WO2024116797A1 - Composition de résine sensible à la lumière active ou sensible au rayonnement, film de réserve, procédé de formation de motif, et procédé de fabrication de dispositif électronique - Google Patents

Composition de résine sensible à la lumière active ou sensible au rayonnement, film de réserve, procédé de formation de motif, et procédé de fabrication de dispositif électronique Download PDF

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WO2024116797A1
WO2024116797A1 PCT/JP2023/040638 JP2023040638W WO2024116797A1 WO 2024116797 A1 WO2024116797 A1 WO 2024116797A1 JP 2023040638 W JP2023040638 W JP 2023040638W WO 2024116797 A1 WO2024116797 A1 WO 2024116797A1
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group
sensitive
formula
radiation
alkyl group
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PCT/JP2023/040638
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Japanese (ja)
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健志 川端
研由 後藤
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富士フイルム株式会社
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  • 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, for example, 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.
  • pattern formation methods using extreme ultraviolet (EUV) and electron beam (EB) as light sources are also being considered in recent years. Under these circumstances, various compositions have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.
  • Patent Document 1 describes a positive resist composition that contains an ⁇ -methylstyrene unit and an ⁇ -methyl chloroacrylate unit, has a molecular weight distribution (Mw/Mn) of 1.24 or more and less than 1.48, has a weight average molecular weight (Mw) of 36,000 or more and 70,000 or less, has a proportion of components having a molecular weight of less than 6,000 of 0.2% or less, and has a proportion of components having a molecular weight of more than 100,000 of 1.0% or more, and includes a polymer and a solvent.
  • Mw/Mn molecular weight distribution
  • Mw weight average molecular weight
  • An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. Another object of the present invention is to provide a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.
  • An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin containing a repeating unit represented by the following formula (Z-1) and a solvent, provided that when Rd in the above formula (Z-1) is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, and Re is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, the above resin further contains a repeating unit represented by the following formula (1):
  • Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent.
  • Y 1 and Y 2 each independently represent -O-, -S-, -CO-, -SO 2 -, -NR-, a divalent aromatic ring group, or a group formed by combining these, or a single bond.
  • R represents a hydrogen atom or an alkyl group.
  • L 1 represents a single bond or a n+1-valent linking group.
  • n represents an integer of 1 or more. When n represents an integer of 2 or more, the multiple Re, Rf and Y 2 may be the same or different.
  • Rc and at least one of Y 1 and L 1 may be bonded to each other to form a ring.
  • Rf and at least one of Y 2 and L 1 may be bonded to each other to form a ring.
  • X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • Ra represents a hydrogen atom or a substituent.
  • R 1 represents a substituent.
  • R 1 and Ra may be bonded to each other to form a ring.
  • An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin in which two or more polymers each containing a repeating unit represented by the following formula (1) are bonded to each other via side chains, and a solvent.
  • X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • Ra represents a hydrogen atom or a substituent.
  • R 1 represents a substituent. R 1 and Ra may be bonded to each other to form a ring.
  • A1 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • Rb represents a hydrogen atom or a substituent.
  • Ar represents an aromatic hydrocarbon group. Ar and Rb may be bonded to each other to form a ring.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin contains one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group.
  • Re is a substituent and Y2 is a divalent aromatic hydrocarbon group.
  • [11] forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9]; exposing the resist film to actinic light or radiation; developing the exposed resist film using a developer;
  • a pattern forming method comprising: [12] A method for manufacturing an electronic device, comprising the pattern formation method according to [11].
  • an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. Furthermore, according to the present invention, there can be provided a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.
  • the present invention will be described in detail below. The following description of the components 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 emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, 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.
  • to means 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 actinic ray-sensitive or radiation-sensitive resin composition of the present invention can typically be used as a resist composition.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition”) is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit represented by the following formula (Z-1) and a solvent, provided that when Rd in formula (Z-1) is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, and Re is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, the resin (A) further contains a repeating unit represented by the following formula (1).
  • Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent.
  • Y 1 and Y 2 each independently represent -O-, -S-, -CO-, -SO 2 -, -NR-, a divalent aromatic ring group, or a group formed by combining these, or a single bond.
  • R represents a hydrogen atom or an alkyl group.
  • L 1 represents a single bond or a n+1-valent linking group.
  • n represents an integer of 1 or more. When n represents an integer of 2 or more, the multiple Re, Rf and Y 2 may be the same or different.
  • Rc and at least one of Y 1 and L 1 may be bonded to each other to form a ring.
  • Rf and at least one of Y 2 and L 1 may be bonded to each other to form a ring.
  • X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • Ra represents a hydrogen atom or a substituent.
  • R 1 represents a substituent.
  • R 1 and Ra may be bonded to each other to form a ring.
  • the resin (A) contained in the resist composition of the present invention is a resin whose main chain is decomposed by irradiation with actinic rays or radiation and has a crosslinked structure. Since the resin (A) has a crosslinked structure, the change in molecular weight before and after the decomposition of the main chain becomes large, and the change in dissolution rate in a developer (dissolution contrast) also becomes large, which is thought to improve the resolution.
  • the resist composition of the present invention contains a resin (A) that contains a repeating unit represented by the above formula (Z-1), provided that when Rd in the above formula (Z-1) is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, and Re is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, the resin (A) further contains a repeating unit represented by the above formula (1).
  • resin (A) is also referred to as "specific resin".
  • the specific resin is typically a resin whose main chain is decomposed when irradiated with actinic rays or radiation, and is preferably a resin whose main chain is decomposed when irradiated with X-rays, electron beams or extreme ultraviolet rays.
  • a specific embodiment of the specific resin is preferably a resin containing a repeating unit represented by the above formula (Z-1) and a repeating unit represented by the above formula (1) (hereinafter also referred to as "specific resin 1").
  • the specific resin in terms of the superior effect of the present invention, as described below, it is preferable that the specific resin contains one or more functional groups (hereinafter also referred to as "specific functional groups") selected from the group consisting of hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, and acetoxy groups, and it is more preferable that the specific resin contains one or more functional groups selected from the group consisting of phenolic hydroxyl groups and carboxyl groups.
