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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
  • C07D211/96—Sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
  • C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the nitrogen-containing ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
  • C07D291/02—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms not condensed with other rings
  • C07D291/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
  • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—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
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes

Definitions

• the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device that can be suitably used in ultra-microlithography processes applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the mold creation process for nanoimprinting, and the manufacturing process of high-density information recording media, as well as other photofabrication processes.
• ultra-microlithography processes applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the mold creation process for nanoimprinting, and the manufacturing process of high-density information recording media, as well as other photofabrication processes.
• Patent Document 1 discloses a resist composition containing a resin, an acid generator containing an onium salt compound, and a crosslinking agent.
• Patent Document 2 discloses a resist composition that contains an onium salt compound represented by a specific formula and a resin that includes a structural unit having an acid-dissociable group.
• Patent Document 3 discloses a resist composition containing a quencher made of an iodonium salt represented by a specific formula, a resin, and a photoacid generator.
• the present invention aims to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent EL performance and can suppress pattern collapse when forming extremely fine patterns (e.g., line width or space width of 50 nm or less).
• Another objective of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition.
• An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) and a salt (B) which is a compound represented by the following general formula (B-1):
• X represents a halogen atom.
• Y represents a single bond or a divalent linking group.
• Ar1 and Ar2 represent aromatic rings.
• a ⁇ represents a counter anion.
• a Q1 - represents a carboxylate anion or a sulfonate anion.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• L Q1 represents a divalent linking group.
• R 3 represents an organic group.
• a Q2 - represents a carboxylate anion or a sulfonate anion.
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom.
• L Q2 represents a divalent linking group.
• W represents an organic group.
• o represents an integer of 1 to 3.
• p represents an integer of 0 to 10.
• q represents an integer of 0 to 10.
• a plurality of Xf may be the same as or different from each other.
• p represents an integer of 2 or more
• R 4 and R 5 may be the same as or different from each other.
• q represents an integer of 2 or more
• a plurality of L Q2 may be the same as or
• a Q3 - represents a carboxylate anion or a sulfonate anion.
• Ar represents an aromatic group.
• n and m represent integers of 0 or more.
• D represents a single bond or a divalent linking group.
• B represents a hydrocarbon group.
• E represents a substituent other than a carboxylate anion, a sulfonate anion, and a -(D-B) group.
• n represents an integer of 2 or more
• a plurality of Ds and Bs may be the same as or different from each other.
• m represents an integer of 2 or more
• a plurality of Es may be the same as or different from each other.
• Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• La1 represents a single bond or a divalent linking group.
• Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group. Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
• Ra 0 represents an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, a hydroxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a halogen atom, or a cyano group.
• the plurality of Ra 0 may be the same or different.
• Two of Ra 1 to Ra 3 , La 1 and Ra 0 may be bonded to each other to form a ring.
• na represents an integer of 0 to 4.
• ma represents an integer of 0 to 2.
• Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• La2 represents a single bond or a divalent linking group.
• Ara represents an aromatic ring group.
• Ra 10 to Ra 12 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, or an alkenyl group. At least two of Ra 10 to Ra 12 may be bonded to each other to form a ring. At least one of Ra 9 to Ra 12 may be bound to Ara.
• a pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of items [1] to [6]; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
• an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in EL performance and capable of suppressing pattern collapse.
• the present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam).
• light means actinic rays or radiation.
• exposure includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV, and the like, but also drawing with particle beams such as electron beams and ion beams.
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• (meth)acrylate refers to at least one of acrylate and methacrylate.
• (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also called molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene equivalent values measured using a Gel Permeation Chromatography (GPC) device (Tosoh Corporation HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: refractive index detector).
• GPC Gel Permeation Chromatography
• the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes groups that have a substituent as well as groups that have no substituent.
• alkyl group includes not only alkyl groups that have no substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups).
• organic group in the present specification refers to a group that contains at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include a monovalent nonmetallic atomic group other than a hydrogen atom, and can be selected from the following substituents T.
• substituent T examples include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups
• examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).
• 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
• solids refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents.
• any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid even if it is in liquid form.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (A) and a salt (B) which is a compound represented by the following general formula (B-1):
• X represents a halogen atom.
• Y represents a single bond or a divalent linking group.
• Ar1 and Ar2 represent aromatic rings.
• a ⁇ represents a counter anion.
• the composition of the present invention contains salt (B), which is a halonium ion compound having a specific structure. Since salt (B) has a specific cationic structure, it is more decomposable by irradiation with actinic rays or radiation than sulfonium salts or iodonium salts generally used in resist compositions.
• salt (B) when salt (B) is used as a photoacid generator, the acid generation efficiency due to the decomposition of salt (B) in the exposed area is high, and the contrast between the exposed area and the unexposed area is further increased.
• salt (B) when salt (B) is used as an acid diffusion control agent, the acid diffusion control function is reduced or lost due to the decomposition of salt (B) in the exposed area more frequently, and the contrast between the exposed area and the unexposed area is further increased. It is presumed that the above-mentioned effect is manifested by this.
• compositions of the present invention are substantially free of crosslinking agents.
• the crosslinking agent is a compound that forms a covalent bond with itself or with a polymer compound by reaction to produce a polymer compound having a crosslinked structure, specifically, a low molecular weight compound having two or more polymerizable groups.
• the polymerizable group refers to a vinyl group, an epoxy group, or a methylol group.
• the phrase "substantially free of crosslinking agent” means that the content of the crosslinking agent is 0.1 mass % or less based on the total solid content of the composition of the present invention.
• the composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition.
• the composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.
• the composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• the composition of the present invention is typically a chemically amplified resist composition.
• the composition of the present invention can be used to form an actinic ray- or radiation-sensitive film.
• the actinic ray- or radiation-sensitive film formed using the composition of the present invention is typically a resist film.
• the composition of the present invention contains a resin (A).
• the resin (A) usually contains a group that decomposes under the action of an acid to increase its polarity (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.
• an acid-decomposable group typically, in a pattern formation method using the composition of the present invention, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
• the 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 the polar group is protected by a group (leaving group) that is eliminated under the action of an acid.
• the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.
• the resin (A) preferably contains at least one repeating unit selected from the group consisting of repeating units represented by general formula (A-1) and repeating units represented by general formula (A-2). At least one repeating unit selected from the group consisting of repeating units represented by general formula (A-1) and repeating units represented by general formula (A-2) is preferably a repeating unit having an acid-decomposable group.
• Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• La1 represents a single bond or a divalent linking group.
• Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group. Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
• Ra 0 represents an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, a hydroxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a halogen atom, or a cyano group.
• the plurality of Ra 0 may be the same or different.
• Two of Ra 1 to Ra 3 , La 1 and Ra 0 may be bonded to each other to form a ring.
• na represents an integer of 0 to 4.
• ma represents an integer of 0 to 2.
• Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• La2 represents a single bond or a divalent linking group.
• Ara represents an aromatic ring group.
• Ra 10 to Ra 12 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, or an alkenyl group. At least two of Ra 10 to Ra 12 may be bonded to each other to form a ring. At least one of Ra 9 to Ra 12 may be bound to Ara.
• Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• the alkyl groups of Ra 1 to Ra 3 may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the number of carbon atoms in the cycloalkyl group of Ra 1 to Ra 3 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
• the halogen atom for Ra 1 to Ra 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferable.
• the alkyl group contained in the alkoxycarbonyl group of Ra 1 to Ra 3 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.
• La 1 in the general formula (A-1) represents a single bond or a divalent linking group.
• the divalent linking group include a carbonyl group (-CO-), -O-, -S-, -SO-, -SO 2 -, an amide group (-CONR-), a sulfonamide group (-SO 2 NR-), an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group in which a plurality of these groups are linked together.
• Each of the R groups represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
• La1 is preferably a single bond or —COO—, and more preferably a single bond.
• Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group.
• the alkyl groups of Ra 4 to Ra 6 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 6.
• the methylene group contained in the alkyl groups of Ra 4 to Ra 6 may be substituted with at least one of -CO- and -O-.
• the number of carbon atoms in the cycloalkyl group of Ra 4 to Ra 6 is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• cycloalkyl group of Ra 4 to Ra 6 monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred.
• the number of carbon atoms in the aryl group of Ra 4 to Ra 6 is not particularly limited, but is preferably from 6 to 20, and more preferably from 6 to 10.
• the aryl group of Ra 4 to Ra 6 is most preferably a phenyl group.
• the aralkyl group of Ra 4 to Ra 6 is preferably a group in which one hydrogen atom in the alkyl group of the above-mentioned Ra 4 to Ra 6 is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples thereof include a benzyl group.
• the number of carbon atoms in the alkenyl group of Ra 4 to Ra 6 is not particularly limited, but is preferably from 2 to 5, and more preferably from 2 to 4.
• the alkenyl group of Ra 4 to Ra 6 is preferably a vinyl group.
• the aromatic heterocyclic group of Ra 4 to Ra 6 preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.
• the number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3.
• the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.
• the aromatic heterocyclic group may be a monocyclic or polycyclic ring.
• Examples of the aromatic heterocyclic group of Ra 4 to Ra 6 include a thienyl group, a furanyl group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a pyrrole group, an oxazolyl group, a thiazolyl group, a pyridyl group, an isothiazolyl group, and a thiadiazolyl group.
• Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
• a cycloalkyl group is preferable.
• 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 is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• -C(Ra 4 )(Ra 5 )(Ra 6 ) is preferably a leaving group, and -COO-C(Ra 4 )(Ra 5 )(Ra 6 ) is preferably such that -C(Ra 4 )(Ra 5 )(Ra 6 ) is eliminated by the action of an acid to generate a carboxyl group.
• Ra 0 represents an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, a hydroxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a halogen atom, or a cyano group.
• the alkyl group of Ra 0 may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the number of carbon atoms in the cycloalkyl group of Ra 0 is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• cycloalkyl groups of Ra 1 to Ra 3 monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred.
• the halogen atom for Ra 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferable.
• the alkyl group contained in the alkoxy group of Ra 0 may be either linear or branched.
• the number of carbon atoms of the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the alkyl group that can be contained in the acyloxy group of Ra 0 may be either linear or branched.
• the number of carbon atoms in the alkyl group that can be contained in the acyloxy group of Ra 0 is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the number of carbon atoms in the aryl group that can be contained in the acyloxy group of Ra 0 is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10.
• the aryl group that can be contained in the acyloxy group of Ra 0 is most preferably a phenyl group.
• the alkyl group contained in the alkoxycarbonyl group of Ra 0 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.
• the number of carbon atoms in the aryl group of Ra 0 is not particularly limited, but is preferably from 6 to 20, and more preferably from 6 to 10.
• the aryl group of Ra 0 is most preferably a phenyl group.
• the aromatic heterocyclic group of Ra 0 preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.
• the number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3.
• the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.
• the aromatic heterocyclic group may be monocyclic or polycyclic.
• Examples of the aromatic heterocyclic group of Ra 0 include a thienyl group, a furanyl group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a pyrrole group, an oxazolyl group, a thiazolyl group, a pyridyl group, an isothiazolyl group, and a thiadiazolyl group.
• na represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• ma represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
• the aromatic ring in general formula (A-1) is benzene when ma represents 0, naphthalene when ma represents 1, and anthracene when ma represents 2.
• repeating unit represented by general formula (A-1) are shown below, but are not limited to these.
• Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
• the explanation, specific examples, and preferred ranges for Ra 7 to Ra 9 are the same as the explanation, specific examples, and preferred ranges for Ra 1 to Ra 3 in the general formula (A-1) described above.
• La2 in the general formula (A-2) represents a single bond or a divalent linking group.
• the description, specific examples, and preferred ranges of La2 are the same as the description, specific examples, and preferred ranges of La1 in the general formula (A-1) described above.
• Ara represents an aromatic ring group.
• the aromatic ring group of Ara is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, even more preferably an arylene group having 6 to 10 carbon atoms, particularly preferably a phenylene group or naphthylene group, and most preferably a phenylene group.
• Ra 10 to Ra 12 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, or an alkenyl group.
• the alkyl groups of Ra 10 to Ra 12 may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the number of carbon atoms in the cycloalkyl group of Ra 10 to Ra 12 is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.
• cycloalkyl group of Ra 10 to Ra 12 monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred.
• the alkyl group contained in the alkoxy group of Ra 10 to Ra 12 may be either linear or branched.
• the number of carbon atoms of the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.
• the number of carbon atoms in the cycloalkyl group contained in the cycloalkyloxy group of Ra 10 to Ra 12 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.
