a resist composition refers to the components contained in the resist composition and contained in the resist film formed using the resist composition. Solvents are not “solid content.” Furthermore, if a component is contained in the resist composition and contained in the resist film formed using the resist composition, it is considered to be a “solid content” even if it is in liquid form. “Total solid content” refers to all solid content.
• the method for producing the solution of the present invention comprises the steps of: 1.
• a method for producing a solution comprising dissolving one or more solid substances in a solvent, the method comprising the steps of:
• the one or more solid substances are used as components of a resist composition,
• the method for producing a solution includes a step of placing the one or more solid substances and the solvent in a container containing a resin on at least a portion of the inner wall surface, and dissolving a part or all of the solid content consisting of the one or more solid substances.
• the one or more solid substances used in the method for producing the solution of the present invention are also referred to as “solid substances (U)".
• the solvent used in the solution producing method of the present invention is also referred to as “solvent (S)”.
• the solution produced by the solution producing method of the present invention is also referred to as "solution (Z)”.
• the present invention is particularly effective when producing a solution by dissolving a compound having a salt structure (salt compound) in a solvent or when producing a solution using a polar solvent as the solvent, and it is believed that this is related to the fact that the above-mentioned scaly marks are easily dissolved in a solution in the presence of a salt compound or a polar solvent.
• the solid substance (U) which is typically a dry powder (dry powder) or a powder moistened with a solvent (wet powder)
• a solution (Z) in which the solid substance (U) is dissolved in the solvent (S).
• a solid substance (U) and a solvent (S) are placed into a container containing a resin on at least a portion of the inner wall surface, and a part or all of the solid content of the solid substance (U) is dissolved in the solvent (S) in the container to obtain a solution (Z).
• the solution-forming step when the solid substance (U) is composed of only one type of solid substance, a part or all of the one type of solid substance may be dissolved in the solvent (S). In addition, in the solution-forming step, when the solid substance (U) contains two or more types of solid substances, a part or all of at least one of the solid substances may be dissolved in the solvent (S).
• the solvent is water
• the solubility of the solid substance in water can be confirmed, for example, by a method based on the flask shake method described in OECD Test Guideline Test No. 105: Water Solubility.
• the solvent is an organic solvent
• the solubility of the solid substance in the organic solvent can be confirmed by the above-mentioned method using an organic solvent instead of water.
• the solubility of the solid substance in the mixed solvent of water and an organic solvent can be confirmed by the above-mentioned method using a mixed solvent of water and an organic solvent instead of water.
• the temperature at which the solid substance is dissolved in the solvent is not particularly limited, but is preferably 0 to 90°C, more preferably 10 to 70°C, and particularly preferably 15 to 50°C.
• the solution may be stirred.
• a stirring blade stir blade
• a magnetic stirrer a rotary mixer, etc.
• the surfaces of the stirring blade and the stirrer tip that come into contact with the solution are covered with a resin.
• the resin include the same resins used in the container described below.
• the stirring blade include a paddle blade, an inclined paddle blade, a disk turbine blade, a propeller blade, a three-blade swept blade, an anchor blade, a helical ribbon blade, a screw blade, a Max Blend blade, a Super Mix blade, and a Full Zone blade.
• a container in which at least a part of the inner wall surface contains a resin.
• a container containing a resin on at least a portion of its inner wall surface refers to a container in which at least a portion of the inner wall surface is made of a resin.
• the container may be entirely made of resin (a resin container), or may be made of a material other than resin, at least a part of the inner wall surface of which is coated with resin. Examples of materials other than resin include glass and metal.
• the container having at least a part of the inner wall surface coated with a resin is preferably a glass or stainless steel container having at least a part of the inner wall surface coated with a resin.
• the resin used for the container is not particularly limited, but examples include polyethylene, polypropylene, polyester, polystyrene, polyvinyl chloride, polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene copolymer, perfluoroalkoxy fluororesin, perfluoroethylene propene copolymer, polyvinylidene fluoride, etc.
• perfluoroalkoxy fluororesin include copolymers of tetrafluoroethylene and perfluoroalkoxyethylene (perfluoroalkoxyalkane, PFA).
• the size and shape of the container are not particularly limited.
• the volume of the container is not particularly limited and may be, for example, 1 L or more. Furthermore, the volume of the container may be, for example, 200 L or less, 100 L or less, or 30 L or less.
• a portable container may be used as the container.
• a portable container is a container that is not fixed to a facility, device, building, etc. and can be sealed. By using a portable container, it is possible to transport and store the solution without the need to open the container or transfer the liquid after dissolution, thereby preventing impurities from being mixed into the solution. Examples of shapes of portable containers include drums, pails, square cans, flat cans, kerosene cans, 18L cans, gallon bottles, and screw-cap bottles.
• the volume of the portable container is not particularly limited, but is preferably 1 L or more.
• the volume of the portable container is preferably 200 L or less, more preferably 100 L or less, and particularly preferably 30 L or less.
• the portable container may be a resin container, or a glass or metal container whose inner wall is partially coated with resin, but is preferably a resin container.
• the solvent (solvent (S)) used in the present invention is not particularly limited.
• the solvent (S) may be water, an organic solvent, or a mixture of water and an organic solvent.
• examples of the organic solvent include ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, sulfoxide-based solvents, sulfone-based solvents, nitrile-based solvents, and carbonate-based solvents.
• Examples of the solvent (S) include water, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 2-ethylhexanol, propylene glycol, ethylene glycol, amyl alcohol, 1,3-butylene glycol, glycerin, diacetone alcohol, diethylene glycol, cyclohexanol, dipropylene glycol, methyl isobutyl carbinol, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, and cyclopentanone.
• the solvent (S) preferably contains a polar solvent.
• the solvent (S) preferably contains at least one selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).
• the solvent (S) preferably contains 20% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and even more preferably 70% by mass or more and 100% by mass or less, of at least one selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2), based on the total mass of the solvent (S).
• X 1 and X 2 each independently represent a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group.
• the two Rc's may be the same or different.
• C 1 and C 2 each independently represent sp 3 carbon or sp 2 carbon.
• L 1 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 1 to R 4 each independently represent a hydrogen atom or an organic group. At least two of X 1 , X 2 , R 1 to R 4 and L 1 may be bonded to each other to form a ring.
• n1 represents 0 or 1. However, when C 1 is an sp 2 carbon, n1 is 0, and when C 1 is an sp 3 carbon, n1 is 1.
• n2 represents 0 or 1.
• X 3 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• C 3 represents sp 3 carbon or sp 2 carbon.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• L 2 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 5 and R 6 each independently represent a hydrogen atom or an organic group.
• R 7 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 8.
• R 8 represents an organic group.
• n3 represents 0 or 1. However, when C3 is an sp2 carbon, n3 is 0, and when C3 is an sp3 carbon, n3 is 1.
• X1 and X2 each independently represent a hydroxy group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• the number of carbon atoms of the alkyl group contained in the alkoxy group represented by X1 and X2 is not particularly limited, and may be, for example, 1 to 20, 1 to 10, or 1 to 6.
• the alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group.
• the alkyl group may have a substituent.
• alkyl group contained in the thioalkoxy group represented by X1 and X2 and the alkyl group in the case where the acyloxy group represented by X1 and X2 is an alkylcarbonyloxy group.
• the aryl group may be either a monocyclic or polycyclic (e.g., 2 to 6 rings, etc.).
• the number of carbon atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group.
• the aryl group may have a substituent.
• 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, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group.
• the cycloalkyl group may have a substituent.
• One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, and a group having a heteroatom such as an ester bond, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group.
• Rx represents a hydrogen atom or an organic group.
• the organic group represented by Rx is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and a group formed by combining these groups.
• the alkyl group represented by Rx 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 Rx 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 Rx may have a substituent.
• the cycloalkyl group represented by Rx 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 Rx include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group.
• the cycloalkyl group represented by Rx may have a substituent.
• One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group represented by Rx may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, or a group having a heteroatom such as an ester bond, or a vinylidene group.
• the cycloalkyl group represented by Rx may have one or more ethylene groups constituting the cycloalkane ring replaced with a vinylene group.
• the aryl group represented by Rx 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 represented by Rx is preferably a phenyl group, a naphthyl group, or an anthryl group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
• the aryl group represented by Rx may have a substituent.
• Ra represents a hydrogen atom or an organic group.
• the description, specific examples, and preferred ranges of Ra are the same as those for Rx described above.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• the explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group represented by Rb are the same as those for Rx described above. The same applies to the alkyl group contained in the alkoxy group and thioalkoxy group represented by Rb.
• Examples of the aralkyl group represented by Rb include a group in which the aryl group represented by Rb is bonded to the alkyl group represented by Rb.
• Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
• Rc represents a hydrogen atom or an organic group.
• the description, specific examples, and preferred ranges for Rc are the same as those for Rx described above.
• L 1 represents a single bond, a double bond, an aromatic carbon-carbon bond or a linking group having 2 or less carbon atoms.
• An example of an embodiment in which L1 is an aromatic carbon-carbon bond is an embodiment in which C1 and C2 in formula (1-1) are sp2 carbons, n1 and n2 are 0, and R1 and R3 are bonded to form an aromatic ring.