  • specific functional groups hereinafter also referred to as "specific functional groups” selected from the group consisting of hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, and acetoxy
  • the repeating unit represented by formula (Z-1) will be described below.
  • the repeating unit represented by formula (Z-1) has a structure (crosslinked structure) in which two or more polymers (main chains) are bonded to each other via side chains.
  • Rc represents a hydrogen atom or a substituent.
  • the substituent represented by Rc is not particularly limited, but is preferably an organic group, and is preferably an alkyl group or a cycloalkyl group.
  • the alkyl group may be linear or branched.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the alkyl group and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • Rc is preferably a hydrogen atom in that the effects of the present invention are more excellent.
  • Rd represents a hydrogen atom or a substituent.
  • Rd preferably represents a substituent.
  • the substituent represented by Rd is not particularly limited, but is preferably a halogen atom or an organic group.
  • a halogen atom represented by Rd a chlorine atom is preferred in that the effects of the present invention are more excellent.
  • the organic group represented by Rd is preferably an alkyl group or a cycloalkyl group.
  • the alkyl group may be linear or branched.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the alkyl group and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • Rd is a fluorinated alkyl group or a fluorinated cycloalkyl group.
  • the fluorinated alkyl group and the fluorinated cycloalkyl group may contain one or more fluorine atoms, but in terms of the superior effect of the present invention, it is preferred that the fluorinated alkyl group or the fluorinated cycloalkyl group is a perfluoroalkyl group or a perfluorocycloalkyl group.
  • Rd is preferably a halogen atom, a fluorinated alkyl group or an unsubstituted alkyl group, in that the effects of the present invention are more excellent.
  • Re represents a hydrogen atom or a substituent.
  • Re has the same meaning as Rd above, and the preferred embodiments are also the same.
  • Rf represents a hydrogen atom or a substituent.
  • Rf has the same meaning as Rc above, and the preferred embodiments are also the same.
  • Y1 and Y2 each independently represent -O-, -S-, -CO-, -SO2- , -NR-, a divalent aromatic ring group, a group formed by combining these, or a single bond, and R represents a hydrogen atom or an alkyl group.
  • the divalent aromatic ring group may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group.
  • the number of carbon atoms in the divalent aromatic hydrocarbon group is preferably from 6 to 20, and more preferably from 6 to 15.
  • the divalent aromatic hydrocarbon group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.
  • the number of carbon atoms in the divalent aromatic heterocyclic group is preferably 2 to 20, and more preferably 3 to 15.
  • the divalent aromatic heterocyclic group is preferably a divalent group containing a heterocycle containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom as a ring member, and examples thereof include divalent groups containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring.
  • the divalent aromatic ring group may have a substituent.
  • the alkyl group represented by R may be linear or branched.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • R is preferably a hydrogen atom.
  • Y1 and Y2 each independently represent -O-, -CO-, -NR-, a divalent aromatic hydrocarbon group, or a group formed by combining these, or a single bond, and it is more preferable that Y1 and Y2 each independently represent -O-, -CO-, -NR-, a divalent aromatic hydrocarbon group, or a group formed by combining these, or a single bond.
  • L1 represents a single bond or a linking group having a valence of n+1.
  • n represents an integer of 1 or more.
  • n preferably represents an integer of 1 to 10, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
  • the (n+1)-valent linking group represented by L1 is a divalent linking group (when n is 1), it is preferably -O-, -S-, -CO-, -SO 2 -, -NR-, a divalent hydrocarbon group, or a group formed by combining these.
  • R represents a hydrogen atom or an alkyl group.
  • R has the same meaning as R in Y1 and Y2 described above, and the preferred embodiments are also the same.
  • Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.
  • the alkylene group may be linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the cycloalkylene group may be a monocyclic or polycyclic ring.
  • the cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the number of carbon atoms in the arylene group is preferably from 6 to 20, and more preferably from 6 to 15.
  • the arylene group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.
  • the divalent hydrocarbon group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom).
  • the n+1-valent linking group represented by L1 is a divalent linking group, it is preferably -O-, -CO-, a divalent hydrocarbon group, or a group formed by combining these, and more preferably a divalent linking group containing a divalent hydrocarbon group.
  • divalent linking group containing a divalent hydrocarbon group a divalent hydrocarbon group or a group formed by combining a divalent hydrocarbon group with at least one of -O- and -CO- is preferred.
  • n is an integer of 2 or more
  • examples of the (n+1)-valent linking group represented by L1 include groups obtained by removing any n-1 hydrogen atoms from a divalent linking group containing a divalent hydrocarbon group, among the divalent linking groups described above.
  • the repeating unit represented by formula (Z-1) is preferably any one of the following (i) to (iv):
  • Re is a substituent and Y2 is a divalent aromatic hydrocarbon group.
  • the content of the repeating unit represented by formula (Z-1) in the specific resin may be 0.1 to 100 mol %, preferably 0.1 to 30 mol %, more preferably 0.5 to 20 mol %, and even more preferably 1 to 15 mol %, based on the total repeating units of the specific resin.
  • the repeating unit represented by formula (Z-1) may be one type or two or more types. When the repeating unit represented by formula (Z-1) is two or more types, the total content thereof is preferably within the above numerical range.
  • the specific resin may contain a repeating unit represented by formula (1) in addition to the repeating unit represented by formula (Z-1), even in cases other than those in which Rd is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group, and Re is not a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • the repeating unit represented by formula (1) the main chain becomes easily decomposable, and therefore, it is preferable that the specific resin includes the repeating unit represented by formula (1).
  • X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • halogen atom represented by X a chlorine atom is preferred in that the effects of the present invention are more excellent.
  • the alkyl group in the fluorinated alkyl group represented by X may be either linear or branched.
  • the number of fluorine atoms substituted on the alkyl group may be one or more, but it is preferable that the alkyl group is a perfluoroalkyl group in terms of better effects of the present invention.