• the number of carbon atoms in the aryl group of Ra 10 to Ra 12 is not particularly limited, but is preferably from 6 to 20, and more preferably from 6 to 10.
• the aryl group of Ra 10 to Ra 12 is most preferably a phenyl group.
• the aralkyl groups of Ra 10 to Ra 12 are preferably groups in which one hydrogen atom in the alkyl groups of Ra 10 to Ra 12 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 number of carbon atoms in the alkenyl group of Ra 10 to Ra 12 is not particularly limited, but is preferably from 2 to 5, and more preferably from 2 to 4.
• the alkenyl group of Ra 10 to Ra 12 is preferably a vinyl group.
• the aromatic heterocyclic groups of Ra 10 to Ra 12 preferably contain at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.
• the number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3.
• the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.
• the aromatic heterocyclic group may be a monocyclic or polycyclic ring.
• Examples of the aromatic heterocyclic groups of Ra 10 to Ra 12 include a thienyl group, a furanyl group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a pyrrole group, an oxazolyl group, a thiazolyl group, a pyridyl group, an isothiazolyl group, and a thiadiazolyl group.
• Ra 10 to Ra 12 may be bonded to each other to form a ring.
• a cycloalkyl group is preferable.
• 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 is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Ra 10 to Ra 12 is an alkoxy group, and it is more preferable that one of Ra 10 to Ra 12 is an alkoxy group and the other two are a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
• -C(Ra 10 )(Ra 11 )(Ra 12 ) is preferably a leaving group
• -O-C(Ra 10 )(Ra 11 )(Ra 12 ) is preferably such that -C(Ra 10 )(Ra 11 )(Ra 12 ) is eliminated by the action of an acid to generate a hydroxy group (this hydroxy group is a phenolic hydroxyl group since it is bonded to Ara).
• repeating unit represented by general formula (A-2) are shown below, but are not limited to these.
• the content of the repeating units selected from the group consisting of the repeating units represented by general formula (A-1) and the repeating units represented by general formula (A-2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in resin (A).
• the content of the repeating units selected from the group consisting of the repeating units represented by general formula (A-1) and the repeating units represented by general formula (A-2) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total repeating units in resin (A).
• the repeating units contained in resin (A) selected from the group consisting of repeating units represented by general formula (A-1) and repeating units represented by general formula (A-2) may be one type or two or more types. When two or more types are contained, it is preferable that the total content is within the above-mentioned preferred content range.
• the resin (A) may contain a repeating unit having an acid-decomposable group other than those mentioned above.
• the acid-decomposable group is preferably a group that is decomposed by the action of an acid to generate a polar group.
• 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), or an alkenyl 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 group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
• the cycloalkyl groups of Rx 1 to Rx 3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• the 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 group of Rx 1 to Rx 3 is preferably a vinyl group.
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
• 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. Furthermore, in these cycloalkyl groups, 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 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 (A).
• 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 (A).
• the repeating units having an acid-decomposable group contained in resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content is within the above-mentioned range of the preferred content. Furthermore, when the repeating units having an acid-decomposable group include repeating units represented by the above-mentioned general formula (A-1) or (A-2), it is preferable that the total content including these is within the above-mentioned range of the preferred content.
• the resin (A) preferably has a repeating unit having a polar group.
• the repeating unit having a polar group is preferably a repeating unit different from the repeating unit represented by the above-mentioned general formula (A-1), the repeating unit represented by the general formula (A-2), and the repeating unit having an acid-decomposable group.
• Examples of the polar group of the repeating unit having a polar group include a hydroxyl group, a lactone group, a sultone group, a lactam group, an imide group, an amide group, a sulfonamide group, a carbonate group, a urethane group, a urea group, a nitrile group, a sulfoxide group, and a sulfonyl group.
• the polar group may be an acid group.
• the polar group is preferably a hydroxyl group or a lactone group, more preferably an aromatic hydroxyl group, and even more preferably a phenolic hydroxyl group.
• the repeating unit having a polar group is preferably a repeating unit represented by the following general formula (A-3):
• 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 bond with Ar A to form a ring, and in that 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 explanation, specific examples and preferred ranges of R 101 , R 102 and R 103 are the same as the explanation, specific examples and preferred ranges of Ra 1 to Ra 3 in the general formula (A-1) described above.
• Ar A in the general formula (A-3) 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 1 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 64 -, an alkylene group, or a group formed by combining two or more of these groups, where R 64 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.
• 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 (A-3) 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.
• resin (A) has at least one repeating unit selected from the repeating units represented by general formula (A-1) and the repeating units represented by general formula (A-2) described above, and further has a repeating unit represented by general formula (A-3).
• repeating unit represented by general formula (A-3) are shown below, but are not limited to these.
• a represents an integer of 1 to 3.
• the content of repeating units having a polar group in resin (A) 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 resin (A).
• the content of repeating units having a polar 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 resin (A).
• the repeating units having a polar group contained in resin (A) may be of one type or of two or more types. When two or more types are contained, it is preferable that the total content is within the range of the preferred content described above.
• the resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferred that the unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure.
• a 5- to 7-membered lactone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure is more preferred.
• the description of [0120] to [0134] in WO 2022/024928 can be incorporated by reference.
• the resin (A) contains a repeating unit (hereinafter also referred to as unit X) which has neither an acid-decomposable group nor an acid group and has a fluorine atom, a bromine atom or an iodine atom.
• unit X a repeating unit which has neither an acid-decomposable group nor an acid group and has a fluorine atom, a bromine atom or an iodine atom.
• the repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom or an iodine atom is preferably different from the repeating unit having a lactone group, a sultone group or a carbonate group described above and the repeating unit having a photoacid generating group described later.
• 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.
• the content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in resin (A).
• the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in resin (A).
• the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom in the repeating units of the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the resin (A).
• the upper limit is not particularly limited, but is, for example, 100 mol% or less based on the total repeating units of the resin (A).
• Examples of the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-decomposable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.
• Resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (preferably electron beams or extreme ultraviolet rays) (hereinafter also referred to as a "photoacid generating group").
• a repeating unit having a photoacid generating group is a repeating unit represented by formula (4).
• R 41 represents a hydrogen atom or a methyl group.
• L 41 represents a single bond or a divalent linking group.
• L 42 represents a divalent linking group.
• R 40 represents a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid in a side chain. Examples of the repeating unit having a photoacid generating group are shown below, but the invention is not limited thereto.