• the linking group having 2 or less carbon atoms may be any of a linking group having 0 carbon atoms, a linking group having 1 carbon atom, and a linking group having 2 carbon atoms.
• Examples of the linking group having 0 carbon atoms represented by L 1 include -O-, -NH-, -S-, -SO- and -SO 2 -.
• Examples of the linking group having one carbon atom represented by L 1 include -CO-, -CH 2 -, and -CH 2 O-.
• the linking group having 2 or less carbon atoms represented by L 1 may have a substituent.
• the carbon number of the substituent is not included in the carbon number of L 1.
• the carbon number is 6 or less.
• Specific examples of L 1 also include those in which one or more hydrogen atoms in the specific examples of L 1 are substituted with a substituent.
• Rd represents a hydrogen atom or a substituent, preferably a hydrogen atom or a substituent having 6 or less carbon atoms, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.
• the multiple Rds may be the same or different.
• alkyl group, cycloalkyl group and aryl group represented by Rd are the same as those of Rx described above.
• R 1 to R 4 each independently represent a hydrogen atom or an organic group.
• the organic group represented by R 1 to R 4 is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group.
• the explanation, specific examples, and preferred ranges of R 1 to R 4 are the same as those for Rx described above.
• At least two of X 1 , X 2 , R 1 to R 4 and L 1 in formula (1-1) may be bonded to each other to form a ring.
• the ring formed by bonding at least two of X 1 , X 2 , R 1 to R 4 and L 1 to each other may be an aromatic ring (e.g., a benzene ring, a naphthalene ring, a pyridine ring, etc.), a non-aromatic ring (e.g., a cyclohexane ring, a tetrahydropyran ring, a pyran ring, etc.), or a ring in which a non-aromatic ring and an aromatic ring are condensed.
• the number of ring atoms of the ring is not particularly limited, but is preferably 5 to 20, for example.
• the ring may have a substituent.
• X3 represents a hydroxy group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group.
• the two Rc's may be the same or different.
• the explanation, specific examples and preferred ranges for X3 are the same as those for X1 and X2 in the above formula (1-1).
• X3 represents -N(Rx) 2
• the explanation, specific examples and preferred ranges for Rx are the same as those for Rx in the explanation of formula (1-1) above.
• X3 represents -NRaCORb
• the description, specific examples and preferred ranges of Ra and Rb are the same as those for Ra and Rb in the description of formula (1-1) above.
• Rb represents -N(Rc) 2
• the description, specific examples, and preferred ranges of Rc are the same as those for Rc in the description of formula (1-1) above.
• L2 in formula (1-2) represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• the explanation, specific examples, and preferred ranges for L2 are the same as those for L1 in formula (1-1) above.
• R5 and R6 each independently represent a hydrogen atom or an organic group.
• the explanation, specific examples and preferred ranges of R5 and R6 are the same as those for Rx in the explanation of formula (1-1) above.
• R 7 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 8.
• R 8 represents an organic group.
• the explanation, specific examples, and preferred ranges for the alkyl group and aryl group represented by R 7 are the same as those for Rx in the explanation of formula (1-1) above.
• the explanation, specific examples, and preferred ranges for the organic group represented by R 8 are the same as those for Rx in the explanation of formula (1-1) above.
• At least two of X3 , R5 to R8, and L2 in formula (1-2) may be bonded to each other to form a ring.
• the explanation, specific examples, and preferred ranges for the ring formed by at least two of X3 , R5 to R8 , and L2 bonded to each other are the same as those for the ring formed by at least two of X1 , X2 , R1 to R4, and L1 in formula (1-1) above.
• the solvent (S) may consist of a single solvent or may be a mixed solvent containing two or more solvents.
• solids concentration is not particularly limited, and may be, for example, 0.1 to 80 mass%, 0.5 to 50 mass%, or 0.1 to 30 mass%.
• the solid substance (solid substance (U)) used in the present invention is used as a component of a resist composition.
• the solid substance is not particularly limited as long as it is used as a component of the resist composition and forms a solid content.
• the solid substance means a component that is contained in the resist composition and a component that is contained in the resist film formed using the resist composition when the solution produced by the solution production method of the present invention is used to prepare the resist composition.
• a solvent is not a "solid substance".
• it is a component that is contained in the resist composition and a component that is contained in the resist film formed using the resist composition, it is considered to be a "solid substance" even if its nature is liquid.
• the solid substance examples include nonionic low molecular weight compounds, compounds having a salt structure (salt compounds), and polymer compounds.
• Specific examples of the solid substance include compounds that generate acid when irradiated with actinic rays or radiation (photoacid generators), acid diffusion control agents, resins (acid decomposable resins, crosslinkable resins, etc.), crosslinkers, and surfactants.
• the photoacid generator is a compound that decomposes when irradiated with actinic rays or radiation to generate acid, and the generated acid becomes an active species and can be a catalyst for the deprotection reaction (elimination reaction of leaving groups) of the acid decomposable resin, cationic polymerization, crosslinking reaction, and the like.
• the acid diffusion control agent traps the acid generated from the photoacid generator, etc., and acts as a quencher that suppresses the reaction of the acid decomposable resin in the unexposed area caused by excess generated acid.
• the solid material (U) preferably comprises a salt compound.
• the salt compound may be a photoacid generator or an acid diffusion controller.
• the salt compound 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.
• the salt compound may be in the form of a low molecular weight compound and in the form of being incorporated into a part of a polymer in combination.
• the molecular weight of the salt compound is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3000 or less. There is no particular lower limit to the molecular weight of the salt compound, but it is preferably 100 or more.
• the salt compound is preferably in the form of a low molecular weight compound.
• Examples of the salt compound include compounds represented by "M + X - " (onium salts), and are preferably compounds that generate an acid upon exposure to light.
• Examples of the acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.
• sulfonic acids aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.
• carboxylic acids aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.
• carbonylsulfonylimide acids bis(alkylsulfonyl)
• M + represents an organic cation.
• the organic cation represented by M + is not particularly limited, but is preferably a cation represented by the following formula (ZaI) (hereinafter also referred to as “cation (ZaI)”) or a cation represented by the following formula (ZaII) (hereinafter also referred to as “cation (ZaII)”):
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic groups of 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.
• groups formed by bonding any two of R 201 to R 203 include alkylene groups (e.g., butylene and pentylene groups) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• the organic group of R 201 , R 202 , and R 203 is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.
• the alkyl group may be either 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 5.
• 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, and a t-butyl group.
• the number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• the cycloalkyl group may be 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.
• 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, further preferably a phenyl group or naphthyl group, and particularly preferably a phenyl group.
• the heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms.
• the heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group.
• 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.
• X - represents an anion, and preferably represents an organic anion.
• the anion include sulfonate anion (aliphatic sulfonate anion, aromatic sulfonate anion, camphorsulfonate anion, etc.), carboxylate anion (aliphatic carboxylate anion, aromatic carboxylate anion, aralkyl carboxylate anion, etc.), sulfonylimide anion, bis(alkylsulfonyl)imide anion, tris(alkylsulfonyl)methide anion, phenoxide anion, etc.
• the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.
• the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
• the aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
• the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
• the substituent is not particularly limited, but examples include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon
• the aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms.
• Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
• sulfonylimide anion is the saccharin anion.
• the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
• Substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
• the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.
• anions include, for example, phosphorus fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
• phosphorus fluorides eg, PF 6 ⁇
• boron fluorides eg, BF 4 ⁇
• antimony fluorides eg, SbF 6 ⁇
• X 1 ⁇ is preferably a phenoxide anion, a sulfonate anion or a carboxylate anion.
• X ⁇ may be an anion represented by the following formula (xa1).
• a 2 X1 represents O - , COO - or SO 3 - .
• Ar 4 represents an aromatic ring.
• R 2 X1 represents a substituent.
• k4 represents an integer of 0 to 7. When k4 is 2 or more, multiple R 2 X1 may be the same or different. When k4 is 2 or more, multiple R 2 X1 may be bonded to each other to form a ring.
• the aromatic ring represented by Ar4 may be an aromatic hydrocarbon ring or an aromatic heterocycle.
• the number of ring-membered carbon atoms of the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15.
• the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
• the number of ring-membered atoms of the aromatic heterocycle is preferably 4 to 20, more preferably 5 to 10.
• the aromatic heterocycle preferably contains at least one of a sulfur atom, a nitrogen atom, and an oxygen atom.
• aromatic heterocycle examples include five-membered aromatic heterocycles such as pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole, furan ring, and thiophene ring, and six-membered aromatic heterocycles such as pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, thiazine ring, and oxazine ring.
• five-membered aromatic heterocycles such as pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole, furan ring, and thiophene ring
• six-membered aromatic heterocycles such as pyridine ring
• the substituent represented by R X1 is not particularly limited, but examples thereof include the above-mentioned substituent T, and preferred are a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, a cycloalkyl group and a halogen atom.
• k4 represents an integer from 0 to 7, preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.
• the salt compound preferably contains at least one selected from the group consisting of a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3).
• M 1 + represents an organic cation.
• a 1 - represents a residue of an acid.
