Actinic ray-sensitive or radiation-sensitive resin composition, resin, resist film, pattern forming method, and electronic device manufacturing method

Abstract

There are provided: an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a solvent (B), wherein the resin (A) has a repeating unit (a1) containing at least one group of a secondary amino group and a tertiary amino group and an aromatic group and has a main chain capable of being decomposed by irradiation with actinic ray or radioactive ray; a resin usable in the actinic ray-sensitive or radiation-sensitive resin composition or the like; 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 an electronic device manufacturing method including the pattern forming method.

Description

Actinic ray- or radiation-sensitive resin composition, resin, resist film, pattern forming method, and method for manufacturing electronic device

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resin, a resist film, a pattern forming method, and a method for producing an electronic device.

[0002] Since the development of resists for KrF excimer lasers (248 nm), pattern formation methods utilizing chemical amplification have been used to compensate for the loss of sensitivity due to light absorption. For example, in positive-tone chemical amplification methods, a photoacid generator contained in the exposed area decomposes upon light irradiation to generate acid. Then, during a post-exposure bake (PEB) process, the catalytic action of the generated acid changes the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition to alkali-soluble groups, thereby changing the solubility in the developer. Development is then performed, for example, using a basic aqueous solution. This removes the exposed areas to obtain the desired pattern. To achieve miniaturization of semiconductor elements, the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher. Currently, exposure machines using an ArF excimer laser with a wavelength of 193 nm as a light source have been developed. Recently, pattern formation methods using extreme ultraviolet (EUV) and electron beam (EB) as light sources have also been studied. Under these circumstances, various configurations have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

[0003] Also known are pattern formation methods that use resins whose main chains are cleaved upon irradiation with actinic rays or radiation (main-chain decomposition resins). Patent Document 1 describes a positive resist composition for EUV lithography that contains a copolymer having α-methylstyrene units and α-chloroacrylic acid-1-adamantyl units, and a solvent. Patent Document 2 describes a resist material that contains a polymer with a specific structure that has a group containing at least one atom selected from a nitrogen atom, a phosphorus atom, and a selenium atom.

[0004] Japanese Patent Publication No. 2019-211531 Japanese Patent Publication No. 2021-9247

[0005] Recently, due to the trend toward finer patterns, the performance required of resist compositions has become increasingly higher. In particular, there is a demand for excellent sensitivity and resolution that enables the formation of ultrafine patterns (e.g., line-and-space patterns with line widths of 20 nm or less and a line:space ratio of 1:1). Through investigations by the present inventors, it has been found that the resist compositions described in Patent Documents 1 and 2 have poor sensitivity and resolution.

[0006] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity and resolution. Another object of the present invention is to provide a resin that can be used in the actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) having a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, the resin (A) having a main chain that decomposes upon irradiation with actinic rays or radiation, and a solvent (B). [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein at least one of the secondary amino group and the tertiary amino group is a group represented by the following formula (N-1):

[0009]

[0010] In formula (N-1), R ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ｎ１ and R ｎ２ At least one of R represents a hydrocarbon group. ｎ１ and R ｎ２ may be bonded to form a ring. ｎ１and R ｎ２ at least one of the repeating units may be bonded to the group to which the group represented by formula (N-1) is bonded to form a ring. * represents the bonding position to an oxygen atom or a carbon atom other than the carbonyl carbon. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin (A) has a repeating unit (a2) represented by the following formula (1):

[0011]

[0012] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ and may be bonded to form a ring. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein X in formula (1) represents a fluorine atom, a chlorine atom, or a bromine atom. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the aromatic group in the repeating unit (a1) is located closer to the main chain of the resin (A) than at least one of the secondary amino group and the tertiary amino group. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the repeating unit (a1) is a repeating unit represented by the following formula (N-2):

[0013]

[0014] In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each, ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x1 R ｎ３ and x1 Rｎ４ At least one of x represents a hydrocarbon group. ｎ３ , x1 R ｎ４ and x2 E ２ [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the repeating unit (a1) is a repeating unit represented by the following formula (N-3):

[0015]

[0016] In formula (N-3), x3 represents an integer of 1 or more and 5 or less. x4 represents an integer of 0 or more and 4 or less. However, the sum of x3 and x4 is an integer of 1 or more and 5 or less. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each, ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x3 R ｎ３ and x3 R ｎ４ At least one of x3 R represents a hydrocarbon group. ｎ３ , x3 R ｎ４ and x4 E ２At least two of these may be bonded to form a ring. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein x3 in formula (N-3) represents 1 or 2. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], further comprising at least one compound selected from the group consisting of an ionic photodegradable compound (C1) and a nonionic photodegradable acidic compound (C2).

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to [9], comprising the ionic photodegradable compound (C1), wherein the ionic photodegradable compound (C1) is a compound containing at least one selected from the group consisting of a sulfonium cation and an iodonium cation.

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to

[10] , wherein the ionic photodegradable compound (C1) is a compound represented by formula (Z-1):

[0017]

[0018] In formula (Z-1), Ar ｍ１ , Ar ｍ２ and Ar ｍ３ Each independently represents an aryl group. ｍ１ , Ar ｍ２ and Ar ｍ３ At least two of the AN may be bonded to each other. － represents an anionic group. ｍ１ represents a g-valent group. g represents an integer of 1 or more. When g represents an integer of 2 or more, a plurality of AN － and may be the same or different.

[12] The actinic ray-sensitive or radiation-sensitive resin composition according to [9], comprising the nonionic photodegradable acidic compound (C2), wherein the nonionic photodegradable acidic compound (C2) has a carboxyl group.

[13] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) having a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, and a repeating unit (a2) represented by the following formula (1), and a solvent (B):

[0019]

[0020] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

[14] A resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (N-2):

[0021]

[0022] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

[0023]

[0024] In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each, ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x1 R ｎ１ and x1 R ｎ２ At least one of x represents a hydrocarbon group. ｎ１ , x1 R ｎ２ and x2 E ２At least two of the above may be bonded to form a ring.

[15] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[13] .

[16] A pattern forming method using the resist film according to

[15] .

[17] A method for manufacturing an electronic device, comprising the pattern forming method according to

[16] .

[0025] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity and resolution. The present invention also can provide a resin that can be used in the actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0026] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is referred to without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0027] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, an acryloyloxy ... Examples of the substituent T include acyl groups such as an alkyl group, a methacryloyl group, and a methoxalyl group; a sulfanyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; an aromatic heterocyclic group (heteroaryl group); a hydroxy group; a carboxyl group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a carbamoyl group; and the like. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, a monoalkylamino group, a dialkylamino group, an arylamino group, a trifluoromethyl group, etc.).

[0028] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beams). As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" as used herein includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams. As used herein, the term "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. The bonding direction of divalent groups described herein 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 either -CO-O- or -O-CO-. In addition, the compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0029] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0030] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0031] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0032] On the other hand, pKa can also be determined by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0033] As described above, the pKa in this specification refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and publicly known literature values, but if the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as described above, the pKa in this specification refers to "pKa in aqueous solution," but if the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0034] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0035] In this specification, the term "solid content" refers to components that form a resist film and does not include solvents. Furthermore, any component that forms a resist film is considered to be a solid content even if it is in a liquid state.

[0036] [Actinic Ray- or Radiation-Sensitive Resin Composition] The actinic ray- or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") is an actinic ray- or radiation-sensitive resin composition containing a resin (A) whose main chain decomposes upon irradiation with actinic rays or radiation, and which has a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, and a solvent (B).

[0037] The reason why the resist composition of the present invention has excellent sensitivity and resolution is not clear in detail, but the inventors speculate as follows. However, the present invention is not limited in any way by the speculated mechanism below. It is believed that resist compositions containing main-chain decomposition resins promote main-chain decomposition reactions by utilizing secondary electrons generated by irradiation with EUV or electron beams. However, it is believed that sensitivity decreases when the generated secondary electrons return to their original state (reverse migration) without reacting with the main chain. It is believed that the resin (A) contained in the resist composition of the present invention has a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, which suppresses the reverse migration of the generated secondary electrons, efficiently promoting the main-chain decomposition reaction and improving sensitivity and resolution.

