Photoactive ray-sensitive or radiation-sensitive resin composition, photoactive ray-sensitive or radiation-sensitive film, pattern forming method, and method for producing electronic device

Abstract

To provide a photoactive ray-sensitive or radiation-sensitive resin composition that is capable of inhibiting generation of development defects and exhibiting excellent resolving power when used in pattern formation, as well as to provide a photoactive ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device producing method employing the photoactive ray-sensitive or radiation-sensitive resin composition.SOLUTION: A photoactive ray-sensitive or radiation-sensitive resin composition includes a resin (A) having a repeating unit having an aromatic group and an organic solvent, the photoactive ray-sensitive or radiation-sensitive resin composition further including a compound (T) which has a specific structure and a molecular weight of 400 or more, as well as a photoactive ray-sensitive or radiation-sensitive film formed using the photoactive ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in ultra-microlithography processes applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. In recent years, with the increasing integration density of integrated circuits, there has been a growing demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technology for further improving resolution, the so-called immersion method, in which a high-refractive-index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed. In addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0003] Patent Document 1 describes a chemically amplified positive resist material containing an organic solvent, an alkali-insoluble or poorly alkali-soluble resin protected with an acid labile group that becomes alkali-soluble when the acid labile group dissociates, a photoacid generator, and a specific photobase generator.

[0004] Patent Document 2 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates a base upon irradiation with actinic rays or radiation, a resin that has a repeating unit with a lactone structure and whose solubility in an alkaline developer increases upon the action of an acid, and a compound that generates an acid upon irradiation with actinic rays or radiation. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 3514590 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-95635 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in recent years, the performance required of resist compositions has become even higher due to the ever-increasing miniaturization of patterns to be formed.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of development defects and has excellent resolution when used in pattern formation, as well as an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) having a repeating unit having an aromatic group and an organic solvent, An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (T) having a structure represented by the following formula (1) and having a molecular weight of 400 or more:

[0010] [ka]

[0011] In formula (1), Rc1 and Rc2 each independently represent a substituent. Rc1 and Rc2 may be bonded to form a ring. B 1 represents a nitrogen atom or a carbon atom. 1 When represents a carbon atom, a hydrogen atom or a substituent may be bonded to the carbon atom in addition to Rc1 and Rc2. * represents the bonding position. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (T) is at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a resin having a repeating unit represented by the following formula (1-3), and a resin having a repeating unit represented by the following formula (1-4):

[0012] [ka]

[0013] In formula (1-1), Rc 11 and Rc 12 Rc each independently represents a substituent. 11 and Rc 12 may be bonded to form a ring. 11 represents a nitrogen atom or a carbon atom. 11 When represents a carbon atom, the carbon atom is 11 and Rc 12 In addition to Rc, a hydrogen atom or a substituent may be bonded. 13 and Rc 14each independently represents a hydrogen atom or a substituent. In formula (1-2), Rc 21 and Rc 22 Rc each independently represents a substituent. 21 and Rc 22 may be bonded to form a ring. 21 represents a nitrogen atom or a carbon atom. 21 When represents a carbon atom, the carbon atom is 21 and Rc 22 In addition to the above, a hydrogen atom or a substituent may be bonded. 21 represents an aromatic ring. 21 may have a substituent bonded thereto. In formula (1-3), Rc 31 and Rc 32 Rc each independently represents a substituent. 31 and Rc 32 may be bonded to form a ring. 31 represents a nitrogen atom or a carbon atom. 31 When represents a carbon atom, the carbon atom is 31 and Rc 32 In addition, a hydrogen atom or a substituent may be bonded. In formula (1-4), Rc 41 and Rc 42 Rc each independently represents a substituent. 41 and Rc 42 may be bonded to form a ring. 41 represents a nitrogen atom or a carbon atom. 41 When represents a carbon atom, the carbon atom is 41 and Rc 42 In addition to the above, a hydrogen atom or a substituent may be bonded. 41 represents an aromatic ring. 41 A substituent may be bonded to L. 41 represents a single bond or a divalent linking group. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin (A) has a repeating unit having a phenolic hydroxyl group. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (A) has a repeating unit represented by the following formula (N-1):