• 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 resin (A).
• the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total repeating units in resin (A).
• the resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• the repeating units represented by the following formulae (V-1) and (V-2) are preferably repeating units different from the repeating units described above.
• R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group.
• R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms
• n3 represents an integer of 0 to 6.
• n4 represents an integer of 0 to 4.
• X4 is a methylene group, an oxygen atom, or a sulfur atom.
• Examples of the repeating unit represented by formula (V-1) or (V-2) are shown below.
• Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph [0100] of WO 2018/193954.
• Resin (A) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development.
• Tg is preferably higher than 90° C., more preferably higher than 100° C., even more preferably higher than 110° C., and particularly preferably higher than 125° C.
• Tg is preferably 400° C. or lower, more preferably 350° C. or lower.
• Tg of a repeating unit is calculated by the following method.
• the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated by the Bicerano method.
• the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated.
• the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the Tg (°C) of the polymer.
• the Bicerano method is described in Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993).
• the calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e). (a) Introduction of a bulky substituent into the main chain; (b) Introduction of a plurality of substituents into the main chain; (c) Introduction of a substituent inducing an interaction between resins (A) in the vicinity of the main chain; (d) Formation of a main chain with a cyclic structure; (e) Linking of a cyclic structure to the main chain.
• resin (A) preferably has a repeating unit showing a homopolymer Tg of 130° C. or higher.
• the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited, and may be any repeating unit exhibiting a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
• the repeating unit may be one exhibiting a homopolymer Tg of 130° C. or higher.
• One example of a specific means for achieving the above (a) is to introduce a repeating unit represented by formula (A) into resin (A).
• R represents a group containing a polycyclic structure.
• Rx represents a hydrogen atom, a methyl group, or an ethyl group.
• the group containing a polycyclic structure is a group containing a plurality of ring structures, and the plurality of ring structures may be condensed or not condensed.
• Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO 2018/193954.
• R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two of R b1 to R b4 represent an organic group.
• the type of the other organic groups is not particularly limited.
• at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.
• Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO 2018/193954.
• R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a group containing a hydrogen-bonding hydrogen atom within three atoms from a main chain carbon.
• R c1 to R c4 is a group containing a hydrogen-bonding hydrogen atom within three atoms from a main chain carbon.
• Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO 2018/193954.
• Cyclic represents a group forming a main chain with a cyclic structure.
• the number of constituent atoms of the ring is not particularly limited.
• Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO 2018/193954.
• each Re independently represents a hydrogen atom or an organic group.
• the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, each of which may have a substituent.
• Cyclic refers to a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO 2018/193954.
• the resin (A) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
• the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the preferred content is also as described above in ⁇ Repeat units having a lactone group, a sultone group, or a carbonate group>.
• the resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves the adhesion to the substrate and the affinity for the developer.
• the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
• the repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP2014-098921A.
• the resin (A) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the ⁇ -position with an electron-withdrawing group, with the carboxyl group being preferred.
• the resin (A) contains a repeating unit having an alkali-soluble group, which increases the resolution in contact hole applications. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP 2014-098921 A.
• Resin (A) may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposability. This can reduce elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure.
• repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposability include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.
• the resin (A) may have a repeating unit represented by formula (III) which has neither a hydroxyl group nor a cyano group.
• R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
• Ra represents a hydrogen atom, an alkyl group or a -CH 2 -O-Ra 2 group, where Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
• Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs [0087] to [0094] of JP2014-098921A.
• the resin (A) may have other repeating units in addition to the repeating units described above.
• resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Specific examples of repeating units other than those mentioned above are given below.
• resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developing solutions, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.
• the resin (A) particularly when the composition of the present invention is used as an ArF actinic ray- or radiation-sensitive resin composition, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate-based repeating units.
• any of the repeating units in which all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, or all of the repeating units are a mixture of methacrylate-based repeating units and acrylate-based repeating units can be used, and it is preferable that the acrylate-based repeating units account for 50 mol % or less of the total repeating units.
• the resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight (Mw) of the resin (A), as calculated in terms of polystyrene by the GPC method, is preferably 30,000 or less, more preferably 1,000 to 30,000, further preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000.
• the dispersity (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern are, and the better the roughness.
• the content of the resin (A) is preferably from 40.0 to 99.9 mass %, more preferably from 60.0 to 90.0 mass %, based on the total solid content of the composition of the present invention.
• Resin (A) may be used alone or in combination of two or more. When two or more resins are used, the total content is preferably within the above-mentioned suitable content range.
• salt (B) The composition of the present invention contains a salt (B) (hereinafter, also simply referred to as “salt (B)”), which is a compound having a halonium ion structure represented by the following general formula (B-1).
• X represents a halogen atom.
• Y represents a single bond or a divalent linking group.
• Ar1 and Ar2 represent aromatic rings.
• a ⁇ represents a counter anion.
• the halogen atom represented by X is not particularly limited, and examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of the stability of the compound, a bromine atom or an iodine atom is preferred, and a bromine atom is more preferred.
• the aromatic ring represented by Ar1 and Ar2 may be an aromatic hydrocarbon ring or an aromatic heterocycle, and may be a monocycle or a polycycle.
• Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and an azulene ring.
• a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
• the aromatic heterocycle is preferably an aromatic heterocycle containing at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom, and examples thereof include a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an indole ring, an isoindole ring, a benzimidazole ring, a purine ring, a benzotriazole ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, and a carbazole ring.
• the aromatic ring represented by Ar1 and Ar2 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
• the aromatic rings represented by Ar1 and Ar2 may have substituents.
• substituents include a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 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 atoms), an alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), an
• Y represents a single bond or a divalent linking group.
• Examples of the divalent linking group represented by Y include an alkylene group, a halogenated alkylene group, -N(Ry)-, a ketone group, an ether group, a thioether group, a sulfinyl group, a sulfonyl group, and groups consisting of combinations thereof, etc.
• Ry represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group.
• alkylene group an alkylene group having 1 to 3 carbon atoms is preferred, a methylene group or an ethylene group is more preferred, and a methylene group is even more preferred.
• Halogenated alkylene groups include the above alkylene groups in which at least one hydrogen atom has been replaced with a halogen atom.
• Ry in --N(Ry)-- represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group.
• the alkyl group may be an alkyl group having 1 to 12 carbon atoms.
• Examples of the aryl group include a phenyl group and a naphthyl group.
