WO2024150663A1 - 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 - Google Patents

感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 Download PDF

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WO2024150663A1
WO2024150663A1 PCT/JP2023/046429 JP2023046429W WO2024150663A1 WO 2024150663 A1 WO2024150663 A1 WO 2024150663A1 JP 2023046429 W JP2023046429 W JP 2023046429W WO 2024150663 A1 WO2024150663 A1 WO 2024150663A1
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group
compound
ring
sensitive
substituent
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French (fr)
Japanese (ja)
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研由 後藤
健志 川端
佑真 楜澤
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to an actinic ray- or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device.
  • a pattern formation method using chemical amplification has been used to compensate for the decrease in sensitivity due to light absorption.
  • a photoacid generator contained in the exposed portion is decomposed by light irradiation to generate an acid.
  • the catalytic action of the generated acid changes the alkali-insoluble group of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition to an alkali-soluble group, thereby changing the solubility in the developer.
  • development is performed using a basic aqueous solution.
  • the exposed portion is removed to obtain a desired pattern.
  • the wavelength of the exposure light source has become shorter and the numerical aperture (NA) of the projection lens has become higher, and currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
  • NA numerical aperture
  • an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
  • a pattern formation method using extreme ultraviolet light (EUV light: Extreme Ultraviolet) and an electron beam (EB: Electron Beam) as a light source has also been considered. Under such circumstances, various compositions have been proposed as resist compositions.
  • Patent Document 1 discloses a positive resist composition that "contains (A) an ionic compound and (B) a resin having a repeating unit (b1) that has an interactive group that interacts with the ionic group in the ionic compound, and whose main chain is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays.”
  • the inventors prepared a resist composition with reference to Patent Document 1 and formed a pattern, and found that there was room for further improvement in the line width roughness (LWR) performance of the pattern.
  • LWR line width roughness
  • Y1 The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin Y further has a repeating unit represented by formula (Y2) described below.
  • a method for producing an electronic device comprising the pattern forming method according to [8] or [9].
  • An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin YS containing a repeating unit represented by formula (Y1) described below and a repeating unit represented by formula (Y2) described below.
  • an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance. Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for producing an electronic device, which relate to the actinic ray-sensitive or radiation-sensitive resin composition.
  • FIG. 1 is a conceptual diagram showing the relationship between the dissolution rate in a developer of a resist film formed from a non-chemically amplified actinic ray-sensitive or radiation-sensitive resin composition of the prior art and the exposure dose (X-axis: exposure dose, Y-axis: dissolution rate).
  • FIG. 2 is a conceptual diagram showing the relationship between the dissolution rate in a developer of a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the exposure dose (X-axis: exposure dose, Y-axis: dissolution rate).
  • the present invention will be described in detail below. The following description of the configuration may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
  • the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention.
  • alkyl group includes not only alkyl groups that do not have a 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.
  • the substituent is preferably a monovalent substituent.
  • actinic rays or “radiation” refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc.
  • light refers to 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 light, 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.
  • the bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
  • 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 HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: refractive index detector).
  • GPC Gel Permeation Chromatography
  • the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and is specifically a value calculated using the following software package 1 based on a database of Hammett's substituent constants and publicly known literature values. All pKa values described in this specification are values calculated using this software package.
  • pKa can also be obtained by molecular orbital calculation.
  • a specific example of this method is a method of calculating H + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
  • the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in literature and are not limited to this.
  • DFT density functional theory
  • the pKa in this specification refers to a value calculated using the software package 1 based on a database of Hammett's substituent constants and known literature values.
  • a value obtained by Gaussian 16 based on DFT density functional theory
  • the pKa in this specification 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
  • halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • solids refers to components that form a resist film and does not include solvents.
  • any component that forms a resist film is considered to be a solid even if it is in liquid form.
  • the ClogP value is a value calculated by the program "CLOGP” available from Daylight Chemical Information System, Inc. This program provides a "calculated logP” value calculated by the fragment approach of Hansch and Leo (see the following literature).
  • the fragment approach is based on the chemical structure of a compound, and divides the chemical structure into partial structures (fragments), and estimates the logP value of the compound by summing up the logP contributions assigned to the fragments. Details are described in the following literature.
  • the ClogP value calculated by the program CLOGP v4.82 is used.
  • A. J. Leo Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds.
  • Log P means the common logarithm of the partition coefficient P, which is a physical property that quantitatively represents how an organic compound is distributed in equilibrium between a two-phase system of oil (generally 1-octanol) and water, and is expressed by the following formula.
  • logP log(Coil/Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the water phase.
  • boiling point means the boiling point at 1 atmosphere (760 mmHg).
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “resist composition”) is A compound XA (hereinafter, abbreviated as "compound XA”) having a conjugate acid with a pKa of 4.0 or more and containing a nitrogen atom;
  • a resin Y (hereinafter, abbreviated as "resin Y”) having a repeating unit represented by formula (Y1) described later and whose main chain is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays. include.
  • the mechanism by which the resist composition of the present invention having the above-mentioned structure is able to solve the problems of the present invention is not necessarily clear, but the present inventors speculate as follows.
  • the mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
  • the characteristics of the resist composition of the present invention will now be described in comparison with a non-chemically amplified resist composition (main chain scission type resist) of the prior art.
  • FIG. 1 is a conceptual diagram showing the relationship between the exposure dose and the dissolution rate in a developer of a resist film formed from a non-chemically amplified resist composition of the prior art (X-axis: exposure dose, Y-axis: dissolution rate), and FIG. 2 is a conceptual diagram showing the relationship between the exposure dose and the dissolution rate in a developer of a resist film formed from a resist composition of the present invention (X-axis: exposure dose, Y-axis: dissolution rate).
  • the relationship between the dissolution rate in a developer of a resist film formed from a non-chemically amplified resist composition of the prior art and the exposure dose can typically show a gentle linearity (solid line portion) as shown in Figure 1 until the exposure dose dependency of the dissolution rate is substantially eliminated.
  • the film dissolution rate is high even with a small exposure dose, so that even in unexposed areas, film dissolution in the developer occurs in response to light of the order of leakage light from exposed areas, and the LWR performance of the formed pattern may be poor.
  • the relationship between the dissolution rate of the resist film formed from the resist composition of the present invention in the developer and the exposure dose may show nonlinearity (solid line portion) until the exposure dose dependency of the dissolution rate is substantially eliminated (region C in FIG. 2), as shown in FIG. 2.
  • the dissolution rate of the film is kept low when the exposure dose is less than a predetermined value (region A in FIG. 2), and the solubility increases sharply when the exposure dose is equal to or greater than a predetermined value (region B in FIG. 2).
  • the film is less likely to dissolve in the developer in the unexposed area with light leaked from the exposed area, and the contrast of solubility between the exposed and unexposed areas is excellent, resulting in excellent LWR performance of the formed pattern.
  • the developer used in the pattern formation using the resist composition of the present invention may be either an organic solvent-based developer or an alkaline developer, but an organic solvent-based developer is preferred. Therefore, the following description will be given by taking an example in which an organic solvent developer is used as the developer.
  • the generated halogen acid forms a salt with the compound XA present in the resist film (hereinafter also referred to as a "specific salt compound").
  • This specific salt compound has low solubility in an organic solvent developer, so when the exposure dose is less than a predetermined value and the compound XA is present in excess of the halogen acid, the dissolution rate of the film is kept low (A region in FIG. 2).
  • the exposure dose is equal to or greater than a predetermined value, the main chain decomposition amount of the resin Y is large, and the halogen acid is present in excess of the compound XA, the solubility of the resist film increases sharply (B region in FIG. 2) until the exposure dose dependency of the dissolution rate is substantially eliminated (A region in FIG.
  • compound XA examples include an ionic compound (hereinafter also referred to as "compound XAI”) that contains a nitrogen atom and is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group, and a nonionic compound (hereinafter also referred to as "compound XANI”) that contains a nitrogen atom.