[0014] [ka]

[0015] In formula (N-1), R 101 , R 102 and R 103 Each independently represents a hydrogen atom, a halogen atom, or an organic group. 102 Ar A may be bonded to form a ring, in which case R 102 represents a single bond or an alkylene group. A represents a single bond or a divalent linking group. A represents an aromatic group. 104 represents a hydroxyl group or a fluorinated alcohol group. 105 represents a halogen atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (A) has a repeating unit represented by the following formula (N-2):

[0016] [ka]

[0017] In formula (N-2), R 101 , R 102 and R 103 Each independently represents a hydrogen atom, an organic group, or a halogen atom. 102 Ar A may be bonded to form a ring, in which case R 102 represents a single bond or an alkylene group. A represents a single bond or a divalent linking group. A represents an aromatic group. k3 represents an integer of 1 to 5. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the compound (T) is at least one selected from the group consisting of compounds represented by the following formula (1-5) and compounds represented by the following formula (1-6):

[0018] [ka]

[0019] In formula (1-5), Rc 51 and Rc 52 Rc each independently represents a substituent. 53 , Rc 54 and Rc 55 Rc each independently represents a hydrogen atom or a substituent. 51 , Rc 52 and Rc 55 At least two of these may be bonded to form a ring. In formula (1-6), Rc 61 and Rc 62 Rc each independently represents a substituent. 63 represents a hydrogen atom or a substituent. 61 , Rc 62 and Rc 63 At least two of A may be bonded to form a ring. 61 represents an aromatic ring. 61 may have a substituent bonded thereto. [7] the compound (T) is at least one selected from the group consisting of a compound represented by the formula (1-1) and a compound represented by the formula (1-2), Rc in the above formula (1-1) 11 and Rc 12 at least one of represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group; Rc in the above formula (1-2) 21 and Rc 22at least one of the groups represented by the formula (1) represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group. [8] the compound (T) is at least one selected from the group consisting of a compound represented by the formula (1-1) and a compound represented by the formula (1-2), The actinic ray-sensitive or radiation-sensitive resin composition according to [2] or [7], wherein the compound (T) has only one structure represented by the formula (1) in the same molecule. [9] the compound (T) is at least one selected from the group consisting of a resin having a repeating unit represented by the formula (1-3) and a resin having a repeating unit represented by the formula (1-4), The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the resin (A) is the compound (T).

[10] the compound (T) is a resin having a repeating unit represented by the formula (1-4), L in the above formula (1-4) 41 represents a single bond.

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , wherein the resin (A) has a group that is decomposed by the action of an acid to generate a polar group.

[12] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , further comprising a compound (B) that generates an acid upon irradiation with actinic rays or radiation.

[13] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[12] , wherein the resin (A) has a repeating unit having a photoacid-generating group.

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

[13] .

[15] A pattern forming method comprising: a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[13] ; an exposure step of exposing the resist film to light; and a development step of developing the exposed resist film using a developer.

[16]

[15] A method for manufacturing an electronic device, comprising the pattern formation method according to

[15] . [Effects of the Invention]

[0020] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of development defects and has excellent resolution when used in pattern formation, as well as an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0022] In this specification, "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), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV, etc., but also drawing using particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values before and after it are included as the lower limit and upper limit.

[0023] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0024] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values measured using a Gel Permeation Chromatography (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: refractive index detector).

[0025] In the present specification, when a group (atomic group) is described 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 the present 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 a monovalent nonmetallic atomic group excluding a hydrogen atom, which can be selected from the following substituents T.

[0026] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; cycloalkyloxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; cycloalkyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. 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 (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0027] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. The compound may be "X-CO-OZ" or "XO-CO-Z".

[0028] 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. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0029] The pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + 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, such as Gaussian 16.