• the acyl group includes acyl groups having the above-mentioned alkyl or aryl groups.
• the alkyl group in the alkoxycarbonyl group includes the above-mentioned alkyl groups.
• Ry preferably represents a hydrogen atom.
• Y is preferably a single bond, a methylene group, a ketone group, a sulfonyl group, -NH-, an ether group, or a thioether group, and more preferably a single bond or a methylene group.
• a 1 ⁇ represents a counter anion.
• the counter anion A- of the salt (B) is not particularly limited, and examples thereof include organic anions such as a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, and a tris(alkylsulfonyl)methide anion. Among these, a carboxylate anion or a sulfonate anion is preferable.
• the counter anion structure is more preferably a structure represented by any one of the following general formulas (AN1) to (AN3).
• a Q1 - represents a carboxylate anion or a sulfonate anion.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• L Q1 represents a divalent linking group.
• R 3 represents an organic group.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• the substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group.
• Examples of the group that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.
• the groups which are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR', where R' is a monovalent hydrocarbon group.
• Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethy
• LQ1 represents a divalent linking group.
• the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these.
• the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 -, or -COO-alkylene group-.
• L Q1 is, for example, preferably a group represented by the following formula (AN1-1). * a - ( CR2a2 ) X - Q - ( CR2b2 ) Y - * b (AN1-1)
• * a represents the bonding position to R 3 in general formula (AN1).
• * b represents the bonding position to --C(R 1 )(R 2 )-- in formula (AN1).
• X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3.
• R 2a and R 2b each independently represent a hydrogen atom or a substituent. When a plurality of R 2a and a plurality of R 2b are present, the plurality of R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in general formula (AN1) is other than a fluorine atom.
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B .
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
• * A represents the bonding position on the R3 side in general formula (AN1)
• * B represents the bonding position on the -A Q1 - side in general formula (AN1).
• R3 represents an organic group.
• the organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group.
• the organic group may or may not have a substituent.
• the organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom).
• R3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be a monocyclic or polycyclic ring and may have a substituent.
• the ring in the organic group having a cyclic structure is preferably directly bonded to LQ1 in general formula (AN1).
• the organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom), for example.
• the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure.
• the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the cyclic hydrocarbon group is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent.
• the cycloalkyl group may be a monocyclic group (such as a cyclohexyl group) or a polycyclic group (such as an adamantyl group), and preferably has 5 to 12 carbon atoms.
• a Q2 - represents a carboxylate anion or a sulfonate anion.
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom.
• L Q2 represents a divalent linking group.
• W represents an organic group.
• o represents an integer of 1 to 3.
• p represents an integer of 0 to 10.
• q represents an integer of 0 to 10.
• a plurality of Xf may be the same as or different from each other.
• p represents an integer of 2 or more
• R 4 and R 5 may be the same as or different from each other.
• q represents an integer of 2 or more
• a plurality of L Q2 may be the same as or
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4.
• the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3 , and further preferably both Xf are fluorine atoms.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R4s and R5s are present, R4s and R5s may be the same or different.
• the alkyl group represented by R4 and R5 preferably has 1 to 4 carbon atoms.
• the alkyl group may have a substituent.
• R4 and R5 are preferably a hydrogen atom.
• LQ2 represents a divalent linking group, and is defined the same as LQ1 in formula (AN1).
• W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group.
• the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
• the alicyclic group may be a monocyclic or polycyclic.
• the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
• the heterocyclic group may be a single ring or a polycyclic ring. In particular, when the heterocyclic group is a polycyclic ring, the diffusion of the acid can be further suppressed.
• the heterocyclic group may have aromaticity or may not have aromaticity.
• heterocyclic rings having aromaticity examples include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
• heterocyclic rings not having aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group.
• the carbon that constitutes the cyclic organic group (the carbon that contributes to the ring formation) may be a carbonyl carbon.
• the anion represented by general formula (AN2) is preferably A Q2A - -CF 2 -CH 2 -OCO-(L Q2 ) q' -W, A Q2A - -CF 2 -CHF-CH 2 -OCO-(L Q2 ) q' -W, A Q2A - -CF 2 -COO-(L Q2 ) q' -W, A Q2A - -CF 2 -CF 2 -CH 2 -CH 2 -(L Q2 ) q -W, or A Q2A - -CF 2 -CH(CF 3 )-OCO-(L Q2 ) q' -W.
• L Q2 , q and W are the same as those in general formula (AN2).
• a Q2A - represents a carboxylate anion or a sulfonate anion
• q' represents an integer of 0 to 10.
• a Q3 - represents a carboxylate anion or a sulfonate anion.
• Ar represents an aromatic group.
• n and m represent integers of 0 or more.
• D represents a single bond or a divalent linking group.
• B represents a hydrocarbon group.
• E represents a substituent other than a carboxylate anion, a sulfonate anion, and a -(D-B) group.
• n represents an integer of 2 or more
• a plurality of Ds and Bs may be the same as or different from each other.
• m represents an integer of 2 or more
• a plurality of Es may be the same as or different from each other.
• Ar represents an aromatic group.
• the aromatic group is preferably an aryl group (e.g., a phenyl group).
• n and m represent integers of 0 or more.
• n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.
• m is preferably 0 to 3, and more preferably 0.
• D represents a single bond or a divalent linking group.
• divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more of these.
• B represents a hydrocarbon group.
• B is preferably an aliphatic hydrocarbon group, and more preferably a branched alkyl group such as an isopropyl group, a cycloalkyl group such as a cyclohexyl group, or an aryl group which may further have a substituent (eg, a tricyclohexylphenyl group).
• E represents a substituent other than a carboxylate anion, a sulfonate anion, and a -(D-B) group.
• substituents include a fluorine atom and a hydroxyl group.
• the anion represented by the non-nucleophilic general formula (AN3) may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.
• the anion represented by the general formula (AN3) may be a benzenecarboxylate anion.
• the counter anion A 1 ⁇ is also preferably a disulfonamide anion.
• An example of a disulfonamide anion is an anion represented by N ⁇ (SO 2 —R q ) 2 .
• R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
• Two R q may be bonded to each other to form a ring.
• the group formed by bonding two R q to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group.
• the number of carbon atoms of the alkylene group is preferably 2 to 4.
• Examples of the counter anion A 1 ⁇ also include anions represented by the following formulas (d1-1) to (d1-4).