  • compound XAI an ionic compound
  • compound XANI nonionic compound
  • compound XA is compound XAI
  • compound XAI is cleaved (decomposed) by exposure treatment (irradiation treatment with X-rays, electron beams, or extreme ultraviolet rays), and the nitrogen-containing component of the cleavage product may form a specific salt compound that has low solubility in an organic solvent developer together with a halogen acid.
  • the resin Y has an interactive group (preferably a phenolic hydroxyl group and a carboxylic acid group, etc.) described later, the specific salt compound forms an association with the interactive group of the resin Y in the resist film, and can further reduce the solubility in an organic solvent developer.
  • the exposure dose is less than a predetermined value (see region A in FIG. 2), the dissolution rate of the film can be further reduced, and when the exposure dose is equal to or greater than a predetermined value, the solubility of the resist film can be more rapidly increased (region B in FIG. 2).
  • the resin Y has an interactive group (preferably a phenolic hydroxyl group and a carboxylic acid group, etc.) described later, the solubility contrast between the exposed and unexposed parts is more excellent, and the LWR performance of the pattern formed is more likely to be excellent.
  • an interactive group preferably a phenolic hydroxyl group and a carboxylic acid group, etc.
  • the resist composition includes compound XA.
  • Compound XA is a compound containing a nitrogen atom, the pKa of the conjugate acid of which is 4.0 or more.
  • compound XA can react with halogen acid (HX 1 ) generated in the exposed resist film to form a specific salt compound.
  • compound XA can function as a basic compound.
  • compound XA Specific examples of the structure of compound XA include an ionic compound (compound XAI) that contains a nitrogen atom and that decomposes upon irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group, and a non-ionic compound containing a nitrogen atom (compound XANI).
  • the ionic compound typically refers to a compound in which an ion pair is formed by a cation and an anion.
  • the anion in the ionic compound is a non-nucleophilic anion (an anion with a significantly low ability to cause a nucleophilic reaction)
  • the anion is likely to be decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group.
  • the "pKa of the conjugate acid of compound XA” refers to the following pKa.
  • the method for measuring pKa is as described above.
  • compound XA is compound XANI:
  • compound XA is compound XANI, it represents the pKa of a compound obtained by adding a hydrogen atom to a nitrogen atom contained in compound XANI (hereinafter also referred to as “compound XANI-A").
  • compound XANI-A when compound XANI-A further has a pKa derived from a site other than the site where a hydrogen atom has been added to the nitrogen atom, the pKa derived from the site where a hydrogen atom has been added to the nitrogen atom is defined as the "pKa of the conjugate acid of compound XA".
  • compound XANI-A when compound XANI-A has a plurality of sites where a hydrogen atom has been added to a nitrogen atom, the largest of the pKa values derived from the sites where a hydrogen atom has been added to a nitrogen atom is defined as the "pKa of the conjugate acid of compound XA".
  • compound XAI When compound XA is compound XAI: When compound XA is compound XAI, and the anion of the ionic compound formed by pairing an anion (preferably an organic anion) and a cation (preferably an organic cation) contains a nitrogen atom, a compound (hereinafter also referred to as "compound XAI-A") in which a hydrogen atom is added to a nitrogen atom contained in an anion constituting compound XAI and the cation constituting compound XAI is replaced with H + is prepared.
  • compound XAI-A a compound in which a hydrogen atom is added to a nitrogen atom contained in an anion constituting compound XAI and the cation constituting compound XAI is replaced with H + is prepared.
  • compound XAI-A the pKa value derived from the site where the hydrogen atom is added to the nitrogen atom is defined as the "pKa value of the conjugate acid of compound XA".
  • compound XAI-A has multiple sites where a hydrogen atom is added to a nitrogen atom, the largest value among the pKa values derived from the site where the hydrogen atom is added to the nitrogen atom is defined as the "pKa value of the conjugate acid of compound XA".
  • compound XA is compound XAI
  • the cation of the ionic compound formed by pairing an anion (preferably an organic anion) and a cation (preferably an organic cation) contains a nitrogen atom
  • only the cation constituting compound XAI is the subject of pKa measurement
  • the pKa of a compound in which a hydrogen atom has been added to the nitrogen atom contained in the cation (hereinafter also referred to as "compound XAI-B") is the "pKa of the conjugate acid of compound XA".
  • compound XAI-B when compound XAI-B further has a pKa derived from a site other than the site in which a hydrogen atom has been added to the nitrogen atom, the pKa derived from the site in which a hydrogen atom has been added to the nitrogen atom is the "pKa of the conjugate acid of compound XA".
  • compound XAI-B when compound XAI-B has a plurality of sites in which a hydrogen atom has been added to the nitrogen atom, the largest value of the pKa derived from the sites in which a hydrogen atom has been added to the nitrogen atom is the "pKa of the conjugate acid of compound XA".
  • compound XA is compound XAI
  • both the anion and the cation of an ionic compound constituted by a pair of an anion (preferably an organic anion) and a cation (preferably an organic cation) contain nitrogen atoms
  • the pKa value of each of compounds XAI-A and XAI-B is determined by the method described above, and the larger value is designated as the "pKa of the conjugate acid of compound XA.”
  • Compounds XANI and XAI will be described below.
  • Compound XAN1 Compound XAN I is a nonionic compound having a conjugated acid with a pKa of 4.0 or more and containing a nitrogen atom.
  • the nitrogen atom contained in compound XAN I is typically a nitrogen atom containing a non-conjugated electron pair.
  • the lower limit of the pKa of the conjugate acid of the compound XAN I is preferably 5.0 or more, more preferably 6.0 or more, and even more preferably 8.0 or more.
  • the upper limit is not particularly limited, but is preferably 15.0 or less, and more preferably 13.0 or less.
  • compound XAN1 include, but are not limited to, aromatic amines; aliphatic amines; amidines; guanidines; organic phosphazenes, etc.
  • aromatic amines include compounds containing a nitrogen-containing aromatic ring.
  • the nitrogen-containing aromatic ring may be either a monocyclic ring or a polycyclic ring.
  • the nitrogen-containing aromatic ring preferably has 5 to 15 member atoms, more preferably 5 to 10 member atoms, and even more preferably 5 or 6 member atoms.
  • the number of nitrogen atoms contained in the nitrogen-containing aromatic ring is not particularly limited, but is, for example, preferably 1 to 3, and more preferably 1 or 2.
  • the nitrogen-containing aromatic ring may contain a heteroatom other than a nitrogen atom.
  • the nitrogen-containing aromatic ring examples include an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an indole ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, and an acridine ring.
  • the nitrogen-containing aromatic ring may further have a substituent, such as the groups exemplified as the substituent T described below.
  • an imidazole ring is particularly preferred.
  • Specific examples of compounds containing an imidazole ring include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, and N-(tert-butoxycarbonyl)-2-phenylbenzimidazole.
  • aliphatic amines examples include compounds containing a nitrogen-containing aliphatic ring and compounds represented by the following formula (XANI-1).
  • the nitrogen-containing aliphatic ring may be either a monocyclic ring or a polycyclic ring.
  • the nitrogen-containing aliphatic ring preferably has 5 to 15 ring atoms, more preferably 5 to 10 ring atoms, and even more preferably 5 or 6 ring atoms.
  • the number of nitrogen atoms contained in the nitrogen-containing aliphatic ring is not particularly limited, but is, for example, preferably 1 to 3, and more preferably 1 or 2.
  • the nitrogen-containing aliphatic ring may contain a heteroatom other than a nitrogen atom.
  • nitrogen-containing aliphatic ring examples include a pyrroline ring, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and among these, a piperidine ring or a pyrrolidine ring is preferred.
  • the nitrogen-containing aliphatic ring may further have a substituent, such as the groups exemplified as the substituent T described below.
  • R 1X , R 2X , and R 3X each independently represent a hydrogen atom or an alkyl group which may have a substituent, provided that at least one of R 1X , R 2X , and R 3X represents an alkyl group which may have a substituent.
  • the alkyl group represented by R 1X , R 2X , and R 3X is preferably a linear or branched alkyl group, more preferably a linear alkyl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably has 4 to 18 carbon atoms, and even more preferably has 6 to 12 carbon atoms.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified as the substituent T described below.