[0038] First, the various components contained in the resist composition will be described below.

[0039] [Resin (A)] The resist composition of the present invention contains a resin (A) that has a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, and whose main chain is decomposed when irradiated with actinic rays or radiation. The resin (A) is preferably a resin whose main chain is decomposed when irradiated with X-rays, electron beams, or extreme ultraviolet rays.

[0040] <Repeating Unit (a1)> (At Least One of Secondary Amino Group and Tertiary Amino Group) The repeating unit (a1) contained in the resin (A) contains at least one of a secondary amino group and a tertiary amino group. The secondary amino group and the tertiary amino group are unsubstituted amino groups (—NH ２) is preferably a group in which at least one of the two hydrogen atoms is substituted with a hydrocarbon group. The hydrocarbon group may be a group consisting of only carbon atoms and hydrogen atoms, or may be a group further containing other atoms (for example, oxygen atoms, nitrogen atoms, sulfur atoms, etc.). When the hydrocarbon group is a group further containing other atoms, the carbon atom of the hydrocarbon group and —NH ２ The tertiary amino group is bonded to the nitrogen atom of -NH ２ In the present invention, an amino group bonded to a carbonyl group (an amide group, -CONR ２ ), and an amino group linked to a sulfonyl group (sulfonamide group, -SO ２ NR ２ ) are not included in the secondary amino group and tertiary amino group. Each R independently represents a hydrogen atom or a hydrocarbon group.

[0041] At least one of the secondary amino group and the tertiary amino group is preferably a group represented by the following formula (N-1).

[0042]

[0043] In formula (N-1), R ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ｎ１ and R ｎ２ At least one of R represents a hydrocarbon group. ｎ１ and R ｎ２ may be bonded to form a ring. ｎ１ and R ｎ２ At least one of these may bond to the group to which the group represented by formula (N-1) is bonded to form a ring. * represents the bonding position to an oxygen atom or a carbon atom other than the carbonyl carbon. * preferably represents the bonding position to a carbon atom other than the carbonyl carbon.

[0044] In the secondary amino group and the tertiary amino group, the hydrocarbon group bonded to the nitrogen atom (in formula (N-1), R ｎ１ and R ｎ２ Examples of the hydrocarbon group represented by (R) include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and a cycloalkynyl group. An alkyl group, a cycloalkyl group, or an aryl group is preferred, and an alkyl group or a cycloalkyl group is more preferred.

[0045] The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. The alkyl group may have a substituent. Examples of the substituent include the aforementioned substituent T, and preferred are a hydroxy group, a carboxyl group, and the like.

[0046] The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The cycloalkyl group may have a substituent. Examples of the substituent include the aforementioned substituent T, and preferred are a hydroxy group, a carboxyl group, and an alkyl group. One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, a group containing a heteroatom such as a carbonyl group, a sulfonyl group, or an ester bond, or a vinylidene group. One or more of the ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group.

[0047] The aryl group may be either monocyclic or polycyclic. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 15. 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. Examples of the substituent include the aforementioned substituent T, and preferred are a hydroxy group, a carboxyl group, an alkyl group, etc.

[0048] The alkenyl group may be either straight-chain or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. The alkenyl group may have a substituent. The cycloalkenyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkenyl group is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15. The cycloalkenyl group may have a substituent. The alkynyl group may be either straight-chain or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. The alkynyl group may have a substituent. The cycloalkynyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkynyl group is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15. The cycloalkynyl group may have a substituent.

[0049] In the tertiary amino group, the hydrocarbon groups bonded to the nitrogen atom (in formula (N-1), R ｎ１ and R ｎ２ The hydrocarbon groups represented by (R) may be bonded to each other to form a ring. The ring may be an aromatic ring or a non-aromatic ring, but is preferably a non-aromatic ring. The ring may contain a nitrogen atom and a carbon atom as ring member atoms, or may contain other atoms (e.g., an oxygen atom, a sulfur atom, etc.) in addition to the nitrogen atom and the carbon atom. The number of ring member atoms of the ring is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15, for example. The ring may have a substituent.

[0050] At least one of the hydrocarbon groups of the secondary amino group and the tertiary amino group may be bonded to the group to which the amino group is bonded to form a ring (R ｎ１ and R ｎ２ At least one of the above may be bonded to the group to which the group represented by formula (N-1) is bonded to form a ring. The ring may be an aromatic ring or a non-aromatic ring, but is preferably a non-aromatic ring. The ring may contain nitrogen atoms and carbon atoms as ring member atoms, or may contain other atoms (e.g., oxygen atoms, sulfur atoms, etc.) in addition to nitrogen atoms and carbon atoms. The number of ring member atoms of the ring is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15, for example. The ring may have a substituent. The group to which the secondary amino group and the tertiary amino group are bonded (the group to which the group represented by formula (N-1) is bonded) is preferably an aromatic group.

[0051] (Aromatic Group) The repeating unit (a1) contained in the resin (A) contains an aromatic group. The aromatic group may be a monovalent group or a divalent or higher valent group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic group may have a substituent. Examples of the substituent include the aforementioned substituent T, and preferred are alkyl groups (e.g., alkyl groups having 1 to 5 carbon atoms), hydroxy groups, carboxyl groups, and halogen atoms.

[0052] The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 15. The aromatic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon such as benzene, naphthalene, or anthracene, more preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and even more preferably a group obtained by removing one or more hydrogen atoms from benzene. The aromatic hydrocarbon group may also be a group obtained by removing one or more hydrogen atoms from a compound (fused ring compound) in which an aromatic hydrocarbon is condensed with at least one selected from the group consisting of cycloalkanes (e.g., cyclopentane, cyclohexane, etc.) and non-aromatic heterocyclic compounds. Examples of non-aromatic heterocyclic compounds include five-membered ring non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, and 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, and piperazine. An oxo group (═O) may be substituted for a carbon atom contained as a ring member in the non-aromatic heterocyclic compound.

[0053] The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 5 to 20, and more preferably 6 to 15. Examples of aromatic heterocyclic groups include groups obtained by removing one or more hydrogen atoms from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, and triazole, or six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The aromatic heterocyclic group may also be a group obtained by removing one or more hydrogen atoms from a compound (e.g., indole, quinoline, isoquinoline, etc.) in which the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is condensed with at least one selected from the group consisting of the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., the above-mentioned five-membered non-aromatic heterocyclic compounds, six-membered non-aromatic heterocyclic compounds, etc.).

[0054] The aromatic group in the repeating unit (a1) is preferably located closer to the main chain of the resin (A) than at least one of the secondary amino group and the tertiary amino group.

[0055] The repeating unit (a1) is preferably a repeating unit represented by the following formula (N-2).

[0056]

[0057] In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each,２ , R ｎ３ and R ｎ４ may be the same or different, provided that x1 R ｎ３ and x1 R ｎ４ At least one of x represents a hydrocarbon group. ｎ３ , x1 R ｎ４ and x2 E ２ At least two of these may be bonded to form a ring.

[0058] The description, specific examples, and preferred range of the aromatic group represented by Ar in formula (N-2) are the same as those described above for the aromatic group contained in the repeating unit (a1). x1 in formula (N-2) represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2. x2 in formula (N-2) represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably 0 or 1. E in formula (N-2) １ Examples of the substituent represented by E include the aforementioned substituent T, and an alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. ２ Examples of the substituent represented by R in formula (N-2) include the aforementioned substituent T, and preferred are an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), a hydroxy group, a carboxyl group, a halogen atom, etc. ｎ３ and R ｎ４ The description, specific examples and preferred range of the hydrocarbon group represented by R in the above formula (N-1) are ｎ１ and R ｎ２ The same applies to the hydrocarbon group represented by x1 R in formula (N-2). ｎ３ , x1 R ｎ４ and x2 E ２ At least two of the above may be bonded to form a ring. The ring may be an aromatic ring or a non-aromatic ring, but is preferably a non-aromatic ring. The number of ring atoms in the ring is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15, for example. The ring may have a substituent.

[0059] The repeating unit (a1) is particularly preferably a repeating unit represented by the following formula (N-3).