  • the fluorinated alkyl group represented by X preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the cycloalkyl group in the fluorinated cycloalkyl group represented by X may be monocyclic or polycyclic.
  • the cycloalkyl group may have one or more fluorine atoms substituted thereon, but is preferably a perfluorocycloalkyl group in terms of the superior effect of the present invention.
  • the fluorinated cycloalkyl group represented by X preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • X is preferably a halogen atom, and more preferably a chlorine atom, in that the effects of the present invention are more excellent.
  • Ra represents a hydrogen atom or a substituent.
  • the substituent represented by Ra is not particularly limited, but is preferably an organic group, and is preferably an alkyl group or a cycloalkyl group.
  • the alkyl group may be linear or branched.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the alkyl group and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • Ra is preferably a hydrogen atom in that the effects of the present invention are more excellent.
  • R 1 represents a substituent.
  • the substituent represented by R1 is not particularly limited, and examples thereof include a group represented by the following formula (1-1), a hydroxyl group, and -NH2 .
  • R X represents a hydrogen atom or an organic group.
  • the organic group represented by R 1 X is not particularly limited, but is preferably, for example, a linear or branched alkyl group or a cycloalkyl group.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • the cycloalkyl group may be either monocyclic or polycyclic.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the alkyl group and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • R 1 X is preferably a hydrogen atom in that the effects of the present invention are more excellent.
  • R 1A represents a hydrogen atom or an organic group.
  • the organic group represented by R 1A is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a group containing an onium salt structure described below.
  • the alkyl group may be either linear or branched.
  • the number of carbon atoms in the alkyl group is not particularly limited, and for example, 1 to 20 is preferable, 1 to 10 is more preferable, and 1 to 6 is even more preferable.
  • the cycloalkyl group may be either a monocyclic or polycyclic group.
  • the number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10.
  • Examples of the cycloalkyl group include 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 and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • the alkyl group includes a group represented by -C(R x1 )(R x2 )(R x3 ), where R x1 to R x3 each independently represent a linear or branched alkyl group or a cycloalkyl group.
  • the number of carbon atoms in the alkyl group represented by R X1 to R X3 is not particularly limited, and is, for example, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
  • the cycloalkyl group may be either monocyclic or polycyclic.
  • the number of carbon atoms in the cycloalkyl group is not particularly limited, and is, for example, preferably 5 to 15, and more preferably 5 to 10.
  • cycloalkyl group examples include 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.
  • R X1 to R X3 each independently represent a linear or branched alkyl group (preferably a linear alkyl group), or two of R X1 to R X3 combine to form a monocyclic or polycyclic 5- to 8-membered alicyclic ring.
  • the alkyl groups represented by R X1 to R X3 may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • L 1A preferably represents -O- or -N(R x )-, and more preferably represents -O-.
  • the aryl group may be either a monocyclic or polycyclic ring, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
  • the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group may have a substituent.
  • the substituent is not particularly limited and may be a halogen atom (preferably a fluorine atom or an iodine atom) or a specific functional group, and among these, a fluorine atom, an iodine atom, or a hydroxyl group is preferable.
  • the aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is replaced with the aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 15.
  • R1 and Ra may be bonded to each other to form a ring.
  • the ring may contain a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member atom.
  • the repeating unit represented by formula (1) is preferably a repeating unit represented by the following formula (1A), in that the effect of the present invention is more excellent.
  • X and Ra have the same meanings as X and Ra in formula (1), and preferred embodiments are also the same.
  • L 2A represents -O- or -N(R x )-.
  • R x represents a hydrogen atom or an organic group. Examples of the organic group represented by R x include the same as R x in formula (1-1) above.
  • R 1A represents a hydrogen atom or an organic group. Examples of the organic group represented by R 1A include the same as R 1A in formula (1-1) above.
  • Ra and R 1A may be bonded to each other to form a ring. Examples of the ring formed by Ra and R 1A bonded to each other include the same rings as those formed by Ra and R 1 in the above formula (1) bonded to each other.
  • the content of the repeating unit represented by formula (1) in the specific resin is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, and even more preferably 20 to 80 mol %, based on the total repeating units of the specific resin.
  • the repeating unit represented by formula (1) may be one type or two or more types. When the repeating unit represented by formula (1) is two or more types, the total content thereof is preferably within the above numerical range.
  • the specific resin contains a repeating unit represented by formula (1)
  • it is preferable that the specific resin is a resin in which two or more polymers containing a repeating unit represented by formula (1) are bonded to each other via side chains.
  • the specific resin may contain repeating units other than the repeating unit represented by formula (Z-1) and the repeating unit represented by formula (1).
  • the specific resin preferably contains a repeating unit represented by the following formula (2):
  • A1 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • Rb represents a hydrogen atom or a substituent.
  • Ar represents an aromatic hydrocarbon group. Ar and Rb may be bonded to each other to form a ring.
  • A1 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • the alkyl group represented by A1 may be either linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
  • the alkyl group may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • the cycloalkyl group represented by A1 may be a single ring or a polycyclic ring.
  • the number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10.
  • the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is even more preferable, a methyl group or an ethyl group is particularly preferable, and a methyl group is most preferable.
  • Rb represents a hydrogen atom or a substituent.
  • the substituent represented by Rb is not particularly limited, but is preferably an organic group, and is preferably an alkyl group or a cycloalkyl group.
  • the alkyl group may be linear or branched.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 5 to 10 carbon atoms.
  • the alkyl group and the cycloalkyl group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • Rb is preferably a hydrogen atom in that the effects of the present invention are more excellent.
  • Ar represents an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group may be either monocyclic or polycyclic.
  • the number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 15, and more preferably 6 to 10.
  • the aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group.
  • the aromatic hydrocarbon group may have a substituent.
  • the substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom) and a specific functional group.
  • the content of the repeating unit represented by formula (2) in the specific resin is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, and still more preferably 20 to 80 mol %, based on the total repeating units of the specific resin.
  • the repeating unit represented by formula (2) may be one type or two or more types. When the repeating unit represented by formula (2) is two or more types, the total content thereof is preferably within the above numerical range.