  • R 1X , R 2X , and R 3X represent an alkyl group which may have a substituent, and it is more preferable that R 1X , R 2X , and R 3X all represent an alkyl group which may have a substituent.
  • amidines include cyclic amidines such as diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene, DBN), diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), and 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene (DBA-DBU).
  • cyclic amidines such as diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene, DBN), diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), and 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene (DBA-DBU).
  • guanidines include linear or cyclic guanidines such as guanidine, tetramethylguanidine (TMG), butylguanidine, diphenylguanidine (DPG), 7-methyl-1,5,7-triazabicyclodec-5-ene (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, MTBD), and 1,5,7-triazabicyclodec-5-ene (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD).
  • organic phosphazenes include 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine (BEMP).
  • Compound XAI is an ionic compound that contains a nitrogen atom and is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group.
  • the nitrogen atom contained in compound XAI is typically a nitrogen atom containing a non-conjugated electron pair.
  • the lower limit of the pKa of the conjugate acid of compound XAI is preferably 5.0 or more, more preferably 6.0 or more, and even more preferably 8.0 or more.
  • the upper limit is not particularly limited, but is preferably 15.0 or less, and more preferably 13.0 or less.
  • Compound XAI contains a nitrogen atom and has a structure in which an ion pair is formed by a cation (preferably an organic cation, and more preferably an organic cation represented by formula (ZaI) or formula (ZaII) described later) and an anion (preferably an organic anion), and the anion is preferably a non-nucleophilic anion (an anion having a significantly low ability to cause a nucleophilic reaction).
  • a cation preferably an organic cation, and more preferably an organic cation represented by formula (ZaI) or formula (ZaII) described later
  • an anion preferably an organic anion
  • the upper limit of pKa derived from the acid group of the compound XAI having an acid group generated by irradiation with X-rays, electron beams, or extreme ultraviolet rays is preferably less than 4.0 in terms of better effects of the present invention.
  • the lower limit is not particularly limited, but is, for example, preferably 1.0 or more, more preferably 3.0 or more, and even more preferably 3.5 or more.
  • the compound XAI may be in the form of either a low molecular weight compound or a high molecular weight compound, but is preferably a low molecular weight compound.
  • the molecular weight of compound XAI is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferred.
  • the nitrogen atom contained in the compound XAI may be contained in either a cation or an anion, but is preferably contained in an anion in that the effects of the present invention are more likely to be excellent.
  • the number of nitrogen atoms contained in the compound XAI may be 1 or more, for example, 1 to 6 is preferable, and 1 to 3 is more preferable.
  • the compound XAI is preferably a compound represented by the following formula (XAI-1) or a compound represented by the following formula (XAI-2).
  • M X + represents an organic cation
  • a X - represents an anionic group
  • R XA represents a monovalent organic group containing a nitrogen atom
  • L XA represents a single bond or a divalent linking group.
  • the nitrogen atom-containing monovalent organic group represented by R 2 XA is not particularly limited, and examples thereof include *-NR 2 XB 2 R 2 XC , a nitrogen-containing aromatic ring group, and a nitrogen-containing aliphatic ring group, etc.
  • * represents a bonding position.
  • R 1 XB and R 1 XC each independently represent a hydrogen atom or an alkyl group which may have a substituent, provided that at least one of R 1 XB and R 1 XC represents an alkyl group which may have a substituent.
  • the alkyl group represented by R 1 XB and R 1 XC may be any of linear, branched, and cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified as the substituent T described below. Among them, it is preferable that R 1 XB and R 1 XC each represent an alkyl group which may have a substituent.
  • the nitrogen-containing aromatic ring group can be a group formed by removing one hydrogen atom from the nitrogen-containing aromatic ring contained in the compound containing the nitrogen-containing aromatic ring represented by the above-mentioned compound XANI.
  • the nitrogen-containing aromatic ring can further have a substituent. Examples of the substituent include the groups exemplified as the substituent T described below.
  • the nitrogen-containing aliphatic ring group can be a group formed by removing one hydrogen atom from the nitrogen-containing aliphatic ring contained in the compound containing the nitrogen-containing aliphatic ring represented by the above-mentioned compound XANI.
  • the nitrogen-containing aliphatic ring can further have a substituent. Examples of the substituent include the groups exemplified as the substituent T described below.
  • the divalent linking group represented by LXA is not particularly limited, and examples thereof include -CO-, -O-, -S-, -SO-, -SO 2 -, an alkylene group, an alkenylene group, an aromatic ring group (for example, a phenylene group), and linking groups in which a plurality of these are linked together.
  • the alkylene group, the alkenylene group, and the aromatic ring group may further have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
  • Examples of the divalent linking group represented by LXA include an optionally substituted phenylene group and an alkylene group (preferably having a total of 1 to 12 carbon atoms) in which a methylene group may be substituted with at least one of -CO- and -O-.
  • a X - and R XA may be bonded to each other to form a ring.
  • the anionic group represented by A X — is a group having an anionic atom and is not particularly limited.
  • a group selected from the group consisting of groups represented by the following formulae (B-1) to (B-14), a group represented by * -O- (a group obtained by removing a proton from a hydroxy group), and a group represented by * -S- (a group obtained by removing a proton from a thiol group) is preferred, and a group selected from the group consisting of a group represented by formula (B-6), a group represented by formula (B-7), a group represented by formula (B-9), a group represented by formula (B-14), and a group represented by * -S- (a group obtained by removing a proton from a thiol group) is more preferred.
  • R X1 each independently represents a monovalent organic group.
  • R X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group. Two R X2 in formula (B-7) may be the same or different.
  • R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group, provided that at least one of the multiple R XF1 represents a fluorine atom or a perfluoroalkyl group.
  • R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n1 represents an integer of 0 to 4. When n1 represents an integer of 2 to 4, multiple R X3 may be the same or different.
  • R XF2 represents a fluorine atom or a perfluoroalkyl group.
  • R X4 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n2 represents an integer of 0 to 4. When n2 represents an integer of 2 to 4, multiple R X4s may be the same or different.
  • R 3 X1 is preferably an alkyl group or an aryl group.
  • the atom in R X1 in formula (B-5) which is directly bonded to N — is neither a carbon atom in —CO— nor a sulfur atom in —SO 2 —.
  • the alkyl group represented by R X1 may be linear, branched, or cyclic.
  • the alkyl group represented by R 1 X1 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
  • the alkyl group represented by R X1 is a cycloalkyl group, it may be a monocyclic or polycyclic group, and the number of carbon atoms is preferably 3 to 20, and more preferably 6 to 10.
  • cycloalkyl group represented by R X1 examples include a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • the aryl group represented by R 3 X1 may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 6 to 20, and more preferably 6 to 10.
  • the aryl group represented by R 3 X1 is preferably a benzene ring group.
  • the alkyl group and aryl group represented by R X1 may further have a substituent.
  • the substituent is not particularly limited, and examples thereof include the groups exemplified as the substituent T described later.
  • the substituent other than a fluorine atom and a perfluoroalkyl group represented by R 3 X2 is preferably an alkyl group other than a perfluoroalkyl group.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms therein is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
  • the alkyl group When the alkyl group is a cycloalkyl group, the alkyl group may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 3 to 20, and more preferably 6 to 10.
  • the alkyl group may further have a substituent.
  • the substituent is not particularly limited, but examples thereof include the groups exemplified as the substituent T described below.
  • each R XF1 independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group, provided that at least one of the multiple R XF1s represents a fluorine atom or a perfluoroalkyl group.
  • the perfluoroalkyl group represented by R 2 XF1 may be any of linear, branched, and cyclic.
  • the perfluoroalkyl group represented by R 1 XF1 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
  • the perfluoroalkyl group represented by R xF1 is cyclic, it may be a monocyclic or polycyclic group and the number of carbon atoms is preferably 3 to 20, and more preferably 6 to 10.
  • R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n1 represents an integer of 0 to 4.