[0060]

[0061] In formula (N-3), x3 represents an integer of 1 or more and 5 or less. x4 represents an integer of 0 or more and 4 or less. However, the sum of x3 and x4 is an integer of 1 or more and 5 or less. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each, ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x3 R ｎ３ and x3 R ｎ４ At least one of x3 R represents a hydrocarbon group. ｎ３ , x3 R ｎ４ and x4 E ２ At least two of these may be bonded to form a ring.

[0062] In formula (N-3), x3 preferably represents an integer of 1 or more and 3 or less, more preferably 1 or 2. In formula (N-3), x4 preferably represents an integer of 0 or more and 3 or less, more preferably 0 or 1. E in formula (N-3) １ Examples of the substituent represented by E include the aforementioned substituent T, and an alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. ２ Examples of the substituent represented by R in formula (N-3) include the aforementioned substituent T, and preferred are an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), a hydroxy group, a carboxyl group, a halogen atom, etc. ｎ３ and R ｎ４ The description, specific examples and preferred range of the hydrocarbon group represented by R in the above formula (N-1) are ｎ１ and R ｎ２The x3 R in formula (N-3) is the same as the hydrocarbon group represented by ｎ３ , x3 R ｎ４ and x4 E ２ At least two of the above may be bonded to form a ring. The ring may be an aromatic ring or a non-aromatic ring, but is preferably a non-aromatic ring. The number of ring atoms in the ring is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15, for example. The ring may have a substituent.

[0063] The content of the repeating unit (a1) in the resin (A) is not particularly limited, but 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 resin (A). The repeating unit (a1) contained in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is within the above range.

[0064] <Repeating Unit (a2)> The resin (A) preferably has a repeating unit (a2) represented by the following formula (1).

[0065]

[0066] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

[0067] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. The halogen atom represented by X is preferably a fluorine atom, a chlorine atom, or a bromine atom, with a chlorine atom being more preferred. The alkyl group in the fluorinated alkyl group represented by X may be either linear or branched. The alkyl group may have one or more fluorine atoms substituted thereon, but is preferably a perfluoroalkyl group. The number of carbon atoms in the fluorinated alkyl group represented by X is not particularly limited, but is preferably, for example, 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group in the fluorinated cycloalkyl group represented by X may be either monocyclic or polycyclic. The cycloalkyl group may have one or more fluorine atoms substituted thereon, but may also be a perfluorocycloalkyl group. The number of carbon atoms in the fluorinated cycloalkyl group represented by X is not particularly limited, but is preferably, for example, 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. X preferably represents a halogen atom, more preferably a fluorine atom, a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

[0068] In formula (1), R ０ represents a hydrogen atom or an organic group. ０ The organic group represented by is not particularly limited, but is preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably, for example, 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, but examples include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy 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. R０ is preferably a hydrogen atom.

[0069] In formula (1), R １ represents a substituent. １ The substituent represented by the formula (1-1) is not particularly limited, and examples thereof include a group represented by the formula (1-1) below, a hydroxy group, -NH ２ etc.

[0070] Formula (1-1): *-L １Ａ -R １Ａ

[0071] In formula (1-1), * represents a bonding position. １Ａ is a single bond, —O— or —N(R ｘ )-. ｘ represents a hydrogen atom or an organic group. ｘ The organic group represented by the formula (I) is not particularly limited, but is preferably, for example, an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is, for example, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. 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), a hydroxy 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. R ｘ is preferably a hydrogen atom.

[0072] In formula (1-1), R １Ａ represents a hydrogen atom or an organic group. １ＡThe organic group represented by the formula (I) 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, as described below. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably, for example, 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, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The 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), a hydroxy 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.

[0073] In addition, one embodiment of the alkyl group is —C(R Ｘ１ ) (R Ｘ２ ) (R Ｘ３ ) groups represented by R Ｘ１ ~R Ｘ３ R each independently represents an alkyl group or a cycloalkyl group. Ｘ１ ~R Ｘ３ The alkyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Ｘ１ ~R Ｘ３The cycloalkyl group represented by the formula (I) may be either monocyclic or polycyclic. 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. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. R Ｘ１ ~R Ｘ３ each independently represents a linear or branched alkyl group (preferably a linear alkyl group), or R Ｘ１ ~R Ｘ３ Preferably, two of the R Ｘ１ ~R Ｘ３ The alkyl group or cycloalkyl group represented by the formula (I) 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), 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. Ｘ１ ) (R Ｘ２ ) (R Ｘ３ ) represents a group represented by the above L １Ａ As the group, —O— or —N(R Ｘ )-, and more preferably -O-.

[0074] The aryl group may be either 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. Of these, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may also have a substituent. The substituent is not particularly limited, and examples include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy 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. Of these, a fluorine atom, an iodine atom, or a hydroxy group is preferred.

[0075] The aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group, and the number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 15.

[0076] In formula (1), R ０ and R １ may be bonded to form a ring. ０ and R １ and are bonded to each other to form a ring containing at least two carbon atoms and one carbonyl (>C=O) carbon atom as specified in formula (1), and is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. The ring may also contain a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member. Furthermore, a carbon atom in the ring other than the carbon atoms (excluding the two carbon atoms specified in formula (1)) may be substituted with a carbonyl (>C=O) carbon atom.

[0077] The repeating unit represented by formula (1) is preferably a repeating unit represented by the following formula (1A).

[0078]

[0079] In formula (1A), X and R ０ represents X and R in formula (1). ０ In formula (1A), L２Ａ is -O- or -N(R ｘ )-. ｘ represents a hydrogen atom or an organic group. ｘ The organic group represented by the formula (1-1) is R ｘ In formula (1A), R １Ａ represents a hydrogen atom or an organic group. １Ａ The organic group represented by the formula (1-1) is R １Ａ The same as above can be mentioned. ０ and R １Ａ may be linked to each other to form a ring. ０ and R １Ａ The ring formed by combining these groups includes R ０ and R １ and the like can be mentioned as rings formed by linking them to each other.

[0080] When the resin (A) has the repeating unit (a2), the content of the repeating unit (a2) in the resin (A) 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 resin (A). The repeating unit (a2) contained in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is within the above range.

[0081] <Other Repeating Units> The resin (A) may further have a repeating unit (also referred to as an "other repeating unit") different from the repeating unit (a1) and the repeating unit (a2). As the other repeating unit, a repeating unit represented by formula (2) is preferred, a repeating unit represented by formula (3) or formula (4) is more preferred, and a repeating unit represented by formula (4) is particularly preferred.

[0082] <Repeating unit represented by formula (2)>

[0083]

[0084] In formula (2), A １ represents a hydrogen atom, a halogen atom or an organic group. ３represents a hydrogen atom or a substituent. １ represents a single bond or a divalent linking group. １ represents a substituent. ３ and L １ and B １ may be bonded to at least one of the groups to form a ring.

[0085] A １ The organic group represented by the formula (I) is preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. 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), a hydroxy 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. A １ The halogen atom represented by the formula (I) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom. １ As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, a methyl group or an ethyl group is particularly preferable, and a methyl group is most preferable.

[0086] R ３The substituent represented by is not particularly limited, but is preferably an organic group, and more preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably, for example, 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. R ３ is preferably a hydrogen atom.

[0087] L １ represents a single bond or a divalent linking group. １ The divalent linking group represented by the formula (I) is not particularly limited, but examples thereof include -CO-, -O-, -SO-, and -SO ２ -, -NR Ａ -, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), arylene groups (preferably having a 6- to 10-membered ring, more preferably a 6-membered ring), and divalent linking groups combining a plurality of these. The alkylene groups, cycloalkylene groups, and arylene groups may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy 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. R Ａ is a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ is a single bond, —COO— or —CONR Ａ - is preferred.

[0088] B １ represents a substituent. １The substituent represented by the formula (I) is not particularly limited, and examples thereof include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, cycloalkenyl groups, alkoxy groups, cycloalkyloxy groups, acyloxy groups, cyano groups, nitro groups, halogen atoms, lactone groups, groups containing the onium salt structure described below, hydroxy groups, carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, and acetoxy groups. The alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, cycloalkenyl groups, alkoxy groups, cycloalkyloxy groups, acyloxy groups, and lactone groups may further have a substituent, and examples of the substituent include halogen atoms, hydroxy groups, carboxyl groups, amino groups, amide groups, imide groups, thiol groups, acetyl groups, sulfonic acid groups, sulfonamide groups, acetoxy groups, and groups containing the onium salt structure described below. When the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.