  • the specific resin preferably contains a repeating unit represented by the above formula (Z-1) and a repeating unit represented by the above formula (1), and particularly preferably contains a repeating unit represented by the above formula (Z-1), a repeating unit represented by the above formula (1), and a repeating unit represented by the above formula (2).
  • the specific resin is a copolymer containing a plurality of types of repeating units, it may be in the form of any one of a random copolymer, a block copolymer, an alternating copolymer, and the like.
  • the onium salt structure is a structural moiety having an ion pair of a cation and an anion, and is preferably a structural moiety represented by “X n ⁇ nM + ” (wherein n represents, for example, an integer of 1 to 3, and preferably represents 1 or 2).
  • M + represents a structural moiety containing a positively charged atom or atomic group
  • Xn- represents a structural moiety containing a negatively charged atom or atomic group.
  • the anion in the onium salt structure is preferably a non-nucleophilic anion (anion with a significantly low ability to cause a nucleophilic reaction).
  • anion in the onium salt structure is a non-nucleophilic anion, it is likely to become a photodegradable onium salt structure. This is the same as the non-nucleophilic anion in the photodegradable onium salt compound described later.
  • the cation in the onium salt structure is the same as the cationic moiety in the photodegradable onium salt compound described later.
  • the specific resin in terms of the better effect of the present invention, as described above, it is preferable that the specific resin contains one or more functional groups (specific functional groups) selected from the group consisting of hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, and acetoxy groups, and it is more preferable that the specific resin contains one or more functional groups selected from the group consisting of phenolic hydroxyl groups and carboxyl groups.
  • functional groups specific functional groups selected from the group consisting of hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, and acetoxy groups
  • the specific resin contains one or more functional groups selected from the group consisting of
  • the specific resin when the specific resin has the specific functional group, it interacts with an ionic compound that the resist composition may contain, thereby further increasing the dissolution contrast between the unexposed and exposed areas in the resist film, and the effect of the present invention is more likely to be excellent.
  • the phenolic hydroxyl group herein refers to a hydroxyl group substituted on a member atom of an aromatic ring.
  • the aromatic ring is not limited to a benzene ring, and may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the aromatic ring may be either a monocyclic ring or a polycyclic ring.
  • An alcoholic hydroxyl group is to be differentiated from a phenolic hydroxyl group, and in this specification it refers to a hydroxyl group which substitutes for an aliphatic hydrocarbon group.
  • the amino group is preferably a group represented by -N(R P ) 2.
  • the amide group is preferably a group represented by -CO-N(R q ) 2 or a group represented by -CO-N(R q )-.
  • the imide group is preferably a group represented by -CO-N(R q )-CO-.
  • the sulfonamide group is preferably a group represented by -SO 2 -N(R q ) 2 or a group represented by -SO 2 -N(R q )-.
  • Each of the above R P and R q independently preferably represents a hydrogen atom or a monovalent organic group (preferably an alkyl group having 1 to 6 carbon atoms), more preferably a hydrogen atom.
  • the case where the specific resin contains a group represented by -CO-N(R q )-, -CO-N(R q )-CO- or -SO 2 -N(R q )- as a specific functional group corresponds to, for example, a case where Ra and R 1A in the repeating unit represented by formula (1) above are linked to each other to form a ring, and the ring has a structural moiety represented by -CO-N(R q )-, a structural moiety represented by -CO-N(R q )-CO- or a structural moiety represented by -SO 2 -N(R q )-.
  • the specific resin preferably contains a repeating unit containing a specific functional group, in that the effects of the present invention are more excellent.
  • the content of the repeating unit containing the specific functional group in the specific resin is preferably 5 to 100 mol %, more preferably 10 to 100 mol %, and even more preferably 20 to 100 mol %, based on all repeating units in the specific resin.
  • the repeating unit containing the specific functional group may be one type or two or more types. When the repeating unit containing the specific functional group is two or more types, the total content thereof is preferably within the above numerical range.
  • the specific resin can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight of the specific resin is preferably 1,000 to 200,000, more preferably 2,500 to 150,000, and even more preferably 4,000 to 90,000.
  • the weight average molecular weight is within the above numerical range, deterioration of heat resistance and dry etching resistance can be further suppressed.
  • deterioration of developability and deterioration of film formability due to an increase in viscosity can be further suppressed.
  • the dispersity (molecular weight distribution, Mw/Mn) of the specific resin is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0.
  • the content of the specific resin (resin (A)) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% by mass or more, and particularly preferably 70% by mass or more, based on the total solid content of the resist composition.
  • the upper limit may be 100% by mass or less, and may be 95% by mass or less.
  • the specific resin 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 of the present invention preferably contains a solvent.
  • the solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate.
  • the solvent may further contain components other than the components (M1) and (M2).
  • component (M1) at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred, with propylene glycol monomethyl ether acetate (PGMEA) being more preferred.
  • PGMEA propylene glycol monomethyl ether acetate
  • the propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferred.
  • the lactate ester is preferably ethyl lactate, butyl lactate, or propyl lactate.
  • the acetate ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Also preferred is butyl butyrate.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred.
  • chain ketone 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone is preferred.
  • the cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.
  • the lactone is preferably ⁇ -butyrolactone.
  • the alkylene carbonate propylene carbonate is preferred.
  • component (M2) is propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, gamma-butyrolactone, or propylene carbonate.
  • PGME propylene glycol monomethyl ether
  • ethyl lactate ethyl 3-ethoxypropionate
  • methyl amyl ketone cyclohexanone
  • butyl acetate pentyl acetate
  • gamma-butyrolactone gamma-butyrolactone
  • the solvent preferably includes an ester-based solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or less heteroatoms.
  • an ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butanoate is preferred, and isoamyl acetate is more preferred.
  • the solvent preferably contains the component (M1). More preferably, the solvent consists essentially of the component (M1) alone, or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent further preferably contains both the component (M1) and the component (M2).