  • n1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • the halogen atom represented by R X3 is preferably a fluorine atom.
  • Examples of the monovalent organic group represented by R X3 include an alkyl group and an aryl group.
  • the alkyl group represented by R X3 may be linear, branched, or cyclic.
  • the alkyl group represented by R 3 X3 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms therein is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
  • the alkyl group represented by R 3 X3 is a cycloalkyl group, it may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 3 to 20, and more preferably 6 to 10.
  • the aryl group represented by R 1 X3 may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 6 to 20, and more preferably 6 to 10.
  • the aryl group represented by R 1 X3 is preferably a benzene ring group.
  • the alkyl group and aryl group represented by R X3 may further have a substituent.
  • the substituent is not particularly limited, and examples thereof include the groups exemplified as the substituent T described below.
  • the perfluoroalkyl group represented by R 2 XF2 may be any of linear, branched, and cyclic.
  • the perfluoroalkyl group represented by R 2 XF2 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
  • the perfluoroalkyl group represented by R is cyclic , it may be a monocyclic or polycyclic group and the number of carbon atoms is preferably 3 to 20, and more preferably 6 to 10.
  • R X4 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the halogen atom represented by R X4 is preferably a fluorine atom.
  • n2 represents an integer of 0 to 4.
  • n2 is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • Examples of the monovalent organic group represented by R X4 include an alkyl group and an aryl group.
  • the alkyl group represented by R X4 may be linear, branched, or cyclic.
  • the alkyl group represented by R 1 X4 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of carbon atoms therein is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 or 2.
  • the alkyl group represented by R X4 is a cycloalkyl group, it may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 3 to 20, more preferably 6 to 10.
  • the aryl group represented by R 1 X4 may be a monocyclic or polycyclic group, and the number of carbon atoms therein is preferably 6 to 20, and more preferably 6 to 10.
  • the aryl group represented by R 1 X4 is preferably a benzene ring group.
  • the alkyl group and aryl group represented by R X4 may further have a substituent.
  • the substituent is not particularly limited, and examples thereof include the groups exemplified as the substituent T described below.
  • M x + is not particularly limited, but is preferably an organic cation represented by the following formula (ZaI) (cation (ZaI)) or an organic cation represented by the following formula (ZaII) (cation (ZaII)).
  • R 201 to R 203 each independently represent an organic group.
  • the number of carbon atoms in the organic groups represented by R 201 to R 203 is preferably 1 to 30, and more preferably 1 to 20.
  • Two of the organic groups represented by R 201 to R 203 may be bonded to form a ring structure, and the ring formed may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • examples of the group formed by bonding two of the organic groups represented by 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 -.
  • R 204 and R 205 each independently represent a monovalent aromatic ring group which may have a substituent or an alkyl group which may have a substituent, and a monovalent aromatic ring group is preferred in that the effects of the present invention are more excellent.
  • the monovalent aromatic ring group for R 204 and R 205 includes an aryl group and a heteroaryl group.
  • the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the ring constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.
  • the alkyl group of R 204 and R 205 is 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, and a pentyl group), or a cyclic alkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, and 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, and a pentyl group
  • a cyclic alkyl group having 3 to 10 carbon atoms e.g., a cyclopent
  • the monovalent aromatic ring group and alkyl group of R 204 and R 205 may further have another substituent.
  • the other substituent include an alkyl group (e.g., having 1 to 15 carbon atoms), a monovalent aromatic ring 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.
  • cation (ZaI) among others, cation (ZaI-1), cation (ZaI-2), or an organic cation represented by formula (ZaI-3b) or formula (ZaI-4b) is preferable.
  • R 201 to R 203 represents a monovalent aromatic ring group which may have a substituent. All of R 201 to R 203 may be monovalent aromatic ring groups, or a part of R 201 to R 203 may be a monovalent aromatic ring group, and the rest may be an alkyl group which may have a substituent.
  • one of R 201 to R 203 may be a monovalent aromatic ring group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, and the ring formed may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • the group formed by bonding two of R 201 to R 203 include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene group, pentylene group, or -CH 2 -CH 2 -O-CH 2 -CH 2 -).
  • the monovalent aromatic ring group includes an aryl group and a heteroaryl group.
  • the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the ring constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.
  • the two or more monovalent aromatic ring groups may be the same or different.
  • the alkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, such as 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, and a cyclohexyl group.
  • the monovalent aromatic ring groups and alkyl groups of R 201 to R 203 may each independently have a substituent, such as an alkyl group (e.g., having 1 to 15 carbon atoms), a monovalent aromatic ring group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., a fluorine atom, a chlorine atom, an iodine atom, etc.), a hydroxyl group, and a phenylthio group.
  • a substituent such as an alkyl group (e.g., having 1 to 15 carbon atoms), a monovalent aromatic ring group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cyclo
  • the above-mentioned substituents may further have other substituents.
  • the above-mentioned alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group.
  • Examples of the cation (ZaI-1) include triarylsulfonium cations which may have a substituent, diarylalkylsulfonium cations which may have a substituent, aryldialkylsulfonium cations which may have a substituent, diarylcycloalkylsulfonium cations which may have a substituent, and aryldicycloalkylsulfonium cations which may have a substituent, but in terms of the superior effect of the present invention, triarylsulfonium cations which may have a substituent are preferred.
  • R 201 to R 203 each independently represent an organic group not having an aromatic ring.
  • the organic groups having no aromatic ring, represented by R 201 to R 203 generally have 1 to 30 carbon atoms, and preferably have 1 to 20 carbon atoms.
  • Each of R 201 to R 203 independently represents preferably an alkyl 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 include linear alkyl groups having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), branched alkyl groups having 3 to 10 carbon atoms, and cyclic alkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
  • the alkyl groups represented by 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.
  • R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a monovalent aromatic ring 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 (such as a t-butyl group), a halogen atom, a cyano group, or an aryl group.
  • R x and R y each independently represent an alkyl group, a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
  • 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 the rings formed may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester group, 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 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having 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.
  • R 14 represents a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. When there are a plurality of R 14 , each independently represents the above group such as a hydroxyl group. Each R 15 independently represents an alkyl group or a naphthyl group. These groups may have a substituent.
  • Two R 15 may be bonded to each other to form a ring.
  • the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
  • it is preferable that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
  • the alkyl group represented by R 15 may be any one of linear, branched, and cyclic.
  • 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, or a t-butyl group.
  • M Y + represents an organic cation containing a nitrogen atom
  • a Y - represents an anionic group
  • R YA represents a monovalent organic group
  • L YA represents a single bond or a divalent linking group.
  • the monovalent organic group represented by RYA is not particularly limited, but preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms.
  • Examples of the monovalent organic group represented by RYA include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group.
  • the monovalent aliphatic hydrocarbon group and the monovalent aromatic group may further have a substituent.
  • the substituent is not particularly limited, and examples thereof include the groups exemplified as the substituent T described later.
  • the monovalent aliphatic hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • Examples of the monovalent aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred.
  • the alkyl group is a linear or branched alkyl group, it preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • the monovalent aromatic ring group may be either an aryl group or a heteroaryl group.
  • the aromatic ring constituting the monovalent aromatic ring group preferably has 6 to 15 ring members, more preferably 6 to 10 ring members, and even more preferably 6 ring members.
  • the aromatic ring constituting the monovalent aromatic ring group may be either a monocyclic ring or a polycyclic ring.
  • the monovalent aromatic ring group is preferably a phenyl group which may have a substituent.
  • a Y - and L YA have the same meanings as A X - and L XA in formula (XAI-1), and the preferred embodiments are also the same.
  • a Y - and R YA may be bonded to each other to form a ring.
  • M Y + represents an organic cation containing a nitrogen atom.
  • M Y + include an organic cation represented by formula (ZaI) represented by M X + in formula (XAI-1) above, in which at least one of R 201 to R 203 represents a monovalent organic group containing a nitrogen atom (hereinafter also referred to as "cation (ZaI-1N)"); and an organic cation represented by formula (ZaII) represented by M X + in formula (XAI-1) above, in which at least one of R 204 and R 205 represents a monovalent aromatic ring group having a substituent containing a nitrogen atom, or an alkyl group having a substituent containing a nitrogen atom (hereinafter also referred to as "cation (ZaII-1N)").