[0089] The alkyl group may be either linear or branched. The number of carbon atoms is not particularly limited, but is 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 is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group may be either monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is preferably 6 to 15, and more preferably 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group. The aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms is also not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. The cycloalkenyl group may be either monocyclic or polycyclic. The number of carbon atoms is also not particularly limited, but is preferably 4 to 20, more preferably 5 to 15, and even more preferably 5 to 10. The alkoxy group may be either linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The cycloalkyloxy group may be either monocyclic or polycyclic. The number of carbon atoms is also not particularly limited, but is preferably 4 to 20, more preferably 5 to 15, and even more preferably 5 to 10. The acyloxy group may be linear, branched, or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.The lactone group is preferably a 5- to 7-membered lactone group, and more preferably a 5- to 7-membered lactone ring condensed with another ring structure to form a bicyclo structure or a spiro structure.

[0090] <Repeating unit represented by formula (3)>

[0091]

[0092] In formula (3), A １ , R ３ and L １ are A in formula (2), respectively. １ , R ３ and L １ It is synonymous with B. ２ represents a linking group having a valence of m1+1. １ represents one or more functional groups selected from the group consisting of a hydroxy 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. m1 represents an integer of 1 or more. R ３ and L １ , B １ and C １ may be bonded to at least one of the groups to form a ring.

[0093] In formula (3), A １ , R ３ and L １ are A in formula (2), respectively. １ , R ３ and L １ The same definition and preferred embodiments are also the same. ２ represents a linking group having a valence of m1+1. ２ Examples of the (m+1)-valent linking group represented by the formula (I) include a group formed by removing m1 hydrogen atoms from a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, a cycloalkyloxy group, an acyloxy group, and a lactone group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group, the cycloalkenyl group, the alkoxy group, the cycloalkyloxy group, the acyloxy group, and the lactone group can further be selected from the group consisting of C１ The alkyl group may have a substituent other than the specific type of functional group represented by the formula (I), and examples of the substituent include a halogen atom. When the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.

[0094] The alkyl group may be either linear or branched. The number of carbon atoms is not particularly limited, but is 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 is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group may be either monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is preferably 6 to 15, and more preferably 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group. The aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms is not particularly limited, but is, for example, preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. The cycloalkenyl group may be either monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is, for example, preferably 4 to 20, more preferably 5 to 15, and even more preferably 5 to 10. The alkoxy group may be either linear or branched, and the number of carbon atoms is not particularly limited, but is, for example, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The cycloalkyloxy group may be either monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is, for example, preferably 4 to 20, more preferably 5 to 15, and even more preferably 5 to 10. The acyloxy group may be linear, branched, or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.The lactone group is preferably a 5- to 7-membered lactone group, and more preferably a 5- to 7-membered lactone ring condensed with another ring structure to form a bicyclo structure or a spiro structure.

[0095] B ２ The m1+1-valent linking group represented by the formula (I) is preferably an m1+1-valent aromatic hydrocarbon ring group (a group formed by removing m1 hydrogen atoms from an aryl group), and more preferably an m1+1-valent benzene ring group or an m1+1-valent naphthalene ring group. The m1+1-valent benzene ring group and the m1+1-valent naphthalene ring group preferably have a halogen atom as a substituent.

[0096] C １ represents one or more functional groups selected from the group consisting of a hydroxy 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. As the functional group, one or more functional groups selected from the group consisting of a phenolic hydroxyl group and a carboxyl group are more preferred. １ represents a phenolic hydroxyl group, B ２ The m1+1 valent linking group represented by the following formula preferably represents an m1+1 valent aromatic hydrocarbon ring group (a group formed by removing m1 hydrogen atoms from an aryl group).

[0097] m1 represents an integer of 1 or more. m1 is, for example, preferably 1 to 6, more preferably 1 to 3. When m1 represents an integer of 2 or more, a plurality of C １ They may be the same or different from each other.

[0098] <Repeating unit represented by formula (4)>

[0099]

[0100] In formula (4), A １ represents a hydrogen atom, a halogen atom or an organic group. ３ represents a hydrogen atom or a substituent. １ represents a benzene ring or a naphthalene ring. ４ represents a substituent. ４If there are multiple R ４ may be the same or different, R ４ They may be bonded to each other to form a ring. ３ and R ４ may be bonded to form a ring. k1 represents an integer of 0 to 7.

[0101] In formula (4), A １ and R ３ are A in formula (2), respectively. １ and R ３ The same definition and preferred embodiments are also the same.

[0102] In formula (4), R ４ represents a substituent. ４ The substituent represented by is not particularly limited, and examples thereof include a group containing an onium salt structure, which will be described later, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a fluorinated alkyl group, a hydroxyl group, a carboxyl group, an acyl group, an acyloxy group, an alkoxy group, a carbamoyl group, a sulfonamide group, an amino group, a thiol group, and an alkylsulfonyl group. ４ If there are multiple R ４ may be the same or different, R ４ They may be bonded together to form a ring. ３ and R ４ may be bonded to form a ring. ３ and R ４ When R ３ In the form of substituting a hydrogen atom represented by R ４ may be bonded to form a ring. ３ and R ４ and R ４ The ring formed by bonding together is not particularly limited and may be either a monocyclic ring or a polycyclic ring. The ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member. The ring may also contain a carbonyl carbon as a ring member. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0103] In formula (4), Ar １represents a benzene ring or a naphthalene ring, and preferably represents a benzene ring. In formula (4), k1 represents an integer of 0 to 7. １ When Ar represents a benzene ring, k1 represents an integer of 0 to 5, and preferably an integer of 0 to 3. １ represents a naphthalene ring, k1 represents an integer of 0 to 7, and preferably an integer of 0 to 3.

[0104] When the resin (A) has other repeating units, the content of the other repeating units in the resin (A) is preferably 1 to 40 mol %, more preferably 5 to 30 mol %, based on the total repeating units of the resin (A). The other repeating units contained in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is in the above range.

[0105] (Group containing an onium salt structure) The group containing an onium salt structure will be described. The onium salt structure is a structural moiety having an ion pair of a cation and an anion, and is represented by "X ｎ－ nM ＋ " (where n represents, for example, an integer of 1 to 3, and preferably represents 1 or 2). M ＋ is a structural moiety containing a positively charged atom or atomic group, and X ｎ－ 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 (an anion with extremely low ability to cause a nucleophilic reaction). When the anion in the onium salt structure is a non-nucleophilic anion, it is likely to become a photodegradable onium salt structure. The non-nucleophilic anion is the same as the non-nucleophilic anion in the onium salt described below.

[0106] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). An example of a method for synthesizing resin (A) will be described in detail in the Examples below. The weight-average molecular weight of resin (A), as measured by GPC in terms of polystyrene, is preferably 1,000 to 200,000, more preferably 2,500 to 150,000, and even more preferably 5,000 to 80,000. When the weight-average molecular weight is within the above range, deterioration of heat resistance and dry etching resistance can be further suppressed. Furthermore, deterioration of developability and deterioration of film-forming properties due to increased viscosity can be further suppressed. The dispersity (molecular weight distribution, Mw / Mn) of resin (A) 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 smaller the dispersity, the better the resolution and resist shape.

[0107] When the resin (A) has two or more types of repeating units, it may be in the form of a random copolymer, a block copolymer, or an alternating copolymer.

[0108] A preferred embodiment of the resin (A) is one in which the total content of the repeating units (a1) and (a2) in the resin (A) is 70 mol % or more and 100 mol % or less, based on all repeating units in the resin (A).

[0109] The content of resin (A) in the resist composition of the present invention 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. Furthermore, the content of resin (A) is 100% by mass or less, or even 95% by mass or less, or even 90% by mass or less, based on the total solid content of the resist composition. The resin (A) contained in the resist composition of the present invention may be one type, or two or more types. When two or more types are used, the total content thereof is preferably within the above-mentioned range.