[0030] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and known literature values, as described above. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0031] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0032] <Actinic ray-sensitive or radiation-sensitive resin composition> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) (also simply referred to as "resin (A)") having a repeating unit having an aromatic group, and an organic solvent, and further containing a compound (T) (also simply referred to as "compound (T)") having a structure represented by the following formula (1) and having a molecular weight of 400 or more:

[0033] [ka]

[0034] In formula (1), Rc1 and Rc2 each independently represent a substituent. Rc1 and Rc2 may be bonded to form a ring. B 1 represents a nitrogen atom or a carbon atom. 1 When represents a carbon atom, a hydrogen atom or a substituent may be bonded to the carbon atom in addition to Rc1 and Rc2. * represents the bonding position.

[0035] The composition of the present invention is typically a resist composition and may be a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention can be used to form an actinic ray- or radiation-sensitive film. The actinic ray- or radiation-sensitive film formed using the composition of the present invention is typically a resist film.

[0036] The reason why the composition of the present invention can suppress the occurrence of development defects and provide excellent resolution when used in pattern formation is not clear in detail, but the present inventors presume it as follows, although the present invention is not limited in any way by the presumed mechanism below. When a resist film containing a resin having aromatic groups is irradiated with actinic rays or radiation (particularly EB or EUV), secondary electrons are generated in the resin having aromatic groups. When the resins containing the generated secondary electrons recombine with each other, they become highly polymerized and less soluble in the developer, leaving residue during development, which is thought to cause development defects and reduce resolution. In the composition of the present invention, when secondary electrons are generated in resin (A), which is a resin having an aromatic group, the generated secondary electrons are absorbed by compound (T) having a structure represented by formula (1). Compound (T), which absorbs the secondary electrons, decomposes to generate radical residues. The radical residues then recombine with the resin having the secondary electrons, thereby suppressing recombination between the resins and preventing the resins from becoming highly polymerized, which is believed to prevent the resins from becoming poorly soluble in the developer. Furthermore, by ensuring that the molecular weight of compound (T) is 400 or greater, volatilization of compound (T) can be prevented when the composition of the present invention is formed into a film, and the above-mentioned effects can be more efficiently achieved. For these reasons, the composition of the present invention is believed to be able to suppress the occurrence of development defects and to have excellent resolution.

[0037] First, the various components of the composition of the present invention will be described in detail below.

[0038] [Compound (T)] The compound (T) contained in the composition of the present invention is a compound having a structure represented by the following formula (1) and a molecular weight of 400 or more.

[0039] [ka]

[0040] In formula (1), Rc1 and Rc2 each independently represent a substituent. Rc1 and Rc2 may be bonded to form a ring. B1 represents a nitrogen atom or a carbon atom. 1 When represents a carbon atom, a hydrogen atom or a substituent may be bonded to the carbon atom in addition to Rc1 and Rc2. * represents the bonding position.

[0041] Rc1 and B in formula (1) 1 The bond between Rc2 and B 1 The bond between (the bond represented by the following formula (W1)) represents a single bond, a double bond, or an aromatic carbon-carbon bond. The same applies to the bond represented by the following formula (W1) in formulas (1-1), (1-2), (1-3), and (1-4) described below.

[0042] [ka]

[0043] In formula (1), Rc1 and Rc2 each independently represent a substituent. The substituents represented by Rc1 and Rc2 are not particularly limited, but are preferably organic groups. The number of carbon atoms in the organic groups represented by Rc1 and Rc2 is not particularly limited, but is preferably 1 to 100, more preferably 3 to 80. Examples of the organic groups represented by Rc1 and Rc2 include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyl groups, arylcarbonyl groups, arylcarbonyloxy groups, aryloxycarbonyl groups, and groups formed by combining two or more of these. Among these, alkyl groups, cycloalkyl groups, alkoxy groups, alkylcarbonyloxy groups, alkoxycarbonyl groups, aryl groups, and groups formed by combining two or more of these are preferred. The organic groups represented by Rc1 and Rc2 may further have a substituent (e.g., the above-mentioned substituent T, etc.).

[0044] The alkyl group represented by Rc1 and Rc2 may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. The alkyl group may have a substituent. The same applies to the alkoxy group, alkylthio group, alkylcarbonyl group, alkylcarbonyloxy group, and alkyl group contained in the alkoxycarbonyl group represented by Rc1 and Rc2.