  • examples of the monovalent organic group containing a nitrogen atom include a monovalent aromatic ring group having a substituent represented by the following formula (ZaI-1N-A).
  • L XB represents a single bond or a divalent linking group.
  • the divalent linking group represented by LXB is not particularly limited, and examples thereof include -CO-, -O-, -S-, -SO-, -SO 2 -, an alkylene group, an alkenylene group, an aromatic ring group (for example, a phenylene group), and linking groups in which a plurality of these are linked together.
  • the alkylene group, the alkenylene group, and the aromatic ring group may further have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
  • Examples of the divalent linking group represented by LXB include a phenylene group which may have a substituent, and an alkylene group (preferably having a total carbon number of 1 to 12) in which a methylene group may be substituted with at least one of -CO- and -O-.
  • R 1 XZ represents *-NR 1 XB 1 R 1 XC or a nitrogen-containing aliphatic ring group, where * represents the bonding position.
  • R 1 XB and R 1 XC each independently represent a hydrogen atom or an alkyl group which may have a substituent, provided that at least one of R 1 XB and R 1 XC represents an alkyl group which may have a substituent.
  • the alkyl group represented by R 1 XB and R 1 XC may be any of linear, branched, and cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified as the substituent T described below. Among them, it is preferable that R 1 XB and R 1 XC each represent an alkyl group which may have a substituent.
  • the nitrogen-containing aliphatic ring group can be a group formed by removing one hydrogen atom from the nitrogen-containing aliphatic ring contained in the compound containing the nitrogen-containing aliphatic ring represented by the above-mentioned compound XANI.
  • the nitrogen-containing aliphatic ring can further have a substituent. Examples of the substituent include the groups exemplified as the substituent T described below.
  • the monovalent aromatic ring group includes an aryl group and a heteroaryl group, preferably an aryl group, more preferably a phenyl group or a naphthyl group, and further preferably a phenyl group.
  • the monovalent aromatic ring group may further have a substituent other than the substituent represented by the formula (ZaI-1N-A) above.
  • the cation (ZaI-1N) is preferably a cation (ZaI-1) represented by M X + in the above formula (XAI-1), in which at least one of R 201 to R 203 represents a monovalent organic group containing a nitrogen atom; more preferably a cation (ZaI-1) represented by M X + in the above formula (XAI-1), in which at least one of R 201 to R 203 represents a monovalent aromatic ring group having a substituent represented by the above formula (ZaI-1N-A); and even more preferably a cation (ZaI-1) represented by M X + in the above formula (XAI-1), in which R 201 to R 203 each independently represent a monovalent aromatic ring group which may have a substituent, and at least one of R 201 to R 203 represents a monovalent aromatic ring group having a substituent represented by the above formula (ZaI-1N-A).
  • the content of compound XA in the resist composition is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, relative to the total solid content of the resist composition.
  • the upper limit is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.
  • Compound XA may be used alone or in combination. When two or more compounds are used, the total content is preferably within the above-mentioned preferred content range.
  • the resist composition contains a resin Y.
  • Resin Y has a repeating unit represented by formula (Y1) described below, and is a resin whose main chain is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays.
  • a resin containing a repeating unit represented by formula (Y1) described later is preferred, and a resin containing a repeating unit represented by formula (Y1) described later and a repeating unit represented by formula (Y2) described later (hereinafter also referred to as "resin YS”) is more preferred.
  • the resin Y is a homopolymer of the repeating unit represented by formula (Y1)
  • the main chain of the resin Y can be decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays, but a resin containing a repeating unit represented by formula (Y1) described later and a repeating unit represented by formula (Y2) described later (resin YS) is more preferred in terms of having a better main chain decomposition efficiency.
  • the resin Y further has at least one interactive group (preferably a phenolic hydroxyl group or a carboxyl group), and more preferably contains a repeating unit having an interactive group.
  • the interactive group will be described later, but in terms of providing a more excellent effect of the present invention, a phenolic hydroxyl group or a carboxyl group is preferable.
  • the repeating unit represented by formula (Y1) and the repeating unit represented by formula (Y2) will be described below.
  • X1 represents a halogen atom.
  • the halogen atom represented by X1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the halogen atom represented by X1 is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom, in terms of the superior effect of the present invention.
  • R 1 represents a hydrogen atom or a monovalent organic group, and of these, a hydrogen atom is preferable.
  • Examples of the monovalent organic group represented by R 1 include an alkyl group which may have a substituent.
  • the alkyl group (the alkyl portion not containing a substituent) preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
  • the alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched, and more preferably linear.
  • alkyl group examples include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group; 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 substituent (hereinafter also referred to as "substituent T") that the alkyl group may have is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxamyl group.
  • substitutedine atom such as fluorine atom, chlorine atom, bromine atom, and iodine atom
  • alkyl group examples include acyl groups such as an aryl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; imino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; thiol groups; thioether groups; and combinations thereof.
  • alkyl group has a fluorine atom, it may be a perflu
  • substituent T for example, a phenolic hydroxyl group, a carboxyl group, a carbonate group, an amino group, an alkylcarbonylamino group, an imide group, a thiol group, an alkoxycarbonyl group, an alkyloxysulfonyl group, a sulfo group, and an alkylsulfonyl group can interact with the above-mentioned specific salt compound (a salt formed by a halogen acid and a compound XA) to form an association state in a form similar to a salt.
  • these groups are sometimes collectively referred to as "interactive groups”.
  • a carboxyl group or a phenolic hydroxyl group is more preferable in that the effect of the present invention is more excellent.
  • the alkyl group moiety in the alkylcarbonylamino group, alkoxycarbonyl group, alkyloxysulfonyl group, and alkylsulfonyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkyl group moiety is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.
  • the amino group may be any one of a primary amino group (-NH 2 ), a secondary amino group (-NHR A1 ; R A1 represents a monovalent aliphatic hydrocarbon group or a monovalent aromatic ring group), and a tertiary amino group (-N(R A2 ) 2 ; R A2 each independently represents a monovalent aliphatic hydrocarbon group or a monovalent aromatic ring group).
  • the monovalent aliphatic hydrocarbon group represented by R A1 or R A2 may be linear, branched, or cyclic. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.
  • Examples of the monovalent aliphatic hydrocarbon group represented by R A1 or R A2 include an alkyl group, an alkenyl group, and an alkynyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.
  • Y 1 represents —O— or —NR 3 —, and among these, —O— is preferred.
  • R 2 represents a hydrogen atom or a monovalent organic group, and preferably represents a monovalent organic group.
  • the monovalent organic group represented by R2 include an alkyl group which may have a substituent, a monovalent aromatic group which may have a substituent, an aralkyl group which may have a substituent, a lactone group which may have a substituent, and an oxacycloalkyl group which may have a substituent.
  • the alkyl group (the alkyl portion not containing a substituent) preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and n-hexyl groups; monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups; and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
  • the alkyl group may have include the groups exemplified as the substituent T described above. Of these, the substituent is preferably a halogen atom, more preferably a fluorine atom. When the alkyl group has a fluorine atom, the alkyl group may be a perfluoroalkyl group.
  • the monovalent aromatic group is not particularly limited and may be either a monocyclic or polycyclic group, and may be either an aryl group or a heteroaryl group.
  • the monovalent aromatic group preferably has 6 to 15 ring atoms, and more preferably has 6 to 10 ring atoms.
  • the monovalent aromatic group is preferably an aryl group, more preferably a phenyl group, a naphthyl group, or an anthracenyl group, and even more preferably a phenyl group.
  • Examples of the substituent that the monovalent aromatic group may have include the groups exemplified above as the substituent T. Among these, the substituent is preferably a hydroxyl group or a halogen atom.
  • the aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group, and the number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 15.
  • substituents that the aralkyl group may have include the groups exemplified as the substituent T above, and a hydroxyl group or a halogen atom is preferred.