[0110] [Solvent (B)] The resist composition of the present invention contains a solvent (B). The solvent (B) preferably contains (M1) a propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of a propylene glycol monoalkyl ether, a lactate ester, an acetate ester, an alkoxypropionate ester, a chain ketone, a cyclic ketone, a lactone, and an alkylene carbonate. The solvent (B) may further contain components other than the components (M1) and (M2).

[0111] As the 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, and propylene glycol monomethyl ether acetate (PGMEA) is more preferred.

[0112] The following are preferred as component (M2). As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferred. As the lactate ester, ethyl lactate, butyl lactate, or propyl lactate is preferred. As the acetate ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred. Butyl butyrate is also preferred. The alkoxypropionic acid ester is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). The chain ketone is preferably 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. The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone. The lactone is preferably γ-butyrolactone, and the alkylene carbonate is preferably propylene carbonate.

[0113] As component (M2), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, methyl 2-hydroxyisobutyrate, γ-butyrolactone, or propylene carbonate is more preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is even more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.

[0114] In addition to the above-mentioned components, the solvent (B) also preferably contains an ester 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. Preferred ester solvents having 7 or more carbon atoms and 2 or less heteroatoms are amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butanoate, and more preferred isoamyl acetate.

[0115] Solvent (B) preferably contains component (M1). Solvent (B) more preferably consists essentially of component (M1) alone, or is a mixed solvent of component (M1) with other components. In the latter case, solvent (B) more preferably contains both component (M1) and component (M2). The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably within the range of 100 / 0 to 15 / 85, more preferably within the range of 100 / 0 to 40 / 60, and even more preferably within the range of 100 / 0 to 60 / 40. In other words, solvent (B) preferably consists solely of component (M1) or contains both component (M1) and component (M2), and the mass ratio between them is as follows: That is, in the latter case, the mass ratio of component (M1) to component (M2) is preferably 15 / 85 or more, more preferably 40 / 60 or more, and even more preferably 60 / 40 or more.

[0116] When the solvent (B) contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) can be, for example, 99 / 1 or less.

[0117] When the solvent (B) further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0118] The content of the solvent (B) in the resist composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass%, and more preferably 1 to 20 mass%, in order to achieve better coatability.

[0119] [Additive (C)] The resist composition of the present invention may further contain at least one compound (also referred to as "additive (C)") selected from the group consisting of an ionic photodecomposable compound (C1) and a non-ionic photodecomposable acidic compound (C2). A preferred embodiment of the resist composition of the present invention comprises an ionic photodecomposable compound (C1), wherein the ionic photodecomposable compound (C1) is a compound containing at least one selected from the group consisting of a sulfonium cation and an iodonium cation. Another preferred embodiment of the resist composition of the present invention comprises a non-ionic photodecomposable acidic compound (C2), wherein the non-ionic photodecomposable acidic compound (C2) has a carboxyl group.

[0120] <Ionic Photodecomposable Compound (C1)> The ionic photodecomposable compound (C1) (also referred to as "compound (C1)") preferably contains an anion and a cation. The compound (C1) is a compound that decomposes upon irradiation with actinic rays or radiation. The compound that decomposes upon irradiation with actinic rays or radiation may be a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid, or may be a compound that decomposes upon irradiation with actinic rays or radiation to generate a base. The compound (C1) is preferably a compound having an onium salt structure that decomposes upon irradiation with actinic rays or radiation to generate an acid (photodecomposable onium salt compound).

[0121] The photodegradable onium salt compound will now be described. The photodegradable onium salt compound preferably has at least one salt structural moiety composed of an anion moiety and a cation moiety, and decomposes upon exposure to generate an acid (preferably an organic acid). The salt structural moiety of the photodegradable onium salt compound is preferably composed of an organic cation moiety and an organic anion moiety with significantly low nucleophilicity, as these moieties are easily decomposed upon exposure and have excellent organic acid generation properties. The salt structural moiety may be a portion or the entirety of the photodegradable onium salt compound. An example of a case where the salt structural moiety is a portion of the photodegradable onium salt compound is a structure in which two or more salt structural moieties are linked, such as the photodegradable onium salt PG2 described below. The number of salt structural moieties in the photodegradable onium salt is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0122] Examples of organic acids generated from the photodegradable onium salt compound by the action of exposure include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methide acids. Furthermore, the organic acid generated from the photodegradable onium salt compound by the action of exposure may be a polyvalent acid having two or more acid groups. For example, when the photodegradable onium salt compound is the photodegradable onium salt compound PG2 described below, the organic acid generated by decomposition of the photodegradable onium salt compound by exposure is a polyvalent acid having two or more acid groups.

[0123] In the photodecomposable onium salt compound, 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)) described later is preferred.

[0124] (Photodecomposable Onium Salt Compound PG1) One example of a preferred embodiment of the photodecomposable onium salt compound is "M ＋ X － " which generates an organic acid upon exposure to light (hereinafter also referred to as "photodecomposable onium salt compound PG1"). ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation, and X － represents an organic anion. The photodecomposable onium salt compound PG1 will be described below.

[0125] M in the photodecomposable onium salt compound PG1 ＋ The organic cation represented by formula (ZaI) (cation (ZaI)) or the organic cation represented by formula (ZaII) (cation (ZaII)) is preferred.

[0126]

[0127] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by R is usually 1 to 30, and preferably 1 to 20. ２０１ ~R ２０３ Two of these 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. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0128] 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.

[0129] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R 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. ２０１ ~R ２０３ Examples of the group formed by combining two of the above include an alkylene group in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., a butylene group, a pentylene group, or a -CH ２ -CH ２ -O-CH ２ -CH ２ Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

[0130] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When 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 optionally contained in the arylsulfonium cation 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.

[0131] R ２０１ ~R ２０３ Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are each independently an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxy group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, etc. The above substituents may further have a substituent if possible, and for example, it is also preferred that the above alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0132] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３The organic group having no aromatic ring as R generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0133] R ２０１ ~R ２０３ Examples of the alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0134] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0135]

[0136] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each 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. ６ｃ and R ７ｃ R each independently represents 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. ｘ and R ｙeach independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0137] R １ｃ ~R ５ｃ Two or more of the following, 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. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0138] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0139] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃand R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0140] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0141]

[0142] In formula (ZaI-4b), l represents an integer of 0 to 2. r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, 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. R １４ represents a hydroxyl group, a halogen atom (for example, 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 (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R 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. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５The ring formed by bonding together may have a substituent.

[0143] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group is preferably linear or branched, and 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.

[0144] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R preferably has 2 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. ２０４ and R ２０５ The aryl group in R 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. ２０４ and R ２０５ The alkyl group and cycloalkyl group 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).

[0145] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

[0146] Specific examples of the cation that can be contained in the compound (C1) are shown below, but the present invention is not limited to these.

[0147]

[0148]

[0149] X in the photodecomposable onium salt compound PG1 － The organic anion represented by the formula (I) is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction). Examples of the non-nucleophilic anion 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.

[0150] The organic anion is preferably, for example, an organic anion represented by the following formula (DA).

[0151]

[0152] In formula (DA), A ３１ － represents an anionic group. ａ１ represents a hydrogen atom or a monovalent organic group. ａ１ represents a single bond or a divalent linking group. ３１ － and R ａ１ may be bonded to each other to form a ring.

[0153] A ３１ － represents an anionic group. ３１－ The anionic group represented by the formula (BA-1) is not particularly limited, but is preferably a group selected from the group consisting of groups represented by formulas (BA-1) to (BA-13), more preferably formula (BA-1), formula (BA-2), formula (BA-3), formula (BA-4), formula (BA-5), formula (BA-6), formula (BA-10), formula (BA-11), formula (BA-12), and formula (BA-13), and particularly preferably formula (BA-4), formula (BA-6), and formula (BA-12).