[0045] The cycloalkyl group represented by Rc1 and Rc2 preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have, for example, one methylene group constituting the ring replaced with a heteroatom such as an oxygen atom or a sulfur atom, a group having a heteroatom such as a carbonyl group, a sulfonyl group, or an ester group, or a vinylidene group. Furthermore, the cycloalkyl group may have one or more ethylene groups constituting the cycloalkane ring replaced with a vinylene group. The cycloalkyl group may have a substituent. The same applies to the cycloalkyl group contained in the cycloalkyloxy group represented by Rc1 and Rc2.

[0046] The aryl group represented by Rc1 and Rc2 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 a phenyl group or a naphthyl group. The aryl group may have a substituent. The same applies to the aryl group contained in the aryloxy group, arylthio group, arylcarbonyl group, arylcarbonyloxy group, and aryloxycarbonyl group represented by Rc1 and Rc2.

[0047] The heteroaryl group represented by Rc1 and Rc2 is preferably an aromatic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom as a ring member. The number of ring atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The heteroaryl group may have a substituent. The same applies to the heteroaryl group contained in the heteroaryloxy group represented by Rc1 and Rc2.

[0048] In a preferred embodiment, at least one of Rc1 and Rc2 represents a substituent having at least one selected from the group consisting of an ether group (—O—), an ester group (—COO—), a carbonyl group (—CO—), and an acetal group. The acetal group is preferably a group represented by the following formula (Ac1).

[0049] [ka]

[0050] In formula (Ac1), Rp1 and Rp2 each independently represent a hydrogen atom or a substituent. Rp3 represents a substituent. Two of Rp1, Rp2, and Rp3 may be bonded to form a ring. * represents the bonding position. The explanation, specific examples and preferred ranges of the substituents represented by Rp1, Rp2 and Rp3 are the same as those of the substituents represented by Rc1 and Rc2 described above. The explanation, specific examples and preferred ranges for the ring formed by combining two of Rp1, Rp2 and Rp3 are the same as those for ring X described above.

[0051] When at least one of Rc1 and Rc2 represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group, the polarity of the decomposition product generated when compound (T) decomposes increases, which, for example, increases the solubility in an alkaline developer, thereby further suppressing the occurrence of development defects when an alkaline developer is used in pattern formation, and further improving resolution.

[0052] Rc1 and Rc2 may be bonded to form a ring. The ring formed by bonding Rc1 and Rc2 is also referred to as "ring X". Ring X may be a non-aromatic carbocyclic ring, a non-aromatic heterocyclic ring, an aromatic carbocyclic ring, or an aromatic heterocyclic ring. Ring X may be a monocyclic ring or a polycyclic ring. Ring X may have a substituent.

[0053] The case where ring X is a non-aromatic carbocyclic ring will be described below. The non-aromatic carbocyclic ring may be saturated or unsaturated. The number of carbon atoms in the non-aromatic carbocyclic ring is not particularly limited, but is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 12. The non-aromatic carbocyclic ring is preferably a cycloalkane ring or a cycloalkene ring, and more preferably a cycloalkane ring. The non-aromatic carbocyclic ring may be a monocyclic hydrocarbon or a polycyclic hydrocarbon. Examples of monocyclic hydrocarbons include cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene. Examples of polycyclic hydrocarbons include cycloalkanes having 6 to 20 carbon atoms, such as norbornane, tetracyclodecane, tetracyclododecane, adamantane, and diamantane, and cycloalkenes having 6 to 20 carbon atoms, such as norbornene. The non-aromatic carbocyclic ring may have a substituent. One or more methylene groups constituting the ring of the non-aromatic carbocyclic ring may be substituted with at least one bond selected from the group consisting of a carbonyl bond, an ester bond, an amide bond and a sulfone bond.