  • the lactone group is preferably a 5- to 7-membered lactone group, and more preferably a 5- to 7-membered lactone ring to which another ring structure is condensed to form a bicyclo or spiro structure.
  • substituents that the lactone group may have include the groups exemplified above for the substituent T, and a hydroxyl group or a halogen atom is preferred.
  • the oxacycloalkyl group may be either a monocyclic or polycyclic group.
  • the oxacycloalkyl group preferably has 6 to 15 ring atoms, and more preferably has 6 to 10 ring atoms.
  • Specific examples of oxacycloalkyl groups include oxacyclohexyl groups.
  • the substituent that the oxacycloalkyl group may have includes the groups exemplified as the substituent T above, and a hydroxyl group or a halogen atom is preferred.
  • R 3 represents a hydrogen atom or a monovalent organic group, and particularly preferably represents a hydrogen atom.
  • Examples of the monovalent organic group represented by R3 include the same as the monovalent organic group represented by R2 , and preferred embodiments are also the same.
  • R 1 and R 2 , and R 2 and R 3 may be linked to each other to form a ring.
  • the ring formed by combining R 1 and R 2 , and R 2 and R 3 with each other is not particularly limited, and may be either a monocyclic ring or a polycyclic ring.
  • the ring may be either an aromatic ring or an alicyclic ring, but is preferably an alicyclic ring.
  • the ring is preferably a 5- or 6-membered alicyclic ring.
  • one embodiment of formula (Y1) in which R 1 and R 2 are linked to each other to form a ring is preferably a repeating unit represented by the following formula (Y1′).
  • Ar 1 represents a benzene ring group or a naphthalene ring group.
  • R4 represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom.
  • the monovalent substituent represented by R4 is not particularly limited, and examples thereof include the groups exemplified for the substituent T described above.
  • an alkyl group which may have a substituent is particularly preferable.
  • the alkyl group (the alkyl portion not containing a substituent) preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
  • the alkyl group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • alkyl group examples include linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
  • linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and n-hexyl groups
  • monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups
  • polycyclic cycloalkyl groups such as norbornyl, tetra
  • the substituents that the alkyl group may have include the groups exemplified above as the substituent T.
  • the alkyl group may be a perfluoroalkyl group.
  • R5 represents a hydrogen atom or a monovalent organic group, and preferably represents a monovalent organic group.
  • the monovalent organic group represented by R5 include an alkyl group which may have a substituent, and a monovalent aromatic group which may have a substituent.
  • the alkyl group (the alkyl portion not containing a substituent) preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
  • the alkyl group may be any one of linear, branched, and cyclic, but is preferably linear or branched, and more preferably linear.
  • alkyl group examples include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group; 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 alkyl group may have include the groups exemplified as the substituent T described above. Of these, the substituent is preferably a halogen atom, more preferably a fluorine atom. When the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.
  • the monovalent aromatic group is not particularly limited and may be either a monocyclic or polycyclic group, and may be either an aryl group or a heteroaryl group.
  • the monovalent aromatic group preferably has 6 to 15 ring atoms, and more preferably has 6 to 10 ring atoms.
  • the monovalent aromatic group is preferably an aryl group, more preferably a phenyl group, a naphthyl group, or an anthracenyl group, and even more preferably a phenyl group.
  • Examples of the substituent that the monovalent aromatic group may have include the groups exemplified above as the substituent T. Among these, the substituent is preferably a hydroxyl group or a halogen atom.
  • R6 represents a monovalent substituent.
  • the monovalent substituent represented by R6 is not particularly limited, and examples thereof include the groups exemplified for the substituent T described above.
  • the monovalent substituent represented by R6 the above-mentioned interactive group, a halogen atom, an alkyl group, or an acyloxy group is preferable, and an interactive group is more preferable in terms of obtaining superior effects of the present invention.
  • the interactive group is preferably a phenolic hydroxyl group or a carboxyl group.
  • the halogen atom is preferably a fluorine atom.
  • the alkyl group represented by R6 may be linear, branched, or cyclic.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the alkyl group represented by Ral may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkyl group represented by Ral is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • k represents an integer from 0 to 7, preferably 0 to 5, more preferably 0 to 3, and even more preferably 1 or 2.
  • R5 and R6 may be bonded to each other to form a ring.
  • k is an integer of 2 or more
  • a plurality of R6 may be the same or different, and R6 may be bonded to each other to form a ring.
  • the ring formed by R5 and R6 and R6 bonding to each other is not particularly limited and may be either a monocyclic ring or a polycyclic ring.
  • the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and/or a carbonyl carbon as a ring member atom.
  • the ring may be either an aromatic ring or an alicyclic ring.
  • resin Y may be a homopolymer of the repeating unit represented by formula (Y1), or may be a copolymer of the repeating unit represented by formula (Y1) with another repeating unit.
  • the resin Y is a copolymer, and the like, includes a copolymer containing a repeating unit represented by the above formula (Y1) and a repeating unit represented by the above formula (Y2).
  • the total content of the repeating units represented by the formula (Y1) and the repeating units represented by the formula (Y2) is preferably 90 mol % or more, more preferably 95 mol % or more, based on the total repeating units, and the upper limit is preferably 100 mol % or less.
  • the copolymer may be in the form of any one of a random copolymer, a block copolymer, and an alternating copolymer (a copolymer in which the repeating unit represented by the above formula (Y1) and the repeating unit represented by the above formula (Y2) are arranged alternately like ABAB); and among these, an alternating copolymer is preferable.
  • a preferred embodiment of the resin Y is one in which the proportion of the alternating copolymer in the resin Y is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the resin Y.
  • the content of the repeating unit represented by the formula (Y1) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units.
  • the upper limit is preferably 100 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units.
  • the repeating unit represented by formula (Y1) may be contained in the resin Y alone or in two or more kinds. When two or more kinds are contained, it is preferable that the total content is within the above-mentioned preferable content range.
  • the content of the repeating unit represented by the formula (Y2) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units.
  • the upper limit is, for example, preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units.
  • the repeating unit represented by formula (Y2) may be contained in the resin Y alone or in two or more kinds. When two or more kinds are contained, it is preferable that the total content is within the above-mentioned preferable content range.
  • Resin Y may further contain repeating units other than the repeating units described above.
  • Resin Y can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight of resin Y is preferably from 1,000 to 200,000, more preferably from 2,500 to 150,000, and even more preferably from 2,500 to 80,000.
  • the dispersity (molecular weight distribution) of Resin Y is usually from 1.0 to 5.0, preferably from 1.0 to 3.0, more preferably from 1.2 to 3.0, and even more preferably from 1.2 to 2.0.
  • the content of the resin Y is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total solid content of the resist composition.
  • the upper limit is preferably 100% by mass or less, and more preferably 95% by mass.
  • Resin Y may be used alone or in combination. When two or more types are used, the total content is preferably within the above-mentioned suitable content range.
  • the resist composition preferably contains a solvent.
  • the solvent preferably contains one or more selected from the group consisting of the following components (M1) and (M2):
  • the solvent may further contain a solvent other than the components (M1) and (M2).
  • (M1) Propylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate (PGMEA)).
  • M2 Propylene glycol monoalkyl ethers (propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), etc.); lactate esters (ethyl lactate, etc.); acetate esters; alkoxypropionate esters; chain ketones (diacetone alcohol, etc.); cyclic ketones (2-heptanone, cyclohexanone, cyclopentanone, etc.); lactones ( ⁇ -butyrolactone, etc.); alkylene carbonates (propylene carbonate, etc.).
  • PGME propylene glycol monomethyl ether
  • PGEE propylene glycol monoethyl ether
  • lactate esters ethyl lactate, etc.
  • acetate esters alkoxypropionate esters
  • chain ketones diacetone alcohol, etc.
  • the solvent preferably contains the component (M1), and more preferably consists essentially of the component (M1) alone or is a mixed solvent of the component (M1) with other components.