[0154]

[0155] In formulae (BA-1) to (BA-13), * represents a bonding position. In formulae (BA-1) to (BA-5) and formula (BA-10), R Ｘ１ Each independently represents a monovalent organic group. Ｘ２ Each of the two R in formula (BA-7) independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group. Ｘ２ may be the same or different. Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer of 0 to 4. When n1 represents an integer of 2 to 4, a plurality of R Ｘ３ may be the same or different. The group that bonds to the bonding position represented by * in Formula (BA-12) and Formula (BA-13) is preferably an alkylene group or an arylene group, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and particularly preferably a phenylene group. The alkylene group and the arylene group may have a substituent, which is not particularly limited and includes, for example, a halogen atom.

[0156] In formulas (BA-1) to (BA-5) and formula (BA-10), R Ｘ１ R each independently represents a monovalent organic group. Ｘ１As the R, 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) is preferred. Ｘ１ The above group represented by the formula (B-5) may have a substituent. Ｘ１ The atom directly bonded to N- in -CO- and -SO ２ It is also preferred that neither of the sulfur atoms in - is present.

[0157] R Ｘ１ The cycloalkyl group in R may be monocyclic or polycyclic. Ｘ１ Examples of the cycloalkyl group in the formula include a norbornyl group and an adamantyl group.

[0158] R Ｘ１ The substituent that the cycloalkyl group in R 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). Ｘ１ One or more of the carbon atoms which are ring members of the cycloalkyl group in the formula (I) may be replaced by a carbonyl carbon atom.

[0159] R Ｘ１ The alkyl group in R preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Ｘ１ 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 include R Ｘ１ is the same as the cycloalkyl group described above when R Ｘ１ When the alkyl group in R has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group. Ｘ１ The alkyl group in ２ - may be substituted with a carbonyl group.

[0160] R Ｘ１The aryl group in R is preferably a phenyl group. Ｘ１ 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. Ｘ１ is the same as the alkyl group described above when it is an alkyl group.

[0161] In formulas (BA-7) and (BA-9), 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). Ｘ２ may be the same or different.

[0162] In formula (BA-8), R Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Ｘ３ Examples of the halogen atom as R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Ｘ３ The monovalent organic group as R 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, a plurality of R Ｘ３ may be the same or different.

[0163] In formula (DA), R ａ１ The number of carbon atoms in the monovalent organic group is not particularly limited, but is preferably 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. ａ１is 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 a heteroatom as a ring member atom. Examples of heteroatoms include, but are not limited to, a nitrogen atom and an oxygen atom. The cycloalkyl group may also contain a carbonyl bond (>C═O) as a ring member atom. The alkyl group, cycloalkyl group, and aryl group may further have a substituent. Furthermore, A ３１ － and R ａ１ may be bonded to each other to form a ring.

[0164] L ａ１The divalent linking group as 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, more preferably 1 to 10 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. The aromatic group is a divalent aromatic group, and preferably has 6 to 20 carbon atoms, more preferably has 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, and examples thereof include aromatic rings having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. The aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The alkylene group, the cycloalkylene group, and the aromatic group may further have a substituent, and the substituent is preferably a halogen atom. ａ１ preferably represents a single bond.

[0165] As 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.

[0166] The molecular weight of the photodecomposable onium salt compound PG1 is not particularly limited, but is preferably not more than 3000, more preferably not more than 2000, and even more preferably not more than 1000. The molecular weight of the photodecomposable onium salt compound PG1 may be 100 or more.

[0167] (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)" will also be referred to as "photodecomposable onium salt compound PG2"). The photodecomposable onium salt compound PG2 has two or more of the above-mentioned salt structural moieties and generates a polyvalent organic acid upon exposure to light. The photodecomposable onium salt compound PG2 will be described below.

[0168] Compound (I) 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: Anionic moiety A １ － and the cationic moiety M １ ＋ and HA is produced by irradiation with actinic rays or radiation. １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and HA is produced by irradiation with actinic rays or radiation. ２ A structural moiety forming a second acidic moiety represented by the following formula (I):

[0169] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by２ 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.

[0170] When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different from each other. １ － , and two or more of the above M １ ＋ may be the same or different. １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0171] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. Ａ represents a monovalent organic group. Ａ Examples of the monovalent organic group represented by the formula (I) include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0172]

[0173]

[0174] In addition, the cationic moiety M １ ＋and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. 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)).

[0175] Compound (II) Compound (II) is a compound having two or more of the structural moieties X and one or more of the structural moieties Z described below, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0176] The compound (II) can be converted into the cation moiety M in the structural moiety X by irradiation with actinic rays or radiation. １ ＋ H ＋ HA is replaced by １ In other words, the compound PII can generate a compound PII (acid) having an acidic site represented by the above HA. １ and a structural moiety Z, which is a nonionic moiety capable of neutralizing the acid. In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I) and the definition of A １ － and M １ ＋ The definition and preferred embodiments are the same as those of the above. In addition, the two or more structural moieties X may be the same or different. In addition, the two or more structural moieties A １ － , and two or more of the above M １ ＋ may be the same or different.

[0177] 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. Examples of the functional group having an electron or a group capable of electrostatically interacting with a proton include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0178]

[0179] Examples of the partial structure of the functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0180] 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.

[0181] Examples of the photodecomposable onium salt compound PG2 include the compounds exemplified in paragraphs

[0023] to

[0095] of WO 2020 / 158313.

[0182] Specific examples of anions that may be contained in compound (C1) are shown below, but the present invention is not limited thereto. The specific examples below also show the pKa of the conjugate acid of each anion. For compounds having two anionic groups, the respective pKas (pKa1 and pKa2) are also shown.

[0183]

[0184] (Preferred Embodiment of Compound (C1)) The compound (C1) is preferably a compound represented by the following formula (Z-1).

[0185]

[0186] In formula (Z-1), Ar ｍ１ , Ar ｍ２and Ar ｍ３ Each independently represents an aryl group. ｍ１ , Ar ｍ２ and Ar ｍ３ At least two of the AN may be bonded to each other. － represents an anionic group. ｍ１ represents a g-valent group. g represents an integer of 1 or more. When g represents an integer of 2 or more, a plurality of AN － may be the same or different.

[0187] Ar ｍ１ , Ar ｍ２ and Ar ｍ３ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. ｍ１ , Ar ｍ２ and Ar ｍ３ The aryl group represented by Ar may have a substituent. The substituent is not particularly limited, but preferable examples thereof include a halogen atom, an alkyl group, a cycloalkyl group, a fluorinated alkyl group, a hydroxy group, a carboxyl group, an acyl group, an alkoxy group, a sulfonamide group, and an alkylsulfonyl group. ｍ１ , Ar ｍ２ and Ar ｍ３ At least two of Ar may be bonded to each other. ｍ１ , Ar ｍ２ and Ar ｍ３ When at least two of the groups are bonded to each other, they may be bonded by a single bond.

[0188] g is preferably an integer of 1 to 5, more preferably 1 or 2. ｍ１ represents a g-valent group. ｍ１ The monovalent group represented by L may be a hydrogen atom or a substituent, and is preferably a hydrogen atom or an organic group (for example, an alkyl group, a cycloalkyl group, an aryl group, or an organic group having 1 to 20 carbon atoms and formed by combining at least two of these groups). ｍ１Examples of the divalent group represented by AN include an alkylene group, a cycloalkylene group, an arylene group, and an organic linking group having 1 to 20 carbon atoms, which is formed by combining at least two of these groups. － The anionic group represented by is A in the above formula (DA). ３１ － The anionic group is the same as the anionic group represented by

[0189] <Nonionic Photodecomposable Acidic Compound (C2)> The nonionic photodecomposable acidic compound (C2) (also referred to as "compound (C2)") is a compound that decomposes when irradiated with actinic rays or radiation. The compound (C2) preferably has a carboxyl group. The compound (C2) is preferably a compound represented by the following formula (Z-2):

[0190]

[0191] In formula (Z-2), Ar ｍ４ represents an aryl group. １ represents an alkyl group. ｍ４ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. ｍ４ The aryl group represented by may have a substituent. The substituent is not particularly limited, but is preferably, for example, a halogen atom, an alkyl group, a cycloalkyl group, a fluorinated alkyl group, a hydroxy group, a carboxyl group, an acyl group, an alkoxy group, a sulfonamide group, or an alkylsulfonyl group. １ The alkyl group represented by 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 10 carbon atoms, and even more preferably an alkyl group having 1 to 5 carbon atoms.