• X 4 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• C 4 and C 5 each independently represent sp 3 carbon or sp 2 carbon.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• L 3 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• R 9 to R 12 each independently represent a hydrogen atom or an organic group. At least two of X 4 , R 9 to R 12 and L 3 may be bonded to each other to form a ring.
• n4 represents 0 or 1, provided that when C 4 is an sp 2 carbon, n4 is 0, and when C 4 is an sp 3 carbon, n4 is 1.
• n5 represents 0 or 1, provided that when C 5 is an sp 2 carbon, n5 is 0, and when C 5 is an sp 3 carbon, n5 is 1.
• M 2 + represents an organic cation.
• a 2 - represents an acid residue.
• L 4 represents a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• C 6 represents an sp 3 carbon or an sp 2 carbon.
• R 13 and R 14 each independently represent a hydrogen atom or an organic group.
• R 15 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 16.
• R 16 represents an organic group. At least two of R 13 to R 16 and L 4 may be bonded to each other to form a ring.
• n6 represents 0 or 1. However, when C 6 is an sp 2 carbon, n6 is 0, and when C 6 is an sp 3 carbon, n6 is 1.
• M 3 + represents an organic cation.
• a 3 - represents a residue of an acid.
• X 5 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. Two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. Two Rc's may be the same or different.
• C 7 represents sp 3 carbon or sp 2 carbon.
• R 17 and R 18 each independently represent a hydrogen atom or an organic group. At least two of X 5 , R 17 , and R 18 may be bonded to each other to form a ring.
• n7 represents 0 or 1. However, if C7 is an sp2 carbon, then n7 is 0, and if C7 is an sp3 carbon, then n7 is 1.
• M 1 + in formula (2-1), M 2 + in formula (2-2), and M 3 + in formula (2-3) each independently represent an organic cation.
• the explanations, specific examples, and preferred ranges of M 1 + , M 2 +, and M 3 + are the same as those for M + described above.
• a 1 - in formula (2-1), A 2 - in formula (2-2), and A 3 - in formula (2-3) each independently represent an acid residue.
• the acid residue is not particularly limited, but is preferably a carboxylate anion group (-COO - ), a sulfonate anion group (-SO 3 - ), a sulfonamide group (represented by -N - -SO 2 R N1 , R N1 represents an organic group, and is preferably an alkyl group, a fluoroalkyl group, or an aryl group), or a phenoxide anion group, and more preferably a carboxylate anion group or a sulfonate anion group.
• X4 in formula (2-1) and X5 in formula (2-3) each independently represent a hydroxy group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group.
• the two Rc's may be the same or different.
• the explanation, specific examples and preferred ranges of X4 and X5 are the same as those of X1 and X2 in the above formula (1-1).
• X4 and X5 represent -N(Rx) 2
• the explanation, specific examples and preferred ranges for Rx are the same as those for Rx in the explanation of formula (1-1) above.
• X4 and X5 represent -NRaCORb
• the explanation, specific examples and preferred ranges of Ra and Rb are the same as those for Ra and Rb in the explanation of formula (1-1) above.
• Rb represents -N(Rc) 2
• the description, specific examples, and preferred ranges of Rc are the same as those for Rc in the description of formula (1-1) above.
• L3 in formula (2-1) and L4 in formula (2-2) each independently represent a single bond, a double bond, an aromatic carbon-carbon bond, or a linking group having 2 or less carbon atoms.
• the explanation, specific examples, and preferred ranges for L3 and L4 are the same as those for L1 in formula (1-1) above.
• R 9 to R 12 in formula (2-1), R 13 and R 14 in formula (2-2), and R 17 and R 18 in formula (2-3) each independently represent a hydrogen atom or an organic group.
• the explanations, specific examples, and preferred ranges of R 9 to R 12 , R 13 , R 14 , R 17 , and R 18 are the same as those for Rx in the explanation of formula (1-1) above.
• R 15 represents a hydrogen atom, an alkyl group, an aryl group, -OH, or -OR 16.
• R 16 represents an organic group.
• the explanation, specific examples, and preferred ranges for the alkyl group and aryl group represented by R 15 are the same as those for Rx in the explanation of formula (1-1) above.
• the explanation, specific examples, and preferred ranges for the organic group represented by R 16 are the same as those for Rx in the explanation of formula (1-1) above.
• At least two of X 4 , R 9 to R 12 and L 3 in formula (2-1) may be bonded to each other to form a ring.
• the explanation, specific examples and preferred ranges for the ring formed by at least two of X 4 , R 9 to R 12 and L 3 bonded to each other are the same as those for the ring formed by at least two of X 1 , X 2 , R 1 to R 4 and L 1 in formula (1-1) above.
• At least two of R 13 to R 16 and L 4 in formula (2-2) may be bonded to each other to form a ring.
• the salt compound is a compound represented by the following formula (2-1-1):
• M 1 + represents an organic cation.
• a 1 - represents a residue of an acid.
• X 4 represents a hydroxyl group, an alkoxy group, an acyloxy group, -N(Rx) 2 , -NRaCORb, a thiol group, or a thioalkoxy group.
• Rx represents a hydrogen atom or an organic group. The two Rx's may be the same or different.
• Ra represents a hydrogen atom or an organic group.
• Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, -N(Rc) 2 , or a thioalkoxy group.
• Rc represents a hydrogen atom or an organic group. The two Rc's may be the same or different.
• R 19 represents a substituent. n8 represents an integer of 0 to 2. n9 represents an integer of 0 to (4+2 ⁇ n8). When a plurality of R 19's are present, the plurality of R 19's may be the same or different.
• the substituent represented by R 19 in formula (2-1-1) is not particularly limited. Examples of the substituent represented by R 19 include the above-mentioned substituent T.
• n8 in formula (2-1-1) When n8 in formula (2-1-1) is 0, the aromatic ring in formula (2-1-1) is a benzene ring. When n8 in formula (2-1-1) is 1, the aromatic ring in formula (2-1-1) is a naphthalene ring. When n8 in formula (2-1-1) is 2, the aromatic ring in formula (2-1-1) is an anthracene ring. n8 preferably represents 0 or 1, and more preferably represents 0.
• n9 preferably represents an integer from 0 to 4, and more preferably an integer from 0 to 3.
• anion represented by X 1 - are shown below, but the anion is not limited thereto.
• the salt compound may be at least one selected from the group consisting of compounds (I) to (II).
• Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation:
• Structural moiety X a structural moiety consisting of an anionic moiety A 1 - and a cationic moiety M 1 + , which forms a first acidic moiety represented by HA 1 when irradiated with actinic rays or radiation.
• Structural moiety Y a structural moiety consisting of an anionic moiety A 2 - and a cationic moiety M 2 + , which forms a second acidic moiety represented by HA 2 when irradiated with actinic rays or radiation.
• the compound (I) satisfies the following condition I.
• Compound PI which is obtained by replacing the cationic moiety M 1 + in the structural moiety X and the cationic moiety M 2 + in the structural moiety Y in compound (I) with H + , has an acid dissociation constant a1 derived from the acidic moiety represented by HA 1 , which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H + , and an acid dissociation constant a2 derived from the acidic moiety represented by HA 2 , which is obtained by replacing the cationic moiety M 2 + in the structural moiety Y with H + , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• compound (I) is, for example, a compound that generates an acid having one of the first acidic site derived from the structural moiety X and one of the second acidic site derived from the structural moiety Y
• compound PI corresponds to a "compound having HA 1 and HA 2.
• the acid dissociation constant a1 and the acid dissociation constant a2 of compound PI are calculated as follows: when compound PI is a "compound having A 1 - and HA 2 ", the pKa is the acid dissociation constant a1; and when the "compound having A 1 - and HA 2 " is a "compound having A 1 - and A 2 - ", the pKa is the acid dissociation constant a2.
• compound (I) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y
• compound PI corresponds to a "compound having two HA 1's and one HA 2.
• the acid dissociation constant of the compound PI is determined, the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " and the acid dissociation constant when the "compound having one A 1 - , one HA 1 and one HA 2 " becomes "a compound having two A 1 - and one HA 2 " correspond to the above-mentioned acid dissociation constant a1.
• the acid dissociation constant when the "compound having two A 1 - and one HA 2 " becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when the compound has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 obtained by replacing the cationic site M 1 + in the structural site X with H + , the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1.
• the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-mentioned method for measuring an acid dissociation constant.
• the compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different from each other.
• the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
• a 1 - and A 2 - , as well as M 1 + and M 2 + may be the same or different, but it is preferable that A 1 - and A 2 - are different.
• the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more.
• the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
• the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less.
• the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
• the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less.
• the lower limit of the acid dissociation constant a1 is preferably -20.0 or more.
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation.
• Structural moiety Z a non-ionic moiety capable of neutralizing an acid
• compound PII which is obtained by replacing the cationic moiety M 1 + in the structural moiety X in compound (II) with H +
• the preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA 1 which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H +
• compound PII corresponds to a "compound having two HA 1s ".
• the acid dissociation constant when compound PII becomes a "compound having one A 1 - and one HA 1 " and the acid dissociation constant when the "compound having one A 1 - and one HA 1 " becomes a "compound having two A 1 -s " correspond to the acid dissociation constant a1.
• the acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant.
• the compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural moieties X may be the same or different, and the two or more A 1 ⁇ and the two or more M 1 + may be the same or different.