• R 51 represents a hydrocarbon group which may have a substituent (for example, a hydroxyl group).
• the hydrocarbon group may be linear or branched, or may have a cyclic structure.
• Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (with the proviso that the carbon atom adjacent to S is not substituted with a fluorine atom).
• the hydrocarbon group in Z 2c may be linear or branched, or may have a cyclic structure.
• a carbon atom in the hydrocarbon group (preferably, when the hydrocarbon group has a cyclic structure, a carbon atom that is a ring atom) may be a carbonyl carbon (-CO-).
• Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent.
• the carbon atom forming the norbornyl group may be a carbonyl carbon.
• R 51 -COO - " in formula (d1-1) and “Z 2c -SO 3 - " in formula (d1-2) are different from the anions represented by the above formulae (AN1) to (AN3).
• R 51 and Z 2c are other than an aryl group.
• the atoms at the ⁇ -position and the ⁇ -position relative to -SO 3 - are preferably atoms other than a carbon atom having a fluorine atom as a substituent.
• the atom at the ⁇ -position and/or the atom at the ⁇ -position relative to -SO 3 - in Z 2c is a ring member atom in a cyclic group.
• R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
• Y 3 represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group
• Rf represents a hydrocarbon group
• R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom), and R 53 and R 54 may be bonded to each other to form a ring.
• the counter anion A 1 ⁇ may have a group which is decomposed by the action of an acid, and may be an anion represented by the following general formula (cN1).
• L c1 represents a single bond or a divalent linking group.
• a c1 represents a group which is decomposed by the action of an acid.
• nc represents an integer of 1 to 5.
• Xc represents an nc+1 valent linking group.
• X represents an nc+1-valent linking group.
• the linking group represented by Xc is not particularly limited, and examples thereof include an aliphatic group (which may be linear, branched, or cyclic), an aromatic group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.
• aliphatic group a group obtained by removing n hydrogen atoms from an alkyl group (which may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms) and a group obtained by removing n hydrogen atoms from a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms) are preferred.
• the aliphatic group may have a substituent, and examples of the substituent include the above-mentioned substituent T.
• the aliphatic group may have a heteroatom (eg, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon atoms.
• the aromatic group is preferably a group obtained by removing n hydrogen atoms from an aryl group (preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms.
• the aryl group is also preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group and a terphenyl group).
• the aromatic group may have a substituent, and examples of the substituent include the substituent T described above.
• the aromatic group may have a heteroatom (eg, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon atoms.
• Xc is preferably an aromatic group with a valence of nc+1.
• nc represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.
• Lc1 represents a single bond or a divalent linking group.
• the divalent linking group represented by L c1 is not particularly limited, and examples thereof include an aliphatic group (which may be linear, branched, or cyclic), an aromatic group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.
• an alkylene group (which may be linear or branched, and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms) and a cycloalkylene group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms) are preferred.
• the aliphatic group may have a substituent, and examples of the substituent include the above-mentioned substituent T.
• the aliphatic group may have a heteroatom (eg, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon atoms.
• the aromatic group is preferably an arylene group (preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms).
• the aromatic group may have a substituent, and examples of the substituent include the substituent T described above.
• the aromatic group may have a heteroatom (eg, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon atoms.
• Lc1 is preferably an arylene group.
• a c1 represents a group which is decomposed by the action of an acid.
• the group (acid decomposable group) decomposed by the action of acid represented by A c1 is not particularly limited, and examples thereof include the acid decomposable groups described in the above resin (A).
• the acid decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that decomposes and leaves by the action of acid.
• the polar group is preferably a carboxy group, a phenolic hydroxyl group, or an alcoholic hydroxyl group.
• the anion represented by the above general formula (cN1) is more preferably an anion represented by the following general formula (cN2).
• L c1 , A c1 and nc have the same meanings as L c1 , A c1 and nc in general formula (cN1), respectively.
• the salt (B) can be used as a photoacid generator described later.
• the salt (B) is a compound represented by general formula (B-1) in the photoacid generator described later.
• the salt (B) can be used as an acid diffusion controller described later.
• the salt (B) is a compound represented by general formula (B-1) in the acid diffusion controller described later.
• the content of the salt (B) is preferably from 0.1 to 60.0 mass %, more preferably from 1.0 to 50.0 mass %, particularly preferably from 1.0 to 40.0 mass %, based on the total solid content of the composition of the present invention.
• the salt (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned suitable content range.
• the composition of the present invention preferably contains a compound that generates an acid when irradiated with actinic rays or radiation (hereinafter, also referred to as a photoacid generator).
• the photoacid generator may be a compound represented by the above general formula (B-1), that is, salt (B), or may not be salt (B).
• the acid generated by the photoacid generator usually reacts with the acid-decomposable group in the resin (A).
• the photoacid generator 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 (e.g., resin (A)).
• the form of a low molecular weight compound and the form of being incorporated into a part of a polymer (e.g., resin (A)) may be used in combination.
• the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
• the photoacid generator is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).
• photoacid generators include compounds (onium salts) represented by "M + X 1 - ", and are preferably compounds that generate an organic acid upon exposure to light.
• organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.
• 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 is not particularly limited, and the valence of the organic cation may be monovalent or divalent or higher.
• the organic cation may or may not be the cation moiety shown in general formula (B-1) above.
• Examples of the group formed by bonding any two of R 201 to R 203 include an alkylene group (e.g., a butylene group and a pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• alkylene group e.g., a butylene group and a pentylene group
• the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
• the arylsulfonium cation all of R 201 to R 203 may be aryl groups, or some of R 201 to R 203 may be aryl groups, with the remainder being alkyl groups or cycloalkyl groups.
• Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group which the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
• Preferred substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have are alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 14 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups.
• alkyl groups e.g., 1 to 15 carbon atoms
• cycloalkyl groups e.g., 3 to 15 carbon atoms
• aryl groups e
• the above-mentioned substituent may further have a substituent if possible, and it is also preferable that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above-mentioned substituents are combined in any desired manner to form an acid-decomposable group.
• the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and is preferably a structure in which the polar group is protected by a group that is eliminated by the action of an acid.
• the polar group and the elimination group are as described above.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.
• Examples of the alkyl group and cycloalkyl group of R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group through any combination of the substituents.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c and R x and R y each independently form an acid-decomposable group through any combination of the substituents.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
• the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
• the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y includes alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom.