  • the solvent is a mixed solvent of component (M1) and other components, the solvent more preferably contains both component (M1) and component (M2).
  • the mass ratio (M1/M2) of the component (M1) to the component (M2) is preferably from 100/0 to 0/100, more preferably from 100/0 to 15/85, still more preferably from 100/0 to 40/60, and particularly preferably from 100/0 to 60/40.
  • the solvent may further contain components other than components (M1) and (M2).
  • the content of components other than components (M1) and (M2) is preferably 5 to 30 mass % relative to the total amount of the solvent.
  • the content of the solvent in the resist composition is preferably determined so that the solids concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %.
  • the resist composition preferably contains an ionic compound (ionic compound XB) which is different from the above-mentioned compound XA and which decomposes upon irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group.
  • ionic compound XB an ionic compound which is different from the above-mentioned compound XA and which decomposes upon irradiation with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group.
  • the ionic compound XB is a compound in which a cation and an anion form an ion pair.
  • the anion is preferably a non-nucleophilic anion (an anion with a significantly low ability to cause a nucleophilic reaction).
  • the ionic compound XB is preferably a compound in which an organic cation and an organic anion form an ion pair.
  • the pKa of the compound having an acid group (generated acid) generated from the ionic compound XB by irradiation with X-rays, electron beams, or extreme ultraviolet rays is not particularly limited, but is preferably -5.0 or more, and more preferably -1.0 or more in terms of better effects of the present invention.
  • the upper limit is not particularly limited, but is preferably less than 4.0, and more preferably 3.5 or less.
  • the ionic compound XB is also preferably a compound that does not contain a nitrogen atom.
  • the ionic compound XB may be in the form of either a low molecular weight compound or a high molecular weight compound.
  • the molecular weight of the ionic compound XB is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferable.
  • the ionic compound XB is preferably a compound represented by the following formula (XB-1):
  • M Z + represents an organic cation
  • a Z - represents an anionic group
  • R ZA represents a monovalent organic group
  • L ZA represents a single bond or a divalent linking group.
  • M Z + , A Z ⁇ , and L ZA have the same meanings as M X + , A X ⁇ , and L XA in formula (XAI-1), respectively, and the preferred embodiments are also the same.
  • R ZA has the same meaning as R YA in formula (XAI-2), and the preferred embodiments are also the same.
  • a Z - and L ZA may be bonded to each other to form a ring structure.
  • the content of the ionic compound XB is preferably from 0.1 to 30 mass %, more preferably from 0.5 to 25 mass %, and even more preferably from 1.0 to 10 mass %, based on the total solid content of the resist composition.
  • the ionic compound XB may be used alone or in combination of two or more. When two or more types are contained, the total amount thereof is preferably within the above range.
  • the resist composition preferably further contains a surfactant.
  • the surfactant is preferably a fluorine-based or silicon-based surfactant. Examples of the fluorine-based surfactant and the silicone-based surfactant 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 mass %, and more preferably from 0.0005 to 1 mass %, based on the total solid content of the composition.
  • the resist composition may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above-mentioned range.
  • the resist composition preferably further contains a hydrophobic resin different from resin Y.
  • 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 the resist film surface with water, and suppression of outgassing.
  • the hydrophobic resin preferably has one or more of "fluorine atoms", “silicon atoms”, and " CH3 partial structures contained in the side chain portion of the resin", and more preferably has two or more 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 the hydrophobic resin include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
  • the content of the hydrophobic resin is preferably 0.01 to 20 mass % relative to the total solid content of the composition, and more preferably 0.1 to 15 mass %.
  • the resist composition may further contain additives other than the above-mentioned components.
  • additives include acid diffusion control agents, dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer.
  • Step 1 Forming a resist film on a substrate using a resist composition.
  • Step 2 Exposing the resist film to light.
  • Step 3 Developing the exposed resist film using an organic solvent-based developer or an alkaline developer to form a positive pattern. The procedures for each of the above steps are described in detail below.
  • Step 1 is a step of forming a resist film on a substrate using a resist composition.
  • the resist composition is the above-mentioned resist composition of the present invention, and preferred embodiments are also as described above.
  • An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto a substrate. It is preferable to filter the resist composition before coating as necessary.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the resist composition can be applied onto a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit elements by a suitable application method such as a spinner or coater.
  • a suitable application method such as a spinner or coater.
  • the application method is preferably spin coating using a spinner.
  • the rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm.
  • the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed under the resist film.
  • the material constituting the workpiece substrate and its outermost layer may be, for example, a silicon wafer in the case of a semiconductor wafer, and examples of the material for the outermost layer include Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG (Boro-Phospho. Silicate Glass), SOG (Spin On Glass), and organic anti-reflective coatings.
  • 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 developing machine, and may 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 resist film can be formed, for example, by pre-baking at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes.
  • the thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm, since this allows for the formation of fine patterns with higher accuracy.
  • the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
  • a top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be applied uniformly over the resist film.
  • the thickness of the top coat is preferably from 10 to 200 nm, more preferably from 20 to 100 nm, and even more preferably from 40 to 80 nm.
  • the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method.
  • the top coat can be formed based on the description in paragraphs [0072] to [0082] of JP2014-059543A.
  • the basic compound that the top coat may contain include basic compounds that may be contained in the resist composition.
  • the top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl group, and an ester group.
  • Step 2 is a step of exposing the resist film to light.
  • the exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask.
  • actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 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.
  • Step 3 is a step of developing the exposed resist film with a developer to form a positive pattern.
  • the developer may be an organic solvent-based developer (a developer containing an organic solvent) or an alkaline developer. Any of the above may be used, but an organic solvent-based developer is preferred.
  • 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 still for a certain period of time for development (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).
  • a step of stopping the development while replacing the solvent with another solvent may be carried out.
  • the developing 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 organic solvent contained in the developer is preferably at least one selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
  • the ClogP value of the organic solvent contained in the developer is not particularly limited, but is preferably 0.00 or more, and more preferably 1.00 or more. When two or more organic solvents are contained, it is preferable that the ClogP value of the mixed solvent is in the above range.
  • Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.
  • ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
  • the alcohol-based solvent amide-based solvent, ether-based solvent, and hydrocarbon-based solvent
  • the solvents disclosed in paragraphs [0715] to [0718] of the specification of U.S. Patent Application Publication No. 2016/0070167 can be used.
  • the developer as a whole preferably has a water content of less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably has no substantial water content.
  • the content of the organic solvent in the developer is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, further preferably from 90 to 100% by mass, and particularly preferably from 95 to 100% by mass, based on the total amount of the developer.
  • the developer contains a first organic solvent and a second organic solvent, and it is more preferable that the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent and that the ClogP value of the first organic solvent is larger than the ClogP value of the second organic solvent.
  • the content ratio of the first organic solvent to the second organic solvent in the developer is not particularly limited, but in terms of the effect of the present invention being more excellent, the mass ratio of the content of the second organic solvent to the content of the first organic solvent is preferably 1 to 50, and more preferably 3 to 20.
  • the above-mentioned ketone-based solvent or the above-mentioned ester-based solvent is preferred, from the viewpoint of providing a better effect of the present invention, and an ester-based solvent is more preferred, with butyl acetate or isoamyl butyrate being even more preferred.
  • the above-mentioned first organic solvent is not particularly limited, but is preferably an organic solvent having a ClogP value of 3.00 or more, and more preferably a hydrocarbon-based solvent (preferably a hydrocarbon-based solvent having 10 or more carbon atoms, such as undecane).
  • the above pattern forming method preferably includes, after step 3, a step 4 of washing the pattern with a rinsing liquid containing an organic solvent.
  • the rinse liquid contains an organic solvent.
  • the organic solvent contained in the rinse liquid is preferably at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.
  • Examples of the hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include those similar to those described in the developer containing an organic solvent.
  • the rinse solution contains a first organic solvent and a second organic solvent, and it is more preferable that the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and that the ClogP value of the first organic solvent is higher than the ClogP value of the second organic solvent.
  • the boiling points refer to the boiling points at 1 atmosphere (760 mmHg).