• the nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton, or a functional group having an electron.
• Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation.
• the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:
• Examples of partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.
• salt compounds include the compounds described in paragraphs [0320] to [0321] of WO 2022/172715. The above descriptions are incorporated herein by reference.
• the content of the salt compound is not particularly limited, but is preferably 0.1 mass % or more and 100 mass % or less, more preferably 0.5 mass % or more and 100 mass % or less, and even more preferably 1.0 mass % or more and 100 mass % or less, relative to the total solid content in the solution (Z).
• the salt compound may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (U) may contain an acid-decomposable resin (also referred to as "resin (P)").
• the resin (P) is a resin that decomposes under the action of an acid and has an increased polarity.
• the resin (P) preferably has a group that decomposes under the action of an acid to increase its polarity (acid-decomposable group), and more preferably contains a repeating unit having an acid-decomposable group.
• the acid-decomposable group is typically 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.
• a polar group is protected by a group (leaving group) that is eliminated under the action of an acid.
• the polarity of the resin (P) increases under the action of an acid, so that the solubility in an alkaline developer increases and the solubility in an organic solvent decreases.
• the acid-decomposable group is a group that decomposes under the action of an acid and has an increased polarity.
• the acid-decomposable group is typically 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.
• the polarity of the resin (P) increases under the action of an acid, so that the solubility in an alkaline developer increases and the solubility in an organic solvent decreases.
• the polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy 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.
• acidic groups
• Examples of the leaving group which is eliminated by the action of an acid include groups represented by the 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 aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched).
• 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.
• Two of Rx 1 to Rx 3 may be bonded to each other to form a ring (which may be either a monocyclic ring or a polycyclic ring).
• the alkyl groups Rx 1 to Rx 3 are preferably alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a t-butyl group, and more preferably an alkyl group having 1 to 5 carbon atoms.
• the number of carbon atoms of the cycloalkyl group of Rx 1 to Rx 3 is preferably 3 to 20, more preferably 4 to 15.
• the cycloalkyl group may be 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.
• the cycloalkyl group may have, for example, one of the methylene groups constituting the ring replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group.
• the cycloalkyl group may have one or more ethylene groups constituting the cycloalkane ring replaced with a vinylene group. That is, Rx 1 to Rx 3 may be a cycloalkenylene 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 aralkyl group of Rx 1 to Rx 3 is preferably a group in which one hydrogen atom in the alkyl group of Rx 1 to Rx 3 described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples thereof include a benzyl group.
• the alkenyl groups of Rx 1 to Rx 3 include alkenyl groups having 2 to 20 carbon atoms, and are preferably alkenyl groups having 2 to 10 carbon atoms, such as vinyl and allyl groups.
• the alkynyl group of Rx 1 to Rx 3 includes an alkynyl group having 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms, for example, an ethynyl 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.
• 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 having 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.
• 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 heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and/or a group having 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.
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may be bonded to each other to form a non-aromatic ring.
• Ar is more preferably an aryl group.
• the resin (P) preferably contains a repeating unit represented by the following formula (Pa1).
• the repeating unit represented by the following formula (Pa1) is a repeating unit having an acid-decomposable group.
• R b1 represents a hydrogen atom or an alkyl group.
• r represents an integer of 0 to 2.
• p represents an integer of 1 to 5.
• R p1 represents -OR p2 or -COOR p3 .
• R p2 and R p3 each independently represent a group that is eliminated by the action of an acid.
• q represents an integer of 0 to (5+2 ⁇ r-p).
• R b2 represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an ester group, or a carboxy group.
• p 2 or more
• multiple R p1s may be the same or different from each other and may be bonded to each other to form a ring.
• q is 2 or more
• multiple R b2s may be the same or different from each other and may be bonded to each other to form a ring.
• the alkyl group represented by R b1 may be linear or branched.
• the alkyl group 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, or a t-butyl group.
• the alkyl group may have a substituent.
• R b1 is preferably a hydrogen atom or a methyl group.
• r represents an integer from 0 to 2, preferably 0 or 1, and more preferably 0.
• the aromatic ring in formula (Pa1) represents a benzene ring.
• the aromatic ring in formula (Pa1) represents a naphthalene ring.
• the aromatic ring in formula (Pa1) represents an anthracene ring.
• p represents an integer from 1 to 5, preferably an integer from 1 to 3, and more preferably 1.
• R p1 represents —OR p2 or —COOR p3 .
• R p2 and R p3 each independently represent a group which is eliminated by the action of an acid. Examples of the group which is eliminated by the action of an acid represented by R p2 and R p3 include the groups represented by the above formulae (Y1) to (Y4).
• Y1 hydroxy group
• Y4 hydroxy group
• R p3 a carboxy group is generated in formula (Pa1).
• q represents an integer from 0 to (5+2 ⁇ r-p), preferably an integer from 0 to 5, more preferably an integer from 0 to 3, even more preferably 0 or 1, and most preferably 0.
• R b2 represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an ester group or a carboxy group.
• the halogen atom for R b2 is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• the alkyl group of R b2 may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
• alkyl group examples include 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 explanation, specific examples and preferred ranges of the alkyl group contained in the alkoxy group and alkylthio group of R b2 are the same as the explanation, specific examples and preferred ranges of the alkyl group of R b2 above.
• the aryl group of R b2 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, further preferably a phenyl group or naphthyl group, and particularly preferably a phenyl group.
• Specific examples and preferred ranges of the aryl group contained in the aryloxy group of R b2 are the same as the specific examples and preferred ranges of the aryl group of R b2 described above.
• the heteroaryl group of R b2 is preferably a heteroaryl group having 3 to 20 carbon atoms.
• the heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom.
• heteroaryl group examples include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• Specific examples and preferred ranges of the heteroaryl group contained in the heteroaryloxy group of R b2 are the same as the specific examples and preferred ranges of the heteroaryl group of R b2 described above.
• the ester group of R b2 is preferably -COOR b3 or -OCOR b3 .
• R b3 represents an organic group, and preferably represents an alkyl group or an aryl group.
• alkyl group of R b3 are the same as the description, specific examples and preferred ranges of the alkyl group of R b2 above.
• the specific examples and preferred ranges of the aryl group of R b3 are the same as the specific examples and preferred ranges of the aryl group of R b2 above.
• a preferred embodiment of the repeating unit having an acid-decomposable group is a repeating unit having a halogen atom.
• the repeating unit has at least one of a fluorine atom and an iodine atom, and more preferably has 1 to 10 fluorine atoms and iodine atoms in total, and further preferably has 1 to 5 fluorine atoms and iodine atoms in one repeating unit.
• a preferred embodiment of the repeating unit having an acid-decomposable group is one having no halogen atom.
• the description in paragraphs [0029] to [0075] of WO 2022/024928 can be cited. The above description is incorporated herein by reference.
• repeating units having an acid-decomposable group are shown below, but are not limited to these.
• the content of repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all repeating units in resin (P).
• the content of repeating units having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on all repeating units in resin (P).
• the repeating unit having an acid-decomposable group contained in the resin (P) may be of one type or of two or more types.
• the resin (P) contains two or more types of repeating units having an acid-decomposable group, it is preferable that the total content thereof is within the above-mentioned preferred content range.
• Resin (P) may contain at least one type of repeating unit selected from the group consisting of Group A below and/or at least one type of repeating unit selected from the group consisting of Group B below.
• Group A A group consisting of the following repeating units (20) to (25).
• a repeating unit having an acid group (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; (22) A repeating unit having a lactone group, a sultone group or a carbonate group; (23) A repeating unit having a photoacid generating group; (24) A repeating unit represented by formula (V-1) or formula (V-2); (25) A repeating unit for reducing the mobility of the main chain; Group B: A group consisting of the following repeating units (30) to (32).
• the resin (P) preferably has an acid group and preferably contains a repeating unit having an acid group.
• the acid group is preferably an acid group having a pKa of not more than 13.
• the pKa of the acid group is preferably not more than 13, more preferably from 3 to 13, and even more preferably from 5 to 10.
• the pKa of the acid group is the pKa of a monomer corresponding to the repeating unit having the acid group.
• the content of the acid group in the resin (P) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
• the content of the acid group is within the above range, development proceeds well, and the formed pattern shape is excellent, and the resolution is also excellent.
• 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 sulfonamide group
• an isopropanol group 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.
• hexafluoroisopropanol group one or more fluorine atoms (preferably one or two) may be substituted with
• one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• the acid group is particularly preferably a phenolic hydroxyl group.
• the repeating unit having an acid group is preferably a repeating unit different from the repeating unit having an acid-decomposable group.
• the repeating unit having an acid group is preferably a repeating unit different from a repeating unit having a lactone group, a sultone group or a carbonate group.
• 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 content of the repeating units having an acid group in the resin (P) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (P).
• the content of the repeating units having an acid group is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (P).
• the repeating unit having an acid group contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units having an acid group, it is preferable that the total content thereof is within the above-mentioned suitable content range.
• the resin (P) preferably contains a repeating unit having a phenolic hydroxyl group.
• the repeating unit having a phenolic hydroxyl group is preferably a repeating unit different from the repeating unit having the acid-decomposable group described above.
• the repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following formula (Pa2).