[0192] When the resist composition of the present invention contains additive (C), the content of additive (C) in the resist composition of the present invention is not particularly limited, but is preferably 0.25 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, relative to the total solid content of the resist composition. Furthermore, the content of additive (C) is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, and even more preferably 30.0 mass% or less, relative to the total solid content of the resist composition.

[0193] [Other Components] The resist composition of the present invention may contain other components in addition to the components described above. There are no particular limitations on the other components, but examples thereof include hydrophobic resins and surfactants.

[0194] <Hydrophobic Resin> The resist composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. Effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with the developer, and suppression of outgassing.

[0195] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0196] When the resist composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% relative to the total solids content of the resist composition. The hydrophobic resin may be used alone or in combination with two or more different resins. When two or more different resins are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0197] <Surfactant> The resist composition may contain a surfactant. When a surfactant is contained, it is possible to form a pattern with better adhesion and fewer development defects. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicon-based surfactants include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954. When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass%, and more preferably 0.0005 to 1 mass%, based on the total solid content of the resist composition. One type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0198] 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 containing a resin (A) having a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group and an aromatic group, and a repeating unit (a2) represented by the following formula (1), and a solvent (B):

[0199]

[0200] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

[0201] The preferred embodiments of the resin (A) and the solvent (B) are as described above. The actinic ray-sensitive or radiation-sensitive resin composition may further contain at least one of the additive (C) and other components. The preferred embodiments of the additive (C) and other components are as described above.

[0202] [Resin] The present invention also relates to a resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (N-2).

[0203]

[0204] In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

[0205]

[0206] In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple of each, ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x1 R ｎ１ and x1 R ｎ２ At least one of x represents a hydrocarbon group. ｎ１ , x1 R ｎ２ and x2 E ２ At least two of these may be bonded to form a ring.

[0207] Preferred embodiments of the repeating unit represented by formula (1) and the repeating unit represented by formula (N-2) are as described above. Other preferred embodiments of the resin are the same as those of resin (A) described above.

[0208] [Resist film, pattern forming method] The present invention also relates to a resist film formed using the resist composition, and a pattern forming method using the 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, and developing the exposed film using a developer.

[0209] The procedure of the pattern formation method is not particularly limited, but preferably includes the following steps: Step 1: forming a resist film on a substrate using a resist composition, Step 2: exposing the resist film to light, and Step 3: developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0210] <Step 1: Resist Film Forming Step> Step 1 is a step of forming a resist film on a substrate using a resist composition.

[0211] A method for forming a resist film on a substrate using a resist composition includes, for example, applying the resist composition to the substrate. It is preferable to filter the resist composition before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0212] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0213] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or 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 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0214] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure and EB exposure are used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, when ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0215] 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 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 JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-061648 A is preferably formed on the resist film. It is also preferable that the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0216] <Step 2: Exposure Step> Step 2 is a step of exposing the resist film. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer laser (157 nm), EUV (13 nm), X-ray, and electron beam.

[0217] After exposure, it is preferable to perform post-exposure heat treatment (also referred to as post-exposure baking) before development. Post-exposure heat treatment promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. 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 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like.

[0218] <Step 3: Development Step> 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 an organic developer is preferred.

[0219] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and then left stationary for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0220] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a 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. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0221] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0222] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or 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, even 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.

[0223] <Other Steps> The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0224] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0225] The rinse liquid used in the rinse step after 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. The rinse liquid is preferably 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.

[0226] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the surface of the substrate (spray method). The pattern formation 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 and within the pattern by 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 typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0227] Alternatively, 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 (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0228] The resist composition and various materials used in the pattern formation method of the present invention (e.g., solvent, developer, rinse, anti-reflective coating composition, top coat composition, etc.) 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. Here, 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.

[0229] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0230] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0231] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution 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.

[0232] The resist composition may also contain water as an impurity. When water is contained as an impurity, the lower the content of water, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition. The resist composition may also contain residual monomers as impurities (for example, monomers derived from the raw material monomers used in the synthesis of the resin (A)). When water is contained as an impurity, the lower the content of residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition.

[0233] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) that have been antistatically treated can be used.

[0234] [Method for Manufacturing Electronic Device] The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitable for installation in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0235] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0236] [Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition (Resist Composition)] [Resin (A)] The resins (A-1 to A-16, RA-1 to RA-3) shown in Table 1 are shown below. Table 1 also shows the content (mol %; corresponding in order from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown below. The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of each repeating unit is １３ Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0237]

[0238] The structural formulas of A-1 to A-16 and RA-1 to RA-3 are shown below. A-1 to A-16 correspond to resin (A). RA-1 to RA-3 do not correspond to resin (A), but for convenience, RA-1 to RA-3 are listed in the column for resin (A) in Table 1 above and Table 2 below.

[0239]

[0240]

[0241]

[0242] [Solvent (B)] The solvents (B) used are as follows: B-1: Propylene glycol monomethyl ether acetate (PGMEA) B-2: Propylene glycol monomethyl ether (PGME) B-3: Cyclohexanone B-4: Ethyl lactate B-5: γ-butyrolactone B-6: Diacetone alcohol

[0243] [Additive (C)] The structural formulas of the additives (C) used are shown below: C-1 to C-10 are ionic photodecomposable compounds (C1), and C-11 and C-12 are nonionic photodecomposable acidic compounds (C2).

[0244]

[0245]

[0246] [Synthesis Example of Resin (A)] [Synthesis of A-1] The synthesis method of A-1, which is an example of Resin (A), is shown below. Resins (A) other than A-1 were also synthesized in the same manner.

[0247]

[0248] Methyltriphenylphosphonium bromide (Ph) in tetrahydrofuran (THF) (1000 g) ３ P ＋ MeBr － ) (273 g) was added, and the mixture was cooled to 0°C. Potassium tert-butoxide (tBuOK) (86.8 g) was added, and the mixture was stirred at 0°C for 30 minutes. A solution of 4-dimethylaminoacetophenone (50.0 g) dissolved in THF (500 g) was then added, and the mixture was further stirred at room temperature (23°C) for 1 hour. 500 mL of saturated aqueous sodium chloride solution and 200 mL of diisopropyl ether were added, and the organic layer was extracted using a separatory funnel. The organic layer was washed with 300 mL of saturated aqueous sodium chloride solution, and the solvent was then distilled off. 500 mL of diisopropyl ether was added to the residue, and the resulting solid was removed. The mixture was then purified by silica gel chromatography (ethyl acetate / n-hexane = 3 / 1 (mass ratio)), yielding 36.5 g of Monomer 1.

[0249]

[0250] Monomer 1 (17.28 g), methyl 2-chloroacrylate (12.84 g), polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.2452 g), and triethylamine (4.31 g) were dissolved in cyclopentanone (CP) (8.42 g). The resulting solution was stirred at 85°C for 6 hours under a nitrogen gas atmosphere, and then allowed to cool to room temperature (23°C). Next, the reaction solution after being allowed to cool was added dropwise to 1,050 g of stirred methanol, and the powder precipitated by the dropwise addition was collected by filtration and dried, yielding 9.01 g of A-1. Regarding A-1, １３The compositional ratio (molar ratio) of repeating units determined by C-NMR was 50 / 50 (repeating units derived from Monomer 1 / repeating units derived from methyl 2-chloroacrylate). The weight average molecular weight of the resulting A-1 measured by GPC was 19,000, and the polydispersity (Mw / Mn) was 1.81. The amount of remaining monomer was measured, and it was found to be 0.1% by mass or less relative to A-1.

[0251] [Preparation of Resist Compositions] Each component other than solvent (B) shown in Table 2 below was used in the content (mass %) shown in Table 2 and mixed with solvent (B) shown in Table 2. The content of each component is the mass ratio relative to the total solid content of the resist composition. The resulting mixture was then filtered through a polyethylene filter with a pore size of 0.03 μm to prepare resist compositions (Re-1 to Re-35, Re-X1 to Re-X3). The solid content concentration of each resist composition was adjusted to 1.6 mass %. The solid content refers to all components other than solvent (B). Table 2 lists the type of solvent (B) used and the mass ratio thereof. The resulting resist compositions were used in the examples and comparative examples.