• the groups formed by combining R5c and R6c , and R5c and Rx are preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may each have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent.
• a halogen atom e.g., a fluorine atom, an iodine atom, etc.
• R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group,
• R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent.
• a halogen atom e.g., a fluorine atom and an iodine atom, etc.
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be bonded to each other to form a ring. When two R 15 are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferable that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
• the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by bonding two R 15 to each other may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like. It is also preferred that each of the substituents R 13 to R 15 and R x and R y independently form an acid-decomposable group through any combination of the substituents.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group of R 204 and R 205 may be an aryl group having a heterocycle with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group of R 204 and R 205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
• a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group
• a cycloalkyl group having 3 to 10 carbon atoms e.g
• the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. It is also preferable that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of the substituents.
• 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.
• substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
• the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.
• non-nucleophilic anions include, for example, phosphorus fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ), although organic anions are preferred.
• phosphorus fluorides eg, PF 6 ⁇
• boron fluorides eg, BF 4 ⁇
• antimony fluorides eg, SbF 6 ⁇
• organic anions are preferred.
• the non-nucleophilic anion is also preferably a disulfonamide anion.
• the disulfonamide anion is, for example, the anion represented by N ⁇ (SO 2 —R q ) 2 described above.
• the organic anion may be used alone or in combination of two or more types.
• L represents a single bond or a divalent linking group.
• A represents a group which is decomposed by the action of an acid.
• nc represents an integer of 1 to 5.
• Xc represents an nc+1 valent linking group.
• Mc + represents a sulfonium ion or an iodonium ion.
• L, A, nc, and Xc in formula (c1) have the same meanings as L c1 , A c1 , nc, and Xc in formula (cN1) above, and preferred examples are also the same.
• Mc + represents a sulfonium ion or an iodonium ion. Specific examples and preferred ranges thereof include the cations represented by formula (ZaI) and formula (ZaII) described above. Among these, the cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) described above are preferred.
• the compound represented by the above general formula (c1) is preferably a compound represented by the following general formula (c2):
• L, A, nc, and Mc + respectively have the same meanings as L, A, nc, and Mc + in the general formula (c1).
• the photoacid generator 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.
• Examples of the compound (I) include the compound (I) described in paragraphs [0176] to [0280] of WO 2022/024928.
• 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
• Examples of the compound (II) include the compound (II) described in paragraphs [0176] to [0280] of WO 2022/024928.
• photoacid generators include compounds b-1 to b-2, b-4 to b-5, b-7 to b-9, and compounds C-1 to C-6 used in the examples, but are not limited to these.
• the content of the photoacid generator is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, based on the total solid content of the composition of the present invention.
• the content of the photoacid generator is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, and even more preferably 25.0 mass% or less, based on the total solid content of the composition of the present invention.
• the photoacid generator 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 suitable content range.
• the photoacid generator may be one of the salts (B) or two or more of them.
• the photoacid generator may be one of the compounds other than the salt (B) or two or more of them.
• the salt (B) and a compound other than the salt (B) may be used in combination.
• compositions of the present invention may also include an acid diffusion control agent.
• the acid diffusion controller traps the acid generated from the photoacid generator or the like upon exposure to light and acts as a quencher that inhibits the reaction of the acid-decomposable resin in the unexposed areas caused by excess acid generated.
• the acid diffusion controller may be a compound represented by the above general formula (B-1), that is, the salt (B), or may not be the salt (B).
• 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) of an acid that is weaker than the acid generated from the photoacid generator, and a basic compound (DE) whose basicity is reduced or lost upon irradiation with actinic rays or radiation.
• Specific examples of the basic compound (DA) include those described in paragraphs [0132] to [0136] of WO 2020/066824.
• Specific examples of the basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs [0137] to [0155] of WO 2020/066824 and those described in paragraph [0164] of WO 2020/066824.
• Specific examples of the low molecular weight compound (DB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs [0156] to [0163] of WO 2020/066824.
• Specific examples of the onium salt compound (DD) that is a weak acid relative to the photoacid generator include those described in paragraphs [0305] to [0314] of WO 2020/158337.
• the onium salt compound (DD) which is a relatively weak acid to the photoacid generator may or may not be the above-mentioned salt (B).
• the counter anion A- in general formula (B-1) represents an anion in which A- in the above-mentioned general formula ( AN1 ) is a carboxylate anion, an anion in which A- in general formula (AN2) is a carboxylate anion, an anion in which A- in general formula ( AN3 ) is a carboxylate anion, or an anion represented by any of the formulae (d1-1) to (d1-4).
• acid diffusion control agents include, but are not limited to, compounds b-3, b-6, b-9, and compounds D-1 to D-6 used in the examples.
• the content of the acid diffusion controller is preferably 0.1 to 15.0 mass %, more preferably 0.5 to 15.0 mass %, based on the total solid content of the composition of the present invention.
• the acid diffusion controller may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the acid diffusion controller may be one of the salts (B) or two or more of them.
• the acid diffusion controller may be one of the compounds other than the salt (B) or two or more of them.
• the salt (B) and a compound other than the salt (B) may be used in combination.
• the composition of the present invention may further contain a hydrophobic resin different from the resin (A).
• the hydrophobic resin is preferably designed 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 a hydrophobic resin include control of the static and dynamic contact angle of water on the resist film surface, and suppression of outgassing.
• the hydrophobic resin preferably has at least one of fluorine atoms, silicon atoms, and CH3 partial structures contained in the side chain portion of the resin, more preferably has at least two of them.
• 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 hydrophobic resins include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
• the content of the hydrophobic resin is preferably from 0.01 to 20.0 mass %, more preferably from 0.1 to 15.0 mass %, based on the total solid content of the composition of the present invention.
• the hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the composition of the present invention may contain a surfactant.
• a surfactant When the composition contains a surfactant, a pattern having better adhesion and fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Examples of fluorine-based and/or silicone-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of WO 2018/193954.
• the content of the surfactant is preferably from 0.0001 to 2.0 mass%, more preferably from 0.0005 to 1.0 mass%, and still more preferably from 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention.
• the surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above-mentioned preferred content range.
• the composition of the present invention preferably contains a solvent.
• the solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate.
• the solvent may further contain components other than the components (M1) and (M2).
• the combination of the above-mentioned solvent and the above-mentioned resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern.