• R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• R 102 may be bonded to Ar A to form a ring, in which case R 102 represents a single bond or an alkylene group.
• L A represents a single bond or a divalent linking group.
• Ar A represents an aromatic ring group.
• k represents an integer of 1 to 5.
• R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• the alkyl group of R 101 , R 102 and R 103 may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
• alkyl group examples include 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 number of carbon atoms in the cycloalkyl group of R 101 , R 102 and R 103 is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group
• a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group are preferred.
• halogen atom for R 101 , R 102 and R 103 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom or an iodine atom being preferred.
• the alkyl group contained in the alkoxycarbonyl group of R 101 , R 102 and R 103 may be either linear or branched.
• the number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• Ar A in formula (Pa2) represents an aromatic ring group, more specifically, an aromatic ring group having a valence of (k+1).
• the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring.
• the aromatic ring group may have a substituent.
• Specific examples of the (k+1)-valent aromatic ring group when k is an integer of 2 or more include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.
• the (k+1)-valent aromatic ring group may further have a substituent.
• the substituent that the (k+1)-valent aromatic ring group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl groups.
• Ar A preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.
• L A represents a single bond or a divalent linking group.
• the divalent linking group represented by L A is not particularly limited, and examples thereof include -COO-, -CONR 104 -, an alkylene group, or a group formed by combining two or more of these groups, where R 104 represents a hydrogen atom or an alkyl group.
• the alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.
• R 104 represents an alkyl group
• examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
• the repeating unit represented by formula (Pa2) preferably has a hydroxystyrene structure, that is, Ar A preferably represents a benzene ring group.
• k preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.
• the content of the repeating unit having a phenolic hydroxyl group in the resin (P) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (P).
• the content of the repeating unit having a phenolic hydroxyl group is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (P).
• the repeating unit having a phenolic hydroxyl group contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units having a phenolic hydroxyl group, it is preferable that the total content thereof is within the above-mentioned suitable content range.
• G1 and G2 each independently represent a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group.
• f1 represents an integer of 1 to 3.
• the resin (P) may have a repeating unit having neither an acid decomposable group nor an acid group, but having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as "unit X").
• the ⁇ repeating unit having neither an acid decomposable group nor an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here is preferably different from other types of repeating units belonging to Group A, such as the ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> and the ⁇ repeating unit having a photoacid generating group> described below.
• the repeating unit X is preferably a repeating unit represented by formula (C).
• L5 represents a single bond or an ester group.
• R9 represents a hydrogen atom, or an alkyl group which may have a fluorine atom or an iodine atom.
• R10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which combines these.
• Specific examples of the repeating unit having a fluorine atom or an iodine atom include the repeating units described in paragraphs [0116] to [0117] of WO 2022/024928. The above descriptions are incorporated herein by reference.
• the content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in resin (P).
• the content of unit X is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in resin (P).
• the resin (P) may have a repeating unit having a lactone group, a sultone group or a carbonate group (hereinafter also referred to as "unit Y"). 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.
• the carbonate group is preferably a cyclic carbonate group.
• For 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 resin (P) preferably has a repeating unit having a lactone group, a sultone group, or a carbonate 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 (LC1-22), a sultone structure represented by any one of the following formulae (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any one of the following formulae (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain.
• the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of the resin (P).
• the lactone group, sultone group, and carbonate group may have a substituent.
• R L represents a substituent.
• the plurality of R Ls may be the same or different.
• R Ls include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group.
• e1 represents an integer of 0 to 4.
• the plurality of e1s may be the same or different.
• e1 is 2 or more, the plurality of R Ls may be the same or different, and the plurality of R Ls may be bonded to each other to form a ring.
• An example of a repeating unit having a lactone group, a sultone group, or a carbonate group 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.
• the alkyl group of Rb 0 may have a substituent.
• substituent that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
• 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, 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 (LC1-22), 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), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any of formulas (CC1-1) to (CC1-2).
• the content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, based on all repeating units in resin (P).
• the content of unit Y is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in resin (P).
• the resin (P) may have 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").
• An example of the 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.
• L 41 represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).
• L 42 is preferably at least one linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -S-, -SO-, -SO 2 -, and -NR-, where R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group).
• the alkylene group may be either linear or branched.
• the number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10.
• the cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group.
• the number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• the number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10.
• the alkylene group, the cycloalkylene group and the arylene group may have a substituent, and examples of the substituent include the above-mentioned substituent T.
• R 40 is preferably a group represented by the following formula (S4-1).
• Q- represents an acid residue
• M + represents a cation
• * represents the bonding position with L41 .
• the acid residue is a group formed by dissociating a proton from an acid.
• Q ⁇ is preferably a carboxylate anion group (COO ⁇ ), a sulfonate anion group (SO 3 ⁇ ), or a sulfonamide group (represented by N ⁇ —SO 2 R N1 , where R N1 represents an organic group, including an organic group having 1 to 10 carbon atoms, and preferably an alkyl group, a fluoroalkyl group, or an aryl group), and more preferably a sulfonate anion group.
• R N1 represents an organic group, including an organic group having 1 to 10 carbon atoms, and preferably an alkyl group, a fluoroalkyl group, or an aryl group
• M + represents an organic group, including an organic group having 1 to 10 carbon atoms, and preferably
• repeating units 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.
• 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 unit having a photoacid generating group is preferably 1 mol% or more, and more preferably 5 mol% or more, based on the total repeating units in the resin (P).
• the content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total repeating units in the resin (P).
• the resin (P) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are preferably different from the above-mentioned respective repeating units.
• R 6 and R 7 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.
• the alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.
• n 3 represents an integer of 0 to 6.
• n 4 represents an integer of 0 to 4.
• X 4 is a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph [0100] of WO 2018/193954.
• the resin (P) may have a high glass transition temperature (Tg) in order to suppress excessive diffusion of the generated acid or pattern collapse during development.
• Tg may be higher than 90° C., higher than 100° C., higher than 110° C., or higher than 125° C.
• the Tg may be 400° C. or lower, or 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.).
• the resin (P) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group.
• Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (P) include the repeating units described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the preferred content is also as described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the resin (P) may 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 (P) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the ⁇ -position with an electron-withdrawing group, with a carboxyl group being preferred.
• the resin (P) contains a repeating unit having an alkali-soluble group, which improves the resolution, particularly in contact hole applications. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP2014-098921A.
• the resin (P) may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposability. This can reduce the 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, and cyclohexyl (meth)acrylate.
• the resin (P) may have a repeating unit represented by formula (III) which does not have either a hydroxyl group or 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 -CH2 -O- Ra2 group, in which Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
• Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs [0087] to [0094] of JP2014-098921A.
• the resin (P) may have repeating units other than the repeating units described above.
• the resin (P) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in [0170] of WO 2022/024928.
• the resin (P) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight (Mw) of the resin (P) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, as determined by GPC in terms of polystyrene.
• the dispersity (molecular weight distribution, Pd, Mw/Mn) of the resin (P) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.0 to 3.0, and particularly preferably from 1.1 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern are, and the better the roughness.
• the content of the resin (P) is not particularly limited, but is preferably 40 to 100 mass %, more preferably 60 to 100 mass %, based on the total solid content in the solution (Z).
• Resin (P) may be used alone or in combination of two or more. When two or more resins (P) are used, the total content thereof is preferably within the above-mentioned preferred content range.
• the solid substance (U) may contain a resin having a phenolic hydroxyl group (also referred to as "resin (N)") different from the above-mentioned resin (P).
• the resin (N) preferably contains a repeating unit having a phenolic hydroxyl group.
• An example of a repeating unit having a phenolic hydroxyl group is the repeating unit represented by the above-mentioned formula (Pa2).
• the content of repeating units having a phenolic hydroxyl group in resin (N) is not particularly limited, but is preferably 10 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 (N).
• the content of repeating units having a phenolic hydroxyl group may be 100 mol% or less, 90 mol% or less, or 80 mol% or less, based on the total repeating units in resin (N).
• the repeating unit having a phenolic hydroxyl group contained in resin (N) may be of one type or of two or more types.
• resin (N) contains two or more types of repeating units having a phenolic hydroxyl group, it is preferable that the total content thereof is within the above-mentioned preferred content range.
• the resin (N) may contain repeating units other than those described above.
• repeating units having a phenolic hydroxyl group groups that the resin (N) preferably has, and other repeating units, the contents of paragraphs [0238] to [0307] of WO 2016/136563 are incorporated by reference.
• the content of the resin (N) is not particularly limited, but may be 40 to 100 mass %, 50 to 100 mass %, or 60 to 100 mass % relative to the total solid content in the solution (Z).
• Resin (N) may be used alone or in combination of two or more. When two or more resins (N) are used, the total content thereof is preferably within the above-mentioned preferred content range.
• the solid material (U) may contain a cross-linking agent.
• the crosslinking agent is preferably a compound capable of forming a bond with a compound having a phenolic hydroxyl group.
• the crosslinking agent is preferably a compound having, as a crosslinkable group, two or more hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups or alkoxymethyl ether groups, or an epoxy compound. More preferred examples of the crosslinking agent include alkoxymethylated or acyloxymethylated melamine compounds, alkoxymethylated or acyloxymethylated urea compounds, hydroxymethylated or alkoxymethylated phenol compounds, and alkoxymethyl etherified phenol compounds.