[0252]

[0253] (Examples 1-1 to 1-35, Comparative Examples 1-1 to 1-3 EUV Exposure) [Pattern Formation] An underlayer film-forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 3 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. This resulted in a silicon wafer having a resist film. The silicon wafer having the resist film obtained by the above procedure was subjected to pattern exposure using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line width of 20 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90°C for 60 seconds, and then developed for 30 seconds with a developer shown in Table 3. Unless otherwise specified, the resist film was further rinsed with a rinse solution shown in Table 3, and then spin-dried to obtain a pattern. In Examples and Comparative Examples where "-" is shown in the "Rinse Solution" column in Table 3, rinsing was not performed.

[0254] [Developer and Rinse] The developers and rinses used are as follows: D-1: butyl acetate D-2: isopropyl acetate D-3: butyl acetate / n-undecane=90 / 10 (mass ratio)

[0255] [Evaluation] <Sensitivity> Using a length-measuring scanning electron microscope (SEM: Scanning Electron Microscope (CG-4100 manufactured by Hitachi High-Technologies Corporation)), the line width of a line and space pattern was measured while changing the exposure dose, and the exposure dose at which the line width became 20 nm was determined. This was designated as the optimum exposure dose (mJ / cm ２ The results are shown in Table 3. The smaller the value indicating the optimum exposure amount, the higher the sensitivity. More specifically, the optimum exposure amount was 70 mJ / cm. ２ Preferably, it is 60 mJ / cm or less. ２ More preferably, it is 50 mJ / cm or less. ２ It is more preferable that:

[0256] <Resolution> Under the exposure and development conditions for the above pattern formation, the exposure dose required to reproduce a mask pattern with a line width of 20 nm was defined as the optimal exposure dose, and when the line width of the line-and-space pattern formed was narrowed by further increasing the exposure dose from the optimal exposure dose, the minimum line width at which the pattern could be resolved without line breaks was defined as the value (nm) indicating resolution. The results are shown in Table 3. A smaller value indicating resolution indicates that a finer pattern can be resolved, indicating higher resolving power. The value indicating resolution is preferably 18.0 nm or less, more preferably 16.0 nm or less, particularly preferably 14.0 nm or less, and most preferably 12.0 nm or less.

[0257]

[0258] (Examples 2-1 to 2-35, Comparative Examples 2-1 to 2-3 EB Exposure) [Pattern Formation] Using ACTM (Tokyo Electron Limited), an anti-reflective coating composition DUV44 (Brewer Science) was applied to a 152 mm square mask blank having a Cr outermost surface, and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 60 nm. The resist composition shown in Table 4 was applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. This resulted in a mask blank with a resist film. The mask blank with the resist film obtained by the above procedure was subjected to pattern irradiation using an electron beam exposure device (EBM-9000, NuFlare Technology Inc., acceleration voltage 50 kV). Writing was performed so that the line width was 22 nm and a 1:1 line and space ratio was formed. The exposed resist film was baked at 100°C for 60 seconds, and then developed by puddling for 30 seconds with the developer shown in Table 4. Unless otherwise specified, the wafer was rinsed by pouring the rinse solution shown in Table 4 over it for 10 seconds while rotating at 1000 rpm, and then the wafer was rotated at 4000 rpm for 30 seconds to obtain a line and space pattern. In Examples and Comparative Examples where "-" is entered in the "Rinse Solution" column in Table 4, rinsing was not performed.

[0259] [Evaluation] Evaluation was carried out using the same procedures as for <Sensitivity> and <Resolution> in [Evaluation] in the above (Examples 1-1 to 1-35, Comparative Examples 1-1 to 1-3 EUV exposure). The results are shown in Table 4. In this evaluation, the optimum exposure dose was 300 μC / cm ２ Preferably, it is 250 μC / cm or less. ２ More preferably, it is 200 μC / cm or less. ２ The resolution is preferably 20 nm or less, more preferably 18 nm or less, further preferably 16 nm or less, and most preferably 14 nm or less.

[0260]

[0261] The results in Tables 3 and 4 show that the resist compositions of the examples are excellent in sensitivity and resolution.

[0262] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity and resolution. The present invention also can provide a resin that can be used in the actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0263] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-130218) filed on August 9, 2023, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray- or radiation-sensitive resin composition comprising: a resin (A) having a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group, and an aromatic group, the main chain of which is decomposed upon exposure to actinic rays or radiation; and a solvent (B).

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of the secondary amino group and the tertiary amino group is a group represented by the following formula (N-1): In formula (N-1), R ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ｎ１ and R ｎ２ At least one of R represents a hydrocarbon group. ｎ１ and R ｎ２ may be bonded to form a ring. ｎ１ and R ｎ２ may be bonded to the group having the group represented by formula (N-1) to form a ring. * represents the bonding position with an oxygen atom or a carbon atom other than the carbonyl carbon.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit (a2) represented by the following formula (1): In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein X in the formula (1) represents a fluorine atom, a chlorine atom or a bromine atom.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the aromatic group in the repeating unit (a1) is located closer to the main chain of the resin (A) than at least one of the secondary amino group and the tertiary amino group.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit represented by the following formula (N-2): In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple E ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x R ｎ３ and x1 R ｎ４ At least one of x represents a hydrocarbon group. ｎ３ , x1 R ｎ４ and x2 E ２ At least two of may be bonded to form a ring.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit represented by the following formula (N-3): In formula (N-3), x3 represents an integer of 1 or more and 5 or less. x4 represents an integer of 0 or more and 4 or less. However, the sum of x3 and x4 is an integer of 1 or more and 5 or less. E １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ３ and R ｎ４ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple E ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x3 R ｎ３ and x3 R ｎ４ At least one of x3 R represents a hydrocarbon group. ｎ３ , x3 R ｎ４ and x4 E ２ At least two of may be bonded to form a ring.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein x3 in formula (N-3) represents 1 or 2.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising at least one compound selected from the group consisting of an ionic photodecomposable compound (C1) and a non-ionic photodecomposable acidic compound (C2).

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9, which contains the ionic photodecomposable compound (C1), and the ionic photodecomposable compound (C1) is a compound containing at least one selected from the group consisting of a sulfonium cation and an iodonium cation.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein the ionic photodecomposable compound (C1) is a compound represented by the following formula (Z-1): In formula (Z-1), Ar ｍ１ , Ar ｍ２ and Ar ｍ３ Each independently represents an aryl group. ｍ１ , Ar ｍ２ and Ar ｍ３ At least two of the A, B and C may be bonded to each other. － represents an anionic group. ｍ１ represents a g-valent group. g represents an integer of 1 or more. When g represents an integer of 2 or more, a plurality of AN － may be the same or different.

12. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9, which contains the nonionic photodecomposable acidic compound (C2), and the nonionic photodecomposable acidic compound (C2) has a carboxyl group.

13. An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin (A) having a repeating unit (a1) containing at least one of a secondary amino group and a tertiary amino group, and an aromatic group, and a repeating unit (a2) represented by the following formula (1); and a solvent (B). In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring.

14. A resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (N-2): In formula (1), X represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. ０ represents a hydrogen atom or an organic group. １ represents a substituent. ０ and R １ may be bonded to form a ring. In formula (N-2), Ar represents an aromatic group. x1 represents an integer of 1 or more. x2 represents an integer of 0 or more. １ represents a hydrogen atom or a substituent. ２ represents a substituent. ｎ１ and R ｎ２ Each independently represents a hydrogen atom or a hydrocarbon group. ２ , R ｎ３ and R ｎ４ If there are multiple E ２ , R ｎ３ and R ｎ４ may be the same or different, provided that x R ｎ１ and x1 R ｎ２ At least one of x represents a hydrocarbon group. ｎ１ , x1 R ｎ２ and x2 E ２ At least two of may be bonded to form a ring.

15. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13.

16. A pattern forming method using the resist film according to claim 15.

17. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 16.

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