  • the mass ratio (M1/M2) of the component (M1) to the component (M2) is preferably in the range of "100/0" to "15/85", more preferably in the range of "100/0" to "40/60", and even more preferably in the range of "100/0" to "60/40".
  • the solvent is preferably composed of only the component (M1) or contains both the component (M1) and the component (M2), and the mass ratio thereof is as follows.
  • the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and even more preferably 60/40 or more.
  • the mass ratio of component (M1) to component (M2) can be, for example, 99/1 or less.
  • the solvent further contains components other than components (M1) and (M2)
  • the content of the components other than components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.
  • the content of the solvent in the resist composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass, in order to provide better coatability.
  • the resist composition of the present invention may contain other components in addition to the resin (A) and the solvent.
  • the other components are not particularly limited, but examples thereof include ionic compounds (specifically, photodecomposable onium salt compounds) and surfactants.
  • the resist composition of the present invention preferably contains an ionic compound.
  • the ionic compound is preferably a component different from the resin (A).
  • the ionic compound may be a compound that decomposes when irradiated with actinic rays or radiation, or may not decompose.
  • the compound that decomposes when irradiated with actinic rays or radiation may be a compound that decomposes when irradiated with actinic rays or radiation to generate an acid, or a compound that decomposes when irradiated with actinic rays or radiation to generate a base.
  • the ionic compound is preferably a compound having an onium salt structure that generates an acid when irradiated with actinic rays or radiation (photodecomposition type onium salt compound).
  • the resin (A) is likely to aggregate with the ionic compound in the unexposed area via the specific functional group that may be contained in the resin (A).
  • the ionic compound and the specific functional group are dissociated or the photodegradable onium salt compound is cleaved, so that the aggregate structure can be released.
  • the dissolution contrast between the unexposed area and the exposed area in the resist film is further increased by the above action, and the effect of the present invention is more likely to be excellent.
  • the resin (A) contained in the resist composition preferably has the above-mentioned specific functional group.
  • the photodecomposable onium salt compound is preferably a compound which has at least one salt structure moiety composed of an anion moiety and a cation moiety and which decomposes upon exposure to generate an acid (preferably an organic acid).
  • the above-mentioned salt structure portion of the photodecomposable onium salt compound is preferably composed of an organic cation portion and an organic anion portion having extremely low nucleophilicity, since this portion is easily decomposed by exposure to light and has excellent organic acid generation properties.
  • the salt structure moiety may be a part or the whole of the photodecomposable onium salt compound.
  • organic acid generated from the photodecomposable onium salt compound by the action of exposure to light examples include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.
  • the organic acid generated from the photodecomposable onium salt compound by the action of exposure may be a polyvalent acid having two or more acid groups.
  • the organic acid generated by decomposition of the photodecomposable onium salt compound by exposure is a polyvalent acid having two or more acid groups.
  • the cationic moiety constituting the salt structure moiety is preferably an organic cationic moiety, and among these, an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)) as described below is preferred.
  • Photodecomposable onium salt compound PG1 An example of a suitable embodiment of the photodecomposable onium salt compound is an onium salt compound represented by "M + X - ", which generates an organic acid upon exposure to light (hereinafter also referred to as "photodecomposable onium salt compound PG1").
  • M + represents an organic cation
  • X - represents an organic anion.
  • the organic cation represented by M + in the photodecomposable onium salt compound PG1 is preferably an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)).
  • R 201 , R 202 and R 203 each independently represent an organic group.
  • the number of carbon atoms in the organic group represented by R 201 , R 202 , and R 203 is usually 1 to 30, and preferably 1 to 20.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (e.g., a butylene group and a pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
  • Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), an organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.
  • one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring.
  • Examples of the group formed by bonding two of R 201 to R 203 include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene group, pentylene group, or -CH 2 -CH 2 -O-CH 2 -CH 2 -).
  • arylsulfonium cation examples include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
  • the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
  • the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group which the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
  • Preferred substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 14 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and the like.
  • an alkyl group e.g., 1 to 15 carbon atoms
  • the above-mentioned substituent may further have a substituent if possible.
  • the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
  • Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represent an organic group not having an aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a heteroatom.
  • the organic group not having an aromatic ring represented by R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms.
  • Each of R 201 to R 203 independently represents preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.
  • the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
  • Each of R 1c to R 5c independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
  • R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
  • R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
  • R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
  • the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
  • the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y includes alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom.
  • the groups formed by combining R5c and R6c , and R5c and Rx are preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
  • R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may each have a substituent.
  • the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
  • l represents an integer of 0 to 2.
  • r represents an integer of 0 to 8.
  • R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group 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.
  • a halogen atom e.g., a fluorine atom, an iodine atom, etc.
  • R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group,
  • R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group 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.
  • a halogen atom e.g., a fluorine atom, an iodine atom, etc.
  • each independently represents the above group such as a hydroxyl group.
  • Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be bonded to each other to form a ring. When two R 15 are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferable that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
  • the alkyl group, the cycloalkyl group, and the naphthyl group, as well as the ring formed by bonding two R 15 to each other may have a substituent.
  • the alkyl groups of R 13 , R 14 , and R 15 are preferably linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10.
  • the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.
  • R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group of R 204 and R 205 preferably has 2 to 20 carbon atoms, more preferably a phenyl group or naphthyl group, and particularly preferably a phenyl group.
  • the aryl group of R 204 and R 205 may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 and R 205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 15 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
  • the organic anion represented by X 1 - in the photodecomposable onium salt compound PG1 is preferably a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
  • non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
  • the organic anion is preferably, for example, an organic anion represented by the following formula (DA):
  • a 31- represents an anionic group.
  • R a1 represents a hydrogen atom or a monovalent organic group.
  • L a1 represents a single bond or a divalent linking group.
  • a 31- and R a1 may be bonded to each other to form a ring.
  • a 31- represents an anionic group.
  • the anionic group represented by A 31- is not particularly limited, but is preferably a group selected from the group consisting of groups represented by formulae (BA-1) to (BA-14), and more preferably formulae (BA-1), (BA-2), (BA-3), (BA-4), (BA-5), (BA-6), (BA-10), (BA-12), (BA-13), and (BA-14).