• the crosslinking agent preferably has a structure represented by the following formula (CL-1):
• R c1 to R c6 each independently represent a hydrogen atom, an organic group, or a bonding site with the linking group or single bond represented by L c1 in formula (CL-3), provided that at least one of R c2 to R c6 is a structure represented by formula (CL-2).
• R c7 represents a hydrogen atom or an organic group (preferably an organic group having 1 to 30 carbon atoms), and * represents a bonding site in any of R c2 to R c6 .
• L c1 represents a linking group or a single bond
• * represents a bonding site in any of R c1 to R c6
• e1 represents an integer of 2 to 5.
• R c1 to R c6 each independently represent a hydrogen atom or an organic group (preferably an organic group having 1 to 50 carbon atoms).
• the organic group include an alkyl group, a cycloalkyl group, an aryl group, or a group in which these groups are linked via an alkylene group, an arylene group, a carboxylate bond, a carbonate bond, an ether bond, a thioether bond, a sulfo group, a sulfone group, a urethane bond, a urea bond, or a group consisting of a combination of these.
• At least one of R c2 to R c6 is a structure represented by formula (CL-2).
• Specific examples of the organic group represented by R c7 in formula (CL-2) include the same as the organic groups represented by R c1 to R c6 described above. It is preferable that one molecule has two or more structures represented by formula (CL-2).
• the crosslinking agent may be a compound in which 1 to 5 structures represented by formula (CL-1) are linked via a linking group or single bond represented by L c1 in formula (CL-3).
• at least one of R c1 to R c6 in formula (CL-1) represents a bonding site with the linking group or single bond represented by formula (CL-3).
• Examples of the linking group represented by L c1 in formula (CL-3) include an alkylene group, an arylene group, a carboxylate bond, a carbonate bond, an ether bond, a thioether bond, a sulfo group, a sulfone group, a urethane bond, a urea bond, or a group formed by combining two or more of these.
• Preferred are an alkylene group, an arylene group, and a carboxylate bond.
• e1 represents 2 or 3.
• crosslinking agents can be found in paragraphs [0064] to [0066] of WO 2016/136563, the contents of which are incorporated herein by reference.
• examples of the crosslinking agent include (i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, and (ii) an epoxy compound.
• the compounds represented by the general formula described in [0294] to [0315] of JP2012-242556A can be preferably used.
• a compound having two or more (more preferably 2 to 8) partial structures represented by the following formula (CLNM-1) is preferred.
• R NM1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an oxoalkyl group.
• More preferred embodiments of the compound having two or more partial structures represented by formula (CLNM-1) include a urea-based crosslinking agent represented by the following formula (CLNM-2), an alkylene urea-based crosslinking agent represented by the following formula (CLNM-3), a glycoluril-based crosslinking agent represented by the following formula (CLNM-4), and a melamine-based crosslinking agent represented by the following formula (CLNM-5).
• R NM1 has the same meaning as R NM1 in formula (CLNM-1). Multiple R NM1 may be the same or different.
• R NM2 represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), or a cycloalkyl group (preferably having 5 to 6 carbon atoms). Multiple R NM2 may be the same or different.
• R NM1 has the same meaning as R NM1 in formula (CLNM-1).
• Multiple R NM1 may be the same or different.
• R NM3 represents a hydrogen atom, a hydroxy group, a linear or branched alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbon atoms), an oxoalkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxy group (preferably having 1 to 6 carbon atoms).
• Multiple R NM3s may be the same or different.
• G represents a single bond, an oxygen atom, a sulfur atom, an alkylene group (preferably having 1 to 3 carbon atoms) or a carbonyl group.
• R NM1 has the same meaning as R NM1 in formula (CLNM-1). Multiple R NM1 may be the same or different.
• R NM4 represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group. Multiple R NM4 s may be the same or different.
• R NM1 has the same meaning as R NM1 in formula (CLNM-1). Multiple R NM1 may be the same or different.
• R NM5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an atomic group represented by the following formula (CLNM-5′): Multiple R NM5s may be the same or different.
• R NM6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following formula (CLNM-5′′).
• R NM1 has the same meaning as R NM1 in formula (CLNM-1).
• R NM5 has the same meaning as R NM5 in formula (CLNM-5).
• the alkyl group for R NM5 and R NM6 is preferably an alkyl group having 1 to 6 carbon atoms
• the cycloalkyl group is preferably a cycloalkyl group having 5 to 6 carbon atoms
• the aryl group is preferably an aryl group having 6 to 10 carbon atoms.
• R NM1 to R NM6 in formulas (CLNM-1) to (CLNM-5) may further have a substituent.
• crosslinking agents are described in paragraphs [0087] to [0089] of WO 2016/136563, the contents of which are incorporated herein by reference.
• the content of the crosslinking agent is not particularly limited, but may be 3 to 100 mass % or 5 to 100 mass % based on the total solid content in the solution (Z).
• the crosslinking agent may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid material (U) may contain 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) that generates an acid that is weaker than the acid generated by a photoacid generator upon exposure to actinic rays or radiation (also referred to as an "onium salt compound that is weaker than the acid generated by a photoacid generator"), and a basic compound (DE) whose basicity is reduced or eliminated upon exposure to actinic rays or radiation.
• Specific examples of the basic compound (DA) include those described in paragraphs [0132] to [0136] of WO 2020/066824.
• the basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs [0137] to [0155] of WO 2020/066824 and those described in paragraph [0164] of WO 2020/066824.
• Specific examples of the low molecular weight compound (DB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs [0156] to [0163] of WO 2020/066824.
• the onium salt compound (DD) which is a relatively weak acid to the photoacid generator the above-mentioned salt compounds can also be used.
• Specific examples of the onium salt compound (DD) that is a weak acid relative to the photoacid generator include those described in paragraphs [0305] to [0314] of WO 2020/158337.
• the content of the acid diffusion controller is not particularly limited, but is preferably 0.1 to 100 mass%, more preferably 0.1 to 100 mass%, and even more preferably 1.0 to 100 mass%, based on the total solid content in the solution (Z).
• 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 solid substance (U) may contain a hydrophobic resin.
• the hydrophobic resin is a resin (also referred to as "hydrophobic resin (E)") different from the above-mentioned resin (P) and resin (N).
• the hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances.
• the effects of adding the hydrophobic resin (E) include control of the static and dynamic contact angles of water on the resist film surface, and suppression of outgassing.
• the hydrophobic resin (E) preferably has one or more of fluorine atoms, silicon atoms, and CH3 partial structures contained in the side chain portion of the resin, more preferably has two or more.
• the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Examples of the hydrophobic resin (E) include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
• the content of the hydrophobic resin (E) is not particularly limited, but is preferably 0.01 to 100 mass%, more preferably 0.1 to 100 mass%, based on the total solid content in the solution (Z).
• the hydrophobic resin (E) may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (U) may contain a compound having a phenolic hydroxyl group (also referred to as "compound (F)") different from the above-mentioned components.
• Compound (F) is a compound containing one or more phenolic hydroxyl groups in the molecule.
• the molecular weight of the compound (F) is preferably 100 or more and 2,000 or less, and more preferably 400 or more and 1,200 or less.
• the compound (F) for example, the compounds described in [0225] to [0233] of JP-A-2021-92779 and the compounds described in [0140] to [0149] of WO 2021/215163 can be used.
• L f1 to L f8 each independently represent a hydrogen atom or a substituent, and at least one in one molecule is a hydrogen atom.
• L f1 to L f8 are substituents, they are preferably an alkyl group, an aryl group, or an aralkyl group.
• the number of carbon atoms in the alkyl group is not particularly limited, and may be, for example, 1 to 20, 1 to 10, or 1 to 6.
• the alkyl group may be either linear or branched.
• alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group.
• the aryl group may be either a monocyclic or polycyclic (e.g., 2 to 6 rings, etc.).
• the number of ring atoms of the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group. The same applies to the aryl group portion in the aralkyl group.
• the content of the compound (F) is not particularly limited, but is preferably 0.01 to 100 mass%, more preferably 0.1 to 100 mass%, based on the total solid content in the solution (Z).
• the compound (F) may be used alone or in combination of two or more. When two or more compounds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (U) may contain a surfactant.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
• fluorine-based and/or silicone-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of WO 2018/193954.
• the surfactant may be used alone or in combination of two or more kinds.
• the content of the surfactant is not particularly limited, but is preferably 0.0001 to 100 mass%, more preferably 0.0005 to 100 mass%, and even more preferably 0.1 to 100 mass%, based on the total solid content in the solution (Z).
• the surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (U) may contain additives other than those described above, such as a crosslinking agent, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (e.g., 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 is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.
• the content of the other additives is not particularly limited, and may be 0.0001 to 100 mass %, 20 mass % or less, 10 mass % or less, or 5 mass % or less, relative to the total solid content in the solution (Z).
• the other additives may be used alone or in combination of two or more. When two or more additives are used, the total content is preferably within the above-mentioned preferred content range.