[0054] The case where ring X is a non-aromatic heterocycle will be described. The non-aromatic heterocycle may be saturated or unsaturated. The non-aromatic heterocycle 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 non-aromatic heterocycle is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 12. The number of carbon atoms in the non-aromatic heterocycle is not particularly limited, but is preferably 1 to 18, more preferably 2 to 15, and even more preferably 2 to 10. The non-aromatic heterocycle may be monocyclic or polycyclic. Examples of non-aromatic heterocycles include five-membered non-aromatic heterocycles such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocycles such as morpholine, piperidine, piperazine, and tetrahydropyran. The non-aromatic heterocycle may also be a fused ring having a structure in which the above-mentioned five-membered non-aromatic heterocycle or the above-mentioned six-membered non-aromatic heterocycle is fused with at least one selected from the group consisting of a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms such as cyclopentane or cyclohexane), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), the above-mentioned five-membered non-aromatic heterocycle, and the above-mentioned six-membered non-aromatic heterocycle. The non-aromatic heterocycle may have a substituent. One or more methylene groups constituting the ring of the non-aromatic heterocycle may be substituted with at least one bond selected from the group consisting of a carbonyl bond, an ester bond, an amide bond and a sulfone bond. When the bond between adjacent atoms contained in the non-aromatic heterocycle is a single bond, the single bond may be replaced with a multiple bond (for example, a double bond).

[0055] The case where ring X is an aromatic carbocyclic ring will be described below. The number of carbon atoms in the aromatic carbocyclic ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aromatic carbocyclic ring may be monocyclic or polycyclic. The aromatic carbocyclic ring is more preferably a benzene ring or a naphthalene ring. The aromatic carbocycle may be a fused ring having a structure in which an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene) is fused with at least one selected from the group consisting of a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), and a non-aromatic heterocyclic compound (for example, the above-mentioned five-membered non-aromatic heterocycle, the above-mentioned six-membered non-aromatic heterocycle, etc.). The aromatic carbocyclic ring may have a substituent.

[0056] The case where ring X is an aromatic heterocycle will be described. The aromatic heterocycle 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 heterocycle is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms in the aromatic heterocycle is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15. The aromatic heterocycle may be monocyclic or polycyclic. Examples of aromatic heterocycles include five-membered aromatic heterocycles such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The aromatic heterocycle may be a fused ring (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic heterocycle or the six-membered aromatic heterocycle is fused with at least one selected from the group consisting of the five-membered aromatic heterocycle, the six-membered aromatic heterocycle, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), and non-aromatic heterocycles (e.g., the five-membered non-aromatic heterocycle, the six-membered non-aromatic heterocycle, etc.). The aromatic heterocycle may have a substituent.

[0057] Ring X may have a substituent. In a preferred embodiment, ring X has a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0058] In formula (1), B 1 represents a nitrogen atom or a carbon atom, and preferably represents a carbon atom. B 1 represents a carbon atom, the carbon atom (B 1 In addition to Rc1 and Rc2, a hydrogen atom or a substituent (also referred to as "substituent Y") may be bonded to the carbon atom represented by Rc1 and Rc2. The description, specific examples, and preferred range of the substituent Y are the same as those for the substituent represented by Rc1 and Rc2 described above. The substituent Y may be bonded to at least one of Rc1 and Rc2. The explanation, specific examples, and preferred ranges for the ring formed by bonding the substituent Y to at least one of Rc1 and Rc2 are the same as those for the ring X described above.

[0059] In formula (1), * represents a bonding position. * preferably represents a bonding position to an atom contained in a structure constituting compound (T) other than the structure represented by formula (1). * may represent a bonding position to a hydrogen atom or a substituent, or may represent a bonding position to the main chain or side chain of a polymer (resin).

[0060] The molecular weight of the compound (T) is 400 or more. The compound (T) may or may not be a resin. When compound (T) is not a resin (in this case, compound (T) is also referred to as "compound (TL)"), the molecular weight is preferably 400 or more and less than 2000, more preferably 450 or more and 1000 or less, and even more preferably 500 or more and 800 or less. From the viewpoint of reducing development defects and improving resolution, it is preferable that the compound (TL) has only one structure represented by formula (1) in the same molecule. Preferred embodiments of the compound (TL) include the compounds represented by the formula (1-1) and the compounds represented by the formula (1-2) described below. Preferred embodiments of the compound (TL) also include the compounds represented by the formula (1-5) and the compounds represented by the formula (1-6) described below.