• the above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, so that it is possible to suppress unevenness in the thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (M1) and (M2) are described in paragraphs [0218] to [0226] of WO 2020/004306, the contents of which are incorporated herein by reference.
• the solvent further contains components other than components (M1) and (M2)
• the content of the components other than components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.
• the content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %. This further improves the applicability of the composition of the present invention.
• composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).
• a dissolution inhibiting compound for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group.
• dissolution-blocking compound is a compound with a molecular weight of 3000 or less that decomposes under the action of acid and reduces its solubility in an organic developer.
• the composition of the present invention is suitably used as a photosensitive composition for EB or EUV exposure.
• EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm) and the like, and therefore the number of incident photons is smaller when exposed at the same sensitivity. Therefore, the effect of "photon shot noise," which is the stochastic variation in the number of photons, is large, leading to deterioration of line edge roughness (LER) and bridge defects.
• One method of reducing photon shot noise is to increase the exposure dose to increase the number of incident photons, but this is a trade-off with the demand for higher sensitivity.
• the resist film formed from the resist composition has high absorption efficiency of EUV light and electron beams, which is effective in reducing photon shot noise.
• the value A represents the absorption efficiency of EUV light and electron beams by mass proportion of the resist film.
• A ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] x 39.5) / ([H] x 1 + [C] x 12 + [N] x 14 + [O] x 16 + [F] x 19 + [S] x 32 + [I] x 127)
• the value A is preferably 0.120 or more.
• the value A is preferably 0.240 or less, and more preferably 0.220 or less.
• [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [C] represents the molar ratio of carbon atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [N] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [O] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition.
• [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [I] represents the molar ratio of iodine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition.
• a resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent
• the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solid content.
• the total atoms of the total solid content corresponds to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion controller.
• [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in the total solids.
• [H] represents the molar ratio of the sum of hydrogen atoms derived from the acid-decomposable resin, the hydrogen atoms derived from the photoacid generator, and the hydrogen atoms derived from the acid diffusion controller to the sum of all atoms derived from the acid-decomposable resin, the photoacid generator, and the acid diffusion controller.
• the A value can be calculated by calculating the ratio of the numbers of atoms contained when the structure and content of all solid components in the resist composition are known. Even if the components are unknown, the ratio of the numbers of atoms contained can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.
• the present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention.
• the actinic ray- or radiation-sensitive film of the present invention is preferably a resist film.
• the procedure for the pattern formation method using the composition of the present invention is not particularly limited, but it is preferable that the method comprises the following steps. Step 1: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention; Step 2: exposing the actinic ray-sensitive or radiation-sensitive film; Step 3: developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
• Step 1 forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention
• Step 2 exposing the actinic ray-sensitive or radiation-sensitive film
• Step 3 developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
• Step 1 Actinic Ray- or Radiation-Sensitive Film Forming Step
• Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention.
• An example of a method for forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention is a method in which the composition of the present invention is applied onto a substrate.
• the composition of the present invention is preferably filtered as necessary before application.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the composition of the present invention can be applied by a suitable application method such as a spinner or coater onto a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit elements.
• 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 an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoats (inorganic films, organic films, anti-reflection films) may be formed under the actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm, since it allows for the formation of fine patterns with higher precision.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
• a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film by using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film, and can be uniformly applied on the actinic ray-sensitive or radiation-sensitive 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 an actinic ray-sensitive or radiation-sensitive film.
• the basic compound that the top coat may contain include the basic compounds that may be contained in the composition of the present invention. It is also preferred that 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 actinic ray- or radiation-sensitive film to light.
• the exposure method may be a method in which the formed actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation through a predetermined mask.
• Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called post-exposure bake.
• Step 3 is a step of developing the exposed actinic ray- or radiation-sensitive 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 discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
• dip method dip method
• spray method a method of spraying the developing solution on the substrate surface
• dynamic dispense method a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed
• 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 an quaternary ammonium salt such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine.
• 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 preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is preferably 10.0 to 15.0.
• the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• the above-mentioned solvents may be mixed in combination, or may be mixed with a solvent other than the above or with water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.
• the above pattern formation method preferably includes, after step 3, a step of cleaning with a rinsing liquid.
• the rinse liquid used in the rinse step following the step of developing with an alkaline developer may be, 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 is not particularly limited, a method is preferred in which the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to form a pattern on the substrate.
• the dry etching is preferably oxygen plasma etching.
• the composition of the present invention and various materials used in the pattern formation method preferably do not contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) 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 can 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 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 specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method.
• Preferred embodiments of the electronic device of the present specification include those mounted in electric and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, and the like).
• A-1 to A-12 were used as the resin (A).
• Resin (A) used was synthesized according to the synthesis method for resin A-1 (Synthesis Example 1) described below. The structures of A-1 to A-12 are shown below.
• the content ratio of the following repeating units is a molar ratio.
• the repeating unit content was measured by 13 C-NMR (nuclear magnetic resonance).
• A-1 to A-12 are acid-decomposable resins.
• Cyclohexanone (45.5 g) was heated to 85°C under a nitrogen stream.
• b-1 The synthesis example of b-1 is shown below.
• b-3, b-4, b-7 to b-9 were also synthesized in the same way.
• b-2 The synthesis example of b-2 is shown below.
• b-5 and b-6 were also synthesized in a similar manner.
• the photoacid generator (C) is a photoacid generator that does not correspond to the above-mentioned salt (B).
• the structures of C-1 to C-6 are shown below.
• D-1 to D-6 were used as the acid diffusion controller (D).
• the acid diffusion controller (D) is an acid diffusion controller that does not correspond to the above-mentioned salt (B).
• the structures of D-1 to D-6 are shown below.
• P-1 was used as the hydrophobic resin.
• the content ratio of the following repeating units is a molar ratio.
• the content ratio of repeating units was measured by 13 C-NMR.
• W-1 Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine-based)
• W-2 Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicone type)
• W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
• W-5 KH-20 (manufactured by Asahi Glass Co., Ltd.; fluorine-based)
• 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
• resist compositions were 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 dried on a hot plate at 130° C. for 300 seconds to obtain a resist film with a thickness of 100 nm.
• 1 inch is 0.0254 m. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate.
• Table 2 below shows the resist compositions used in each example and comparative example, as well as the results of each example and comparative example.
• an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in EL performance and capable of suppressing pattern collapse.
• the present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

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• 2023
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