• the method for producing a solution of the present invention may further include a concentration step. That is, in the method for producing a solution of the present invention, the solution obtained in the solution-forming step may be concentrated. By performing the concentration, the remaining low-boiling point compounds can be removed. When concentrating, it is preferable to use a container containing a resin on at least a part of the inner wall surface, as in the solution-forming step.
• the concentration can be carried out by a known concentration method. The concentration can be carried out either at normal pressure or under reduced pressure, but is preferably carried out under reduced pressure.
• the degree of reduced pressure is preferably 50 kPa or less, more preferably 40 kPa or less, and even more preferably 30 kPa or less.
• the lower limit of the degree of reduced pressure is not particularly limited, but may be, for example, 0.05 kPa or more.
• the temperature during concentration is not particularly limited, but is preferably 20° C. or higher, more preferably 30° C. or higher, and even more preferably 40° C. or higher.
• the temperature during concentration is preferably 90° C. or lower, more preferably 70° C. or lower, and even more preferably 50° C. or lower. Concentration is preferably carried out with stirring.
• a stirring blade For stirring, a stirring blade, a magnetic stirrer, a rotary evaporator, etc. can be used.
• a stirring blade or a magnetic stirrer is used, the surfaces of the stirring blade and the stirrer tip that come into contact with the solution are preferably covered with a resin.
• the method for producing a resist composition of the present invention may be a method for producing a resist composition (also referred to as a "first aspect of the method for producing a resist composition") in which a resist composition is prepared using a solution (solution (Z)) produced by the above-mentioned method for producing a solution.
• the resist composition may be prepared using only the solution (Z), or other components may be used in addition to the solution (Z).
• the other components include a solid substance (also referred to as a "solid substance (V)”) and a solvent (also referred to as a "solvent (T)”). ) etc.
• the solid substance (V) may be the same solid substance (solid substance (U)) contained in the solution (Z), may be a solid substance different from the solid substance (U), or may be a mixture of the same solid substance as the solid substance (U) and a solid substance different from the solid substance (U).
• the solvent (T) may be the same solvent as the solvent (S) contained in the solution (Z), may be a solvent different from the solvent (S), or may be a mixed solvent of the same solvent as the solvent (S) and a solvent different from the solvent (S).
• a container containing a resin on at least a portion of the inner wall surface.
• the container containing a resin on at least a portion of the inner wall surface is the same as that in the method for producing the solution (Z) described above.
• the solvent (T) is preferably an organic solvent.
• the solvent (T) may consist of a single solvent or may be a mixed solvent containing two or more solvents.
• the organic 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 components (M1) and (M2) are described in paragraphs [0218] to [0226] of WO 2020/004306, the contents of which are incorporated herein by reference.
• the content of the component other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent (T).
• the amount of solvent (T) used it is preferable to set the amount so that the solids concentration of the resist composition produced by the first aspect of the method for producing a resist composition is 0.5 to 30 mass %, and it is more preferable to set the amount so that the solids concentration is 1 to 20 mass %.
• Solid substance (V) The description, specific examples and preferred ranges of the solid material (V) are the same as those of the solid material (U) described above.
• the solid substance (V) contains a salt compound
• the amount of the salt compound contained it is preferably from 0.1 mass % to 60.0 mass % relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition, more preferably from 0.5 mass % to 50.0 mass %, and even more preferably from 1.0 mass % to 40.0 mass %.
• the salt compound may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains a resin (P)
• the amount of resin (P) contained is preferably from 40.0 to 99.9 mass %, and more preferably 60.0 to 90.0 mass %, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• Resin (P) may be used alone or in combination of two or more. When two or more resins (P) are used, the total content thereof is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains a resin (N)
• the amount of resin (N) contained is preferably from 40.0 to 99.9 mass %, and more preferably 60.0 to 90.0 mass %, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• Resin (N) may be used alone or in combination of two or more. When two or more resins (N) are used, the total content thereof is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains a crosslinking agent
• the amount of the crosslinking agent contained there are no particular limitations on the amount of the crosslinking agent contained, and it may be 3 to 65 mass %, or 5 to 50 mass %, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• the crosslinking agent may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains an acid diffusion controller
• the amount of the acid diffusion controller contained 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 %, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• 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 solid substance (V) contains a hydrophobic resin (E)
• hydrophobic resin (E) there are no particular limitations on the amount of hydrophobic resin (E) contained, but it is preferably from 0.01 to 20.0 mass %, and more preferably from 0.1 to 15.0 mass %, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• the hydrophobic resin (E) may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains the compound (F)
• the amount of compound (F) contained is preferably from 0.01 to 40.0 mass%, and more preferably from 0.1 to 30.0 mass%, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• the compound (F) may be used alone or in combination of two or more. When two or more compounds are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (V) contains a surfactant
• the amount of the surfactant contained is preferably from 0.0001 to 2.0 mass%, more preferably from 0.0005 to 1.0 mass%, and even more preferably from 0.1 to 1.0 mass%, relative to the total solid content in the resist composition produced by the first aspect of the method for producing a resist composition.
• the surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above-mentioned preferred content range.
• the solid substance (V) when a solid substance (V) is used, it is preferable to dissolve a part or all of the solid substance (V) in the solution (Z) or the solvent (T). In this case, when the solid substance (V) is composed of only one type of solid substance, a part or all of the one type of solid substance may be dissolved. In addition, when the solid substance (V) contains two or more types of solid substances, a part or all of at least one of the solid substances may be dissolved.
• the temperature at which the solid substance (V) is dissolved in the solution (Z) or the solvent (T) is not particularly limited, but is preferably 0 to 90°C, more preferably 10 to 70°C, and particularly preferably 15 to 50°C.
• the solution (Z) or the solvent (T) may be stirred.
• a stirring blade stirrring blade
• a magnetic stirrer a rotary mixer, or the like
• the surfaces of the stirring blade and the stirrer tip that come into contact with the solution (Z) or the solvent (T) are covered with a resin.
• the resin include the same resins as those used in the above-mentioned container.
• the method for producing a resist composition of the present invention may be a method for producing a resist composition (also referred to as a "second aspect of the method for producing a resist composition”), which comprises the steps of pouring one or more solid substances used as components of the resist composition and a solvent into a container containing a resin on at least a portion of the inner wall surface, and dissolving a part or all of the solid content consisting of the one or more solid substances.
• a resist composition is prepared using solution (Z), whereas in the second embodiment of the method for producing a resist composition, solution (Z) may not be used.
• a solid substance that is a dry powder or a wet powder may be used without using solution (Z).
• solution (Z) may also be used in the second embodiment of the method for producing a resist composition.
• the container containing a resin on at least a portion of the inner wall surface used in the second embodiment of the method for producing a resist composition is the same as that used in the method for producing the solution (Z) described above.
• the solid substance used in the second embodiment of the method for producing a resist composition is the same as the solid substance (U) described above.
• the solid substance used in the second embodiment of the method for producing a resist composition contains a salt compound
• the solid substance contains a resin (P) when the solid substance contains a resin (P), when the solid substance contains an acid diffusion controller, when the solid substance contains a hydrophobic resin (E), the content of the hydrophobic resin (E) and when the solid substance contains a surfactant are each the same as those in the first embodiment of the method for producing a resist composition described above.
• the solvent used in the second embodiment of the method for producing a resist composition is the same as the above-mentioned solvent (S).
• the amount of the solvent used is determined so that the solids concentration of the resist composition produced in the second aspect of the method for producing a resist composition is preferably from 0.5 to 30 mass %, and more preferably from 1 to 20 mass %.
• the temperature at which the solid substance is dissolved in the solvent is not particularly limited, but is preferably 0 to 90°C, more preferably 10 to 70°C, and particularly preferably 15 to 50°C.
• the solution may be stirred.
• a stirring blade stirrring blade
• a magnetic stirrer a rotary mixer, etc.
• the surfaces of the stirring blade and the stirrer tip that come into contact with the solution are covered with a resin.
• the resin include the same resins used for the above-mentioned container.
• the dissolution of the solid substance in the solvent can be confirmed, for example, by the same method as that described in the above-mentioned method for producing solution (Z).
• the resist composition produced by the first aspect of the method for producing a resist composition and the second aspect of the method for producing a resist composition may be a positive resist composition or a negative resist composition.
• the resist composition may be a resist composition for alkaline development or a resist composition for organic solvent development.
• the resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• a resist film can be formed using the resist composition.
• the present invention also relates to a pattern formation method including a resist film formation step of forming a resist film using a resist composition produced by the above-mentioned first aspect of the method for producing a resist composition or the second aspect of the method for producing a resist composition, an exposure step of exposing the resist film to light, and a development step of developing the exposed resist film using a developer.
• the procedure of the pattern forming method of the present invention preferably includes the following steps. Step 1: A step of forming a resist film on a substrate using a resist composition produced by the first aspect of the method for producing a resist composition or the second aspect of the method for producing a resist composition. Step 2: A step of exposing the resist film. Step 3: A step of developing the exposed resist film using a developer.
• Step 1 is a step of forming a resist film on a substrate using a resist composition produced by the first aspect of the method for producing a resist composition or the second aspect of the method for producing a resist composition.
• An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto a substrate. It is preferable to filter the resist composition before coating as necessary.
• 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 resist composition can be applied onto 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.
• the actinic ray or radiation 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.