  • R 1 X1 each independently represents a monovalent organic group.
  • each R X2 independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group.
  • Two R X2 in formula (BA-7) may be the same or different.
  • R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. Of the two R XF1 , at least one represents a fluorine atom or a perfluoroalkyl group.
  • R XF1 in formula (BA-8) may be the same or different.
  • R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n1 represents an integer of 0 to 4.
  • R 2 XF2 represents a fluorine atom or a perfluoroalkyl group.
  • the bond to the bonding position represented by * in formula (BA-14) is preferably a phenylene group which may have a substituent. Examples of the substituent which the phenylene group may have include a halogen atom.
  • R 1 X1 each independently represents a monovalent organic group.
  • R X1 is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms), or an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms).
  • the above group represented by R X1 may have a substituent.
  • the atom in R X1 in formula (B-5) that is directly bonded to N- is neither a carbon atom in --CO-- nor a sulfur atom in --SO 2 --.
  • the cycloalkyl group in R X1 may be a monocyclic or polycyclic group.
  • Examples of the cycloalkyl group in R X1 include a norbornyl group and an adamantyl group.
  • the substituent that the cycloalkyl group in R X1 may have is not particularly limited, but is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms). One or more of the carbon atoms that are ring members of the cycloalkyl group in R X1 may be replaced with a carbonyl carbon atom.
  • the alkyl group in R 3 X1 preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • the substituent that the alkyl group in R may have is not particularly limited, but is preferably, for example, a cycloalkyl group, a fluorine atom, or a cyano group. Examples of the cycloalkyl group as the substituent are the same as those described when R is a cycloalkyl group.
  • the alkyl group in R X1 has a fluorine atom as the above-mentioned substituent, the above-mentioned alkyl group may be a perfluoroalkyl group.
  • the alkyl group in R X1 may have one or more -CH 2 - substituted with a carbonyl group.
  • the aryl group in R X1 is preferably a phenyl group.
  • the substituent that the aryl group in R may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group as the substituent are the same as those described when R is an alkyl group .
  • R X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group (for example, an alkyl group not containing a fluorine atom and a cycloalkyl group not containing a fluorine atom).
  • Two R X2 in formula (BA-7) may be the same or different.
  • R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, among the multiple R XF1 , at least one represents a fluorine atom or a perfluoroalkyl group.
  • the two R XF1 in formula (BA-8) may be the same or different.
  • the number of carbon atoms of the perfluoroalkyl group represented by R XF1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.
  • R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the halogen atom represented by R X3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the monovalent organic group represented by R 1 X3 is the same as the monovalent organic group described as R 1 X1 .
  • n1 represents an integer of 0 to 4.
  • n1 is preferably an integer of 0 to 2, and more preferably 0 or 1. When n1 represents an integer of 2 to 4, multiple R 3 X3 may be the same or different.
  • R 2 XF2 represents a fluorine atom or a perfluoroalkyl group.
  • the perfluoroalkyl group represented by R 2 XF2 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • the number of carbon atoms of the monovalent organic group of R a1 is not particularly limited, but preferably is 1 to 30 carbon atoms, and more preferably is 1 to 20 carbon atoms.
  • R a1 is preferably an alkyl group, a cycloalkyl group or an aryl group.
  • the alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.
  • the aryl group may be monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
  • the cycloalkyl group may contain heteroatoms as ring members.
  • the heteroatom is not particularly limited, but examples thereof include a nitrogen atom and an oxygen atom.
  • the alkyl group, cycloalkyl group and aryl group may further have a substituent.
  • a 31- and R a1 may be bonded to each other to form a ring.
  • the divalent linking group represented by L a1 is not particularly limited, and examples thereof include an alkylene group, a cycloalkylene group, an aromatic group, -O-, -CO-, -COO-, and a group formed by combining two or more of these.
  • the alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.
  • the cycloalkylene group may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms, and more preferably has 3 to 10 carbon atoms.
  • the aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
  • the aromatic ring constituting the aromatic group may be an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the aromatic ring is not particularly limited, but may be, for example, an aromatic ring having 6 to 20 carbon atoms, specifically, a benzene ring, a naphthalene ring, an anthracene ring, a thiophene ring, etc.
  • the aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
  • the alkylene group, cycloalkylene group and aromatic group may further have a substituent, and the substituent is preferably a halogen atom.
  • L a1 preferably represents a single bond.
  • the photodecomposable onium salt compound PG1 it is also preferable to use, for example, the photoacid generators disclosed in paragraphs [0135] to [0171] of WO 2018/193954, paragraphs [0077] to [0116] of WO 2020/066824, and paragraphs [0018] to [0075] and [0334] to [0335] of WO 2017/154345.
  • the molecular weight of the photodegradable onium salt compound PG1 is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
  • Photodecomposable onium salt compound PG2 Another example of a suitable embodiment of the photodecomposable onium salt compound includes the following compound (I) and compound (II) (hereinafter, "compound (I) and compound (II)” are also referred to as “photodecomposable onium salt compound PG2").
  • the photodecomposable onium salt compound PG2 has two or more of the above-mentioned salt structure moieties and is a compound that generates a polyvalent organic acid upon exposure to light.
  • the photodecomposable onium salt compound PG2 will now be described.
  • Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation:
  • Structural moiety X a structural moiety consisting of an anionic moiety A 1 - and a cationic moiety M 1 + , and which forms a first acidic moiety represented by HA 1 upon exposure to actinic rays or radiation.
  • Structural moiety Y a structural moiety consisting of an anionic moiety A 2 - and a cationic moiety M 2 + , and which forms a second acidic moiety represented by HA 2 upon exposure to actinic rays or radiation.
  • compound (I) satisfies the following condition I.