  • the ratio of the contents of the first organic solvent and the second organic solvent in the rinse solution is not particularly limited, but in terms of the effect of the present invention being more excellent, the mass ratio of the content of the second organic solvent to the content of the first organic solvent is preferably 1 to 50, and more preferably 3 to 20.
  • the above-mentioned ketone-based solvent or the above-mentioned ester-based solvent is preferred, from the viewpoint of providing a better effect of the present invention, and an ester-based solvent is more preferred, with butyl acetate or isoamyl butyrate being even more preferred.
  • the above-mentioned first organic solvent is not particularly limited, but is preferably an organic solvent having a ClogP value of 3.00 or more, and more preferably a hydrocarbon-based solvent (preferably a hydrocarbon-based solvent having 10 or more carbon atoms, such as undecane).
  • 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 of the present invention 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 preferably performed at 40 to 250°C (preferably 90 to 200°C) for 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, which is the object to be etched.
  • the pattern formed in step 3 may be used as an etching mask to process the substrate (or the underlayer film and the substrate) to form a pattern on the substrate.
  • the method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, a method 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 developer contains two or more types of organic solvents
  • the pattern formation method includes step 4
  • at least one of the developer and the rinsing liquid contains two or more types of organic solvents.
  • the two or more organic solvents contained in the developer and the rinse liquid a combination of the above-mentioned first organic solvent and second organic solvent is preferable.
  • the resist composition and various materials used in the pattern formation method of the present invention preferably do not contain impurities such as metals.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
  • examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
  • methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials that make up the various materials, filtering the raw materials that make up the various materials, and performing distillation under conditions that minimize contamination as much as possible, such as lining the inside of the equipment with Teflon (registered trademark).
  • impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used.
  • adsorbent known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • inorganic adsorbents such as silica gel and zeolite
  • organic adsorbents such as activated carbon.
  • metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment.
  • the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.
  • the present invention also relates to a method for producing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device produced by this production method.
  • the electronic device of the present invention is suitably mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
  • Resins (A) (resins A-1 to A-11) shown in Table 5 below are shown below. Note that resins A-1 to A-11 correspond to resin Y described above. Resin A-1 was synthesized by the synthesis method (Synthesis Example 1) described later. Resins A-1 to A-11 were synthesized according to the synthesis method (Synthesis Example 1) of Resin A-1 described later or by known methods. Table 1 shows the content (mol %; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw/Mn) of each repeating unit shown below.
  • the weight average molecular weight (Mw) and dispersity (Mw/Mn) of Resins A-1 to A-11 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent).
  • the content of each repeating unit was measured by 13 C-NMR (Nuclear Magnetic Resonance).
  • reaction solution after cooling was dropped into 660 g of stirred methanol, and the powder precipitated by the dropwise addition was filtered and dried to obtain 11.5 g of A-1a.
  • 11.5 g of A-1a, 36.0 g of cyclohexanone, and 36.0 g of methanol were placed in a three-necked flask under a nitrogen stream and dissolved by stirring.
  • 8.0 g of triethylamine was added to the three-necked flask and reacted at 80° C. for 16 hours.
  • reaction solution was allowed to cool, 300 g of ethyl acetate was added, washed with 100 g of 1 mol/l hydrochloric acid, and further washed three times with 100 g of water.
  • the obtained ethyl acetate solution was concentrated and dissolved in 20 g of methanol, and the obtained solution was dropped into 200 g of water, and the precipitated powder was collected by filtration and dried, to obtain 8.8 g of A-1.
  • composition ratio (molar ratio) of the repeating units of the above resin A-1 determined by NMR (nuclear magnetic resonance) was 45/55 (repeating units derived from the deacetylated (OH) monomer M-1)/repeating units derived from methyl ⁇ -chloroacrylate.
  • the weight average molecular weight of the obtained resin A-1 measured by GPC was 25,000 in terms of standard polystyrene, and the polydispersity (Mw/Mn) was 2.0.
  • Basic Compound (B) The structures of basic compounds (B) (basic compounds B-1 to B-10 and basic compounds CB-1 to CB-2) shown in Table 5 below are shown below. Note that basic compounds B-1 to B-10 correspond to compound XA (basic compounds B-1 to B-3, B-9: correspond to compound XANI; basic compounds B-4 to B-8, B-10: correspond to compound XAI). Basic compounds CB-1 and CB-2 are comparative compounds. In addition, the pKa of each of the conjugate acids of basic compounds B-1 to B-10 and basic compounds CB-1 to CB-2 is shown in Table 2 below. The method for measuring the pKa of the conjugate acid of the basic compound is as described above. Hereinafter, the method for measuring the pKa will be described by taking basic compounds B-4 and B-6 as examples.
  • Basic compound B-4 is the compound shown below in which a hydrogen atom is added to the nitrogen atom contained in the anion and the triphenylsulfonium cation is replaced with H + .
  • the pKa of the compound is determined by a method using the above-mentioned software package 1 or the like, and the pKa derived from the site where the hydrogen atom is added to the nitrogen atom is regarded as the "pKa of the conjugate acid of basic compound B-4.”
  • the pKa of the conjugate acid of basic compound B-4 is 9.6.
  • surfactant The surfactants shown in Table 5 below (surfactants W-1 to W-2) are shown below.
  • W-1 Megafac F176 (DIC Corporation; fluorine-based)
  • W-2 Megafac R08 (DIC Corporation; fluorine and silicon type)
  • SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • PGME Propylene glycol monomethyl ether
  • SL-3 Cyclohexanone
  • SL-4 ⁇ -butyrolactone
  • SL-5 Ethyl lactate
  • SL-6 Diacetone alcohol
  • Table 5 is shown below.
  • the case where resin Y has at least one of a phenolic hydroxyl group and a carboxy group is indicated as "X”, and the case where this does not apply is indicated as "Y".
  • compound XA is an ionic compound that decomposes when irradiated with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group, it is indicated as "X,” and if not, it is indicated as "Y.”
  • the case where the resist composition contains the ionic compound XB is indicated as "X"
  • the case where this does not apply is indicated as "Y".
  • the silicon wafer having the resist film obtained by the above-mentioned procedure was subjected to pattern irradiation using an EUV exposure device (Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech).
  • EUV exposure device Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech.
  • the pattern obtained in the above ⁇ Pattern formation> was observed from above the pattern using a critical dimension scanning electron microscope (SEM (S-9380II, Hitachi, Ltd.)).
  • SEM critical dimension scanning electron microscope
  • the line width of the pattern was observed at 250 points, and the standard deviation ( ⁇ ) was determined.
  • the measurement variation of the line width was evaluated at 3 ⁇ , and the value of 3 ⁇ was defined as LWR (nm).
  • the results are shown in Table 6.
  • the LWR rating is preferably 4.0 or less, more preferably 3.6 or less, still more preferably 3.3 or less, particularly preferably 3.1 or less, and most preferably 2.9 or less.
  • A1 Resin Y has at least one of a phenolic hydroxyl group and a carboxy group
  • A2 Compound XA is an ionic compound (compound XAI) that decomposes when irradiated with X-rays, electron beams, or extreme ultraviolet rays to generate a compound having an acid group.
  • A3 The resist composition contains an ionic compound XB.
  • A4 The resist composition contains an ionic compound XB which generates an acid with a pKa of ⁇ 1.0 or more.

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WO2020137935A1 (ja) * 2018-12-27 2020-07-02 三菱瓦斯化学株式会社 化合物、（共）重合体、組成物、パターン形成方法、及び化合物の製造方法
WO2021153466A1 (ja) * 2020-01-31 2021-08-05 富士フイルム株式会社 ポジ型レジスト組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法

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* Cited by examiner, † Cited by third party
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WO2020137935A1 (ja) * 2018-12-27 2020-07-02 三菱瓦斯化学株式会社 化合物、（共）重合体、組成物、パターン形成方法、及び化合物の製造方法
WO2021153466A1 (ja) * 2020-01-31 2021-08-05 富士フイルム株式会社 ポジ型レジスト組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法

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