• a proximity effect correction software for electron beams may be used. By using the software, it becomes possible to correct the irradiation energy for each drawing position, and it becomes possible to improve the uniformity of the pattern shape between the center and the outer periphery of the pattern.
• 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 pattern forming method preferably includes, after step 3, a step of cleaning 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 resist composition 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.
• impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
• Methods for reducing metal and other impurities contained in various materials include, for example, selecting raw materials with low metal content as the raw materials that make up the various materials, filtering the raw materials that make up the various materials, and performing distillation under conditions that minimize contamination as much as possible, such as lining the inside of the equipment with Teflon (registered trademark).
• impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used.
• adsorbent known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• inorganic adsorbents such as silica gel and zeolite
• organic adsorbents such as activated carbon.
• the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferable.
• An organic processing liquid such as a rinse liquid may contain a conductive compound to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge.
• the conductive compound is not particularly limited, but an example thereof is methanol.
• the amount added is not particularly limited, but from the viewpoint of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. There is no particular lower limit, and 0.01% by mass or more is preferable.
• the chemical liquid piping may be made of, for example, stainless steel (SUS), or various piping coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the filter and O-ring may be made of antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method.
• a preferred embodiment of the electronic device of the present invention is one in which it is mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
• A-1 to A-5 are resins (A-1 to A-3 are resins (P), and A-4 and A-5 are resins (N)).
• the subscripts in parentheses of the repeating units of A-1 to A-5 indicate the content of each repeating unit.
• the content of the repeating unit is a molar ratio to the total repeating units in each resin.
• the content of the repeating unit was measured by 13 C-NMR (nuclear magnetic resonance).
• the weight average molecular weight (Mw) and dispersity (Pd) of A-1 to A-5 are also shown. Mw and Pd were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent).
• B-1 to B-8, C-1, C-2 and D-2 are salt compounds.
• B-6 to B-8, C-1 and C-2 were used as photoacid generators.
• B-1 to B-5, D-1 and D-2 were used as acid diffusion control agents.
• E-1 and E-2 are crosslinking agents.
• W-1 to W-6 are surfactants.
• W-1 Megafac F176 (manufactured by DIC Corporation; fluorine-based)
• W-2 Megafac R08 (manufactured by DIC Corporation; fluorine and silicon type)
• W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
• W-4 Troisol S-366 (manufactured by Trois Chemical Co., Ltd.)
• W-5 KH-20 (manufactured by Asahi Glass Co., Ltd.)
• W-6 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
• SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
• SL-2 Propylene glycol monomethyl ether propionate
• SL-3 2-heptanone
• SL-4 Ethyl lactate
• SL-5 Propylene glycol monomethyl ether (PGME)
• SL-6 Cyclohexanone
• SL-7 ⁇ -butyrolactone
• SL-8 Propylene carbonate
• SL-9 Diacetone alcohol
• a synthesis example of A-1 is shown below.
• Other resins were synthesized by the same method or other known methods.
• Cyclohexanone (31.3 g) was heated to 85° C. under a nitrogen stream. While stirring this liquid, a mixed solution of 4-vinylphenol (14.4 g), AS-1 (15.4 g), cyclohexanone (58.0 g), and 2,2'-azobisisobutyric acid dimethyl [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] (3.4 g) was added dropwise to this liquid over 3 hours to obtain a reaction liquid. After the dropwise addition was completed, the reaction liquid was stirred at 85° C. for another 3 hours. The obtained reaction liquid was allowed to cool, and then reprecipitated with 1400 g of ethyl acetate/heptane (mass ratio 1:9), filtered, and the obtained solid was vacuum dried to obtain A-1 (24.1 g).
• B-1 was synthesized by the method described in WO 2015/019983.
• Other salt compounds were synthesized by the same method or other known methods.
• Example 2 Preparation of Solution B-1-2
• B-1 (15 g) was placed in a 500 mL PTFE separable flask manufactured by Fluorochemical Co., Ltd., and then SL-5 (135 g) was added thereto. The mixture was stirred at 25° C. for 1 hour using a PTFE stirring blade (shape: half-moon, size: 4 cm) to obtain a 10% by mass solution of B-1 (solution B-1-2).
• Example 3 Preparation of solution B-1-3
• B-1 (15 g) was placed in a 300 mL PFA-coated eggplant flask manufactured by Sansho Co., Ltd., and then SL-5 (150 g) was added and dissolved by stirring for 1 hour at 25° C. using a PTFE stirring blade (shape: half-moon, size: 4 cm). This liquid was then concentrated at 45° C. using a rotary evaporator to obtain a 10% by mass solution of B-1 (solution B-1-3).
• Example 4 Preparation of Solution B-2-1
• a 10% by mass solution of B-2 (solution B-2-1) was obtained in the same manner as in Example 2, except that B-2 was used instead of B-1 and SL-2 was used instead of SL-5.
• Example 5 Preparation of Solution B-3-1) A 10% by mass solution of B-3 (solution B-3-1) was obtained in the same manner as in Example 2, except that B-3 was used instead of B-1 and SL-9 was used instead of SL-5.
• Example 6 Preparation of Solution B-4-1 A 10% by mass solution of B-4 (solution B-4-1) was obtained in the same manner as in Example 3, except that B-4 was used instead of B-1 and SL-1/SL-5 (mass ratio 7/3) was used instead of SL-5.
• Example 7 Preparation of Solution B-5-1) A 10% by mass solution of B-5 (solution B-5-1) was obtained in the same manner as in Example 3, except that B-5 was used instead of B-1 and SL-4 was used instead of SL-5.
• Example 8 Preparation of Solution B-6-1 A 10% by mass solution of B-6 (solution B-6-1) was obtained in the same manner as in Example 1, except that B-6 was used instead of B-1 and SL-6 was used instead of SL-5.
• Example 9 Preparation of Solution B-7-1) A 10% by mass solution of B-7 (solution B-7-1) was obtained in the same manner as in Example 2, except that B-7 was used instead of B-1 and SL-7 was used instead of SL-5.
• Example 10 Preparation of Solution B-8-1 A 10% by mass solution of B-8 (solution B-8-1) was obtained in the same manner as in Example 3, except that B-8 was used instead of B-1 and SL-8 was used instead of SL-5.
• Example 11 Preparation of solution A-1-1) A 10% by mass solution of A-1 (solution A-1-1) was obtained in the same manner as in Example 2, except that A-1 was used instead of B-1 and SL-1 was used instead of SL-5.
• Example 12 B-1 (60 g) was placed in a 1 L clean bottle (product name AC-1L) manufactured by Aicello, and then SL-5 (540 g) was added thereto. The mixture was stirred at 25° C. for 1 hour using a roller mixer to obtain a 10% by mass solution of B-1 (solution B-1-1-2).
• Example 13 B-1 (1,500 g) was placed in a 20 L clean bottle (product name AS050C) manufactured by Aicello, and then SL-5 (13,500 g) was added thereto. The mixture was stirred at 25° C. for 1 hour using a roller mixer to obtain a 10% by mass solution of B-1 (solution B-1-1-3).
• Resist compositions (R-1 to R-15 and RX-1 to RX-3) were prepared by the following solution preparation method 1 or 2.
• the prepared resist composition was applied onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130° C. for 300 seconds to obtain a resist film with a thickness of 100 nm. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate.
• HMDS hexamethyldisilazane
• ⁇ Pattern formation method (1) EB exposure, alkaline development (positive)>
• the wafer on which the resist film obtained above was formed was subjected to pattern irradiation using an electron beam lithography device (Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, lithography was performed so that a 1:1 line and space was formed.
• the wafer was heated on a hot plate at 100° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer for 60 seconds, rinsed with water for 30 seconds, and dried. Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, baked at 95° C. for 60 seconds, and dried.
• TMAH tetramethylammonium hydroxide
• Resist compositions (Q-1 to Q-6 and QX-1) were prepared by the following solution preparation method 3 or 4.
• the prepared resist composition was applied onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130° C. for 300 seconds to obtain a resist film with a thickness of 100 nm. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate.
• HMDS hexamethyldisilazane
• ⁇ Pattern formation method (2) EB exposure, alkaline development (negative)>
• the wafer on which the resist film obtained above was formed was subjected to pattern irradiation using an electron beam lithography device (Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, lithography was performed so that a 1:1 line and space was formed.
• the wafer was heated on a hot plate at 100° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer for 60 seconds, rinsed with water for 30 seconds, and dried. Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, baked at 95° C. for 60 seconds, and dried.
• TMAH tetramethylammonium hydroxide
• Resist compositions (T-1 to T-7 and TX-1) were prepared by the following solution preparation method 5 or 6.
• the prepared resist composition was applied onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130° C. for 300 seconds to obtain a resist film with a thickness of 100 nm. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate.
• HMDS hexamethyldisilazane
• ⁇ Pattern formation method (3) EUV exposure, organic solvent development (negative)>
• the wafer was heated on a hot plate at 100° C. for 90 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.
• the present invention provides a method for producing a solution that can be used to prepare a resist composition that can suppress the occurrence of development defects when used in pattern formation, a method for producing the resist composition, a pattern formation method using the resist composition produced by the method for producing the resist composition, and a method for producing an electronic device.

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