  • Compound PI which is obtained by replacing the cationic moiety M 1 + in the structural moiety X and the cationic moiety M 2 + in the structural moiety Y in compound (I) with H + , has an acid dissociation constant a1 derived from the acidic moiety represented by HA 1 , which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H + , and an acid dissociation constant a2 derived from the acidic moiety represented by HA 2 , which is obtained by replacing the cationic moiety M 2 + in the structural moiety Y with H + , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
  • the compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
  • the structural moieties X may be the same or different from each other.
  • the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
  • the A 1 - and A 2 - , and the M 1 + and M 2 + may be the same or different, but it is preferable that the A 1 - and A 2 - are different.
  • the anionic moiety A 1 - and the anionic moiety A 2 - are structural moieties containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6). In the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position.
  • R A represents a monovalent organic group. Examples of the monovalent organic group represented by R A include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
  • the cationic moiety M 1 + and the cationic moiety M 2 + are structural moieties containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge.
  • the organic cation is not particularly limited, but is preferably an organic cation represented by the above formula (ZaI) (cation (ZaI)) or an organic cation represented by the above formula (ZaII) (cation (ZaII)).
  • Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation.
  • Structural moiety Z a non-ionic moiety capable of neutralizing an acid
  • the compound (II) can generate a compound PII (acid) having an acidic site represented by HA 1 in which the cationic site M 1 + in the structural site X is replaced with H + .
  • the compound PII represents a compound having the acidic site represented by HA 1 and a structural site Z which is a nonionic site capable of neutralizing an acid.
  • the definition of the structural moiety X and the definitions of A 1 - and M 1 + in compound (II) are the same as the definition of the structural moiety X and the definitions of A 1 - and M 1 + in compound (I) described above, and the preferred embodiments are also the same.
  • the two or more structural moieties X may be the same or different from each other, and the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
  • the nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a functional group having an electron or a group capable of electrostatically interacting with a proton.
  • functional groups having a group or electrons capable of electrostatically interacting with a proton include functional groups having a macrocyclic structure such as cyclic polyether, or functional groups having a nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:
  • Examples of partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.
  • the molecular weight of the photodegradable onium salt compound PG2 is preferably 100 to 10,000, more preferably 100 to 2,500, and even more preferably 100 to 1,500.
  • the content of the ionic compound is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the resist composition.
  • the content of the ionic compound is preferably 50.0 mass% or less, and more preferably 40.0 mass% or less, based on the total solid content of the resist composition.
  • the ionic compound may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
  • the resist composition of the present invention may further contain a hydrophobic resin different from the resin (A).
  • the hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances.
  • the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to the developer, and suppression of outgassing.
  • the hydrophobic resin preferably has at least one of fluorine atom, silicon atom, and CH3 partial structure contained in the side chain portion of the resin, more preferably has at least two of them.
  • the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
  • the content of the hydrophobic resin is preferably from 0.01 to 20.0 mass %, and more preferably from 0.1 to 15.0 mass %, based on the total solid content of the resist composition.
  • the hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
  • the resist composition may contain a surfactant, which can provide a pattern with better adhesion and fewer development defects.
  • the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
  • fluorine-based and/or silicone-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of WO 2018/193954.
  • the 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 resist composition.
  • the surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above-mentioned preferred content range.
  • a preferred embodiment of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is an actinic ray-sensitive or radiation-sensitive resin composition that contains a resin in which two or more polymers containing a repeating unit represented by the following formula (1) are bonded to each other via side chains, and a solvent.
  • X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group.
  • Ra represents a hydrogen atom or a substituent.
  • R 1 represents a substituent. R 1 and Ra may be bonded to each other to form a ring.
  • the resin in which two or more polymers containing a repeating unit represented by formula (1) are bonded to each other via side chains is typically a resin having a structure in which two or more polymers containing a repeating unit represented by formula (1) are crosslinked, and can be obtained, for example, by reacting a monomer corresponding to the repeating unit represented by formula (1) with a crosslinking agent (e.g., a compound having two or more polymerizable groups).
  • a crosslinking agent e.g., a compound having two or more polymerizable groups
  • the present invention also relates to a resist film formed using the above resist composition, and a pattern forming method using the above resist film.
  • the pattern forming method of the present invention is preferably a pattern forming method comprising the steps of forming a film using the resist composition, exposing the film to light, and developing the exposed film using a developer.
  • the procedure of the above pattern formation method is not particularly limited, but it is preferable that the method includes the following steps. Step 1: Forming a resist film on a substrate using a resist composition; Step 2: Exposing the resist film to actinic rays or radiation; Step 3: Developing the exposed resist film using a developer. The procedure for each of the above steps will be described in detail below.
  • Step 1 is a step of forming a resist film on a substrate using a resist composition.
  • An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto a substrate. It is preferable to filter the resist composition before coating as necessary.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the resist composition can be applied onto a substrate (e.g., silicon, silicon 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 (rotations per minute).
  • the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed under the resist film.
  • the drying method may be, for example, a method of drying by heating. Heating can be performed by a means provided in a normal exposure machine and/or a developing machine, and may also be performed using a hot plate or the like.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
  • the thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm, since it allows for the formation of fine patterns with higher accuracy.
  • the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
  • the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
  • a top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film.
  • the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs [0072] to [0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-061648 on the resist film.
  • 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 bond, and an ester bond.
  • Step 2 is a step of exposing the resist film to light.
  • the exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask.
  • the active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.
  • the active light or radiation include extreme ultraviolet light, 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 pattern.
  • the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), but is preferably an organic developer.
  • Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the substrate surface by surface tension and leaving it still for a certain period of time to develop (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
  • dip method a method of immersing a substrate in a tank filled with a developing solution for a certain period of time
  • spray method a method of spraying the developing solution on the substrate surface
  • dynamic dispense method a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed
  • the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds.
  • the temperature of the developer is preferably from 0 to 50°C, and more preferably from 15 to 35°C.
  • the alkaline developer is preferably an aqueous alkaline solution containing an alkali.
  • aqueous alkaline solution containing an quaternary ammonium salt such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine.
  • the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • Appropriate amounts of alcohols, surfactants, etc. may be added to the alkaline developer.
  • the alkaline concentration of the alkaline developer is preferably 0.1 to 20% by mass.
  • the pH of the alkaline developer is preferably 10.0 to 15.0.
  • the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • the above-mentioned solvents may be mixed in combination, or may be mixed with a solvent other than the above or with water.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.
  • the above pattern forming method preferably includes, after step 3, a step of washing with a rinsing liquid.
  • the rinse liquid used in the rinse step following the step of developing with an alkaline developer is, for example, pure water, to which an appropriate amount of a surfactant may be added.
  • a suitable amount of a surfactant may be added to the rinse solution.
  • the rinse liquid used in the rinse step following the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. It is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
  • the method of the rinsing step is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method).
  • the pattern forming method 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 usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
  • the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate.
  • the method for processing the substrate is not particularly limited, a method is preferred in which the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to form a pattern on the substrate.
  • the dry etching is preferably oxygen plasma etching.
  • the 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 (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
  • 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.
  • the content of metal components contained in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.
  • the resist composition may contain water as an impurity.
  • water When water is contained as an impurity, the smaller the water content, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water as a whole.
  • the resist composition may contain residual monomers as impurities (for example, monomers derived from the raw material monomers used in the synthesis of the resin (A)).
  • residual monomers when residual monomers are contained as impurities, the smaller the content of the residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass relative to the total solid content of the resist composition.
  • An organic processing liquid such as a rinse liquid may contain a conductive compound to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static electricity buildup and subsequent static electricity discharge.
  • the conductive compound is not particularly limited, but an example thereof is methanol.
  • the amount added is not particularly limited, but from the viewpoint of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the chemical liquid piping may be made of, for example, stainless steel (SUS), or various piping coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
  • the filter and O-ring may be made of antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
  • the present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method.
  • 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).
  • C-1 to C-5 are photodecomposable onium salt compounds.
  • Example 1-1 to 1-23, Comparative Examples 1-1 to 1-2: EUV Exposure ⁇ Preparation of Resist Composition>
  • the components shown in Table 1 were dissolved in the solvent shown in Table 1 to prepare a solution with a solids concentration of 2.0 mass %, and this was filtered through a polyethylene filter having a pore size of 0.02 ⁇ m to prepare a resist composition.
  • the solid content means all components other than the solvent.
  • the resist composition thus obtained was used in the examples and comparative examples.
  • the content of each component indicates the content (mass %) of each component relative to the total solid content in the resist composition.
  • Table 1 also shows the amount (mass ratio) of the solvent used.
  • An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm.
  • a resist composition immediately after production shown in Table 1 was applied onto the underlayer film and baked at 100° C. for 60 seconds to form a resist film having a thickness of 30 nm.
  • the silicon wafer having the resist film thus obtained was subjected to pattern irradiation using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36).
  • a mask with a line size of 20 nm and a line:space ratio of 1:1 was used as a reticle.
  • the exposed resist film was baked at 100° C. for 60 seconds, and then developed by puddling with the developer shown in Table 1 for 30 seconds. Only when otherwise specified, the wafer was rotated at 1000 rpm while being rinsed by pouring in the rinse solution shown in Table 1 below for 10 seconds, and then the wafer was rotated at 4000 rpm for 30 seconds to obtain a line and space pattern with a pitch of 40 nm.
  • the exposure amount for reproducing a mask pattern with a line width of 20 nm is defined as the optimal exposure amount, and when the line width of the line-and-space pattern formed is narrowed by further increasing the exposure amount from the optimal exposure amount, the minimum line width at which the pattern can be resolved without breaking is defined as the value (nm) indicating the resolution.
  • the resolution is preferably 17 nm or less, more preferably 16 nm or less, and even more preferably 15 nm or less.
  • the mask blank having the resist film obtained by the above-mentioned procedure was subjected to pattern irradiation using an electron beam exposure device (EBM-9000 manufactured by NuFlare Technology, Inc., acceleration voltage 50 kV). At this time, drawing was performed so that a line size of 22 nm and a 1:1 line and space were formed.
  • the exposed resist film was baked at 100° C. for 60 seconds, and then developed by puddling with the developer shown in Table 2 for 30 seconds. Only when otherwise specified, the wafer was rotated at 1000 rpm while being rinsed by pouring in the rinse solution shown in Table 2 below for 10 seconds, and then the wafer was rotated at 4000 rpm for 30 seconds to obtain a line and space pattern with a pitch of 44 nm.
  • the exposure amount for reproducing a mask pattern with a line width of 22 nm is defined as the optimal exposure amount, and when the line width of the line-and-space pattern formed is narrowed by further increasing the exposure amount from the optimal exposure amount, the minimum line width at which the pattern can be resolved without breaking is defined as the value (nm) indicating the resolution.
  • the resolution is preferably 22 nm or less, more preferably 20 nm or less, and even more preferably 18 nm or less.
  • an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. Furthermore, according to the present invention, there can be provided a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.

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Abstract

L'invention fournit une composition de résine sensible à la lumière active ou sensible au rayonnement d'une excellente résolution, un film de réserve, un procédé de formation de motif, et un procédé de fabrication de dispositif électronique incluant ledit procédé de formation de motif.　Plus précisément, l'invention concerne une composition de résine sensible à la lumière active ou sensible au rayonnement qui comprend : une résine spécifique qui possède une structure réticulée, et dont la chaîne principale est décomposée sous l'effet d'une irradiation de lumière active ou de rayonnement ; et un solvant. L'invention concerne également un film de réserve formé à l'aide de ladite composition de résine sensible à la lumière active ou sensible au rayonnement, un procédé de formation de motif mettant en œuvre ladite composition de résine sensible à la lumière active ou sensible au rayonnement, et un procédé de fabrication de dispositif électronique incluant ledit procédé de formation de motif.
PCT/JP2023/040638 2022-11-30 2023-11-10 Composition de résine sensible à la lumière active ou sensible au rayonnement, film de réserve, procédé de formation de motif, et procédé de fabrication de dispositif électronique WO2024116797A1 (fr)

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