[0061] When compound (T) is a resin (compound (T) in this case is also referred to as "compound (TH)"), the molecular weight is preferably at least 2000. The weight average molecular weight (Mw) of compound (TH) is more preferably at least 2000 and at most 30000, further preferably at least 3000 and at most 25000, and particularly preferably at least 5000 and at most 15000. The dispersity (molecular weight distribution, Mw / Mn) of the compound (TH) is preferably from 1 to 5, more preferably from 1 to 3, still more preferably from 1.0 to 3.0, and particularly preferably from 1.1 to 2.0. The compound (TH) preferably has a repeating unit having a structure represented by formula (1). A preferred embodiment of the compound (TH) is at least one selected from the group consisting of a resin having a repeating unit represented by formula (1-3) and a resin having a repeating unit represented by formula (1-4) described below. Although the compound (TH) may be a resin different from the resin (A), it is preferable that the compound (TH) is the resin (A) (that is, the compound (TH) also serves as the resin (A)). That is, the compound (TH) is preferably a resin having a repeating unit having an aromatic group. When the compound (TH) also serves as the resin (A), the composition of the present invention may or may not contain a separate compound (T). When the compound (TH) is the resin (A), the compound (TH) may absorb secondary electrons generated by exposure and decompose to generate a repeating unit having an acid group, which may increase the solubility in an alkaline developer and decrease the solubility in an organic solvent. In this case, in the pattern formation method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0062] The compound (T) is preferably at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a resin having a repeating unit represented by the following formula (1-3), and a resin having a repeating unit represented by the following formula (1-4).

[0063] [ka]

[0064] In formula (1-1), Rc 11 and Rc 12 Rc each independently represents a substituent. 11 and Rc 12 may be bonded to form a ring. 11 represents a nitrogen atom or a carbon atom. 11 When represents a carbon atom, the carbon atom is11 and Rc 12 In addition to Rc, a hydrogen atom or a substituent may be bonded. 13 and Rc 14 each independently represents a hydrogen atom or a substituent. In formula (1-2), Rc 21 and Rc 22 Rc each independently represents a substituent. 21 and Rc 22 may be bonded to form a ring. 21 represents a nitrogen atom or a carbon atom. 21 When represents a carbon atom, the carbon atom is 21 and Rc 22 In addition to the above, a hydrogen atom or a substituent may be bonded. 21 represents an aromatic ring. 21 may have a substituent bonded to it. In formula (1-3), Rc 31 and Rc 32 Rc each independently represents a substituent. 31 and Rc 32 may be bonded to form a ring. 31 represents a nitrogen atom or a carbon atom. 31 When represents a carbon atom, the carbon atom is 31 and Rc 32 In addition, a hydrogen atom or a substituent may be bonded. In formula (1-4), Rc 41 and Rc 42 Rc each independently represents a substituent. 41 and Rc 42 may be bonded to form a ring. 41 represents a nitrogen atom or a carbon atom. 41 When represents a carbon atom, the carbon atom is 41 and Rc 42 In addition to the above, a hydrogen atom or a substituent may be bonded. 41 represents an aromatic ring. 41 A substituent may be bonded to L. 41 represents a single bond or a divalent linking group.

[0065] In formula (1-1), Rc 11and Rc 12 Rc each independently represents a substituent. 11 and Rc 12 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. Rc 11 and Rc 12 may be bonded to form a ring. 11 and Rc 12 The explanation, specific examples and preferred ranges for the ring formed by bonding are the same as those for ring X described above. Rc 11 and Rc 12 It is preferable that at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0066] In formula (1-1), B 11 represents a nitrogen atom or a carbon atom, and preferably represents a carbon atom. B 11 When represents a carbon atom, the carbon atom is 11 and Rc 12 In addition to the above, a hydrogen atom or a substituent ("substituent Y 1 ) may be bonded. 1 The explanation, specific examples and preferred ranges for are the same as those for the substituent Y described above. Substituent Y 1 is Rc 11 and Rc 12 The substituent Y may be bonded to at least one of the following: 1 and Rc 11 and Rc 12 The explanation, specific examples, and preferred ranges for the ring formed by bonding at least one of the above are the same as those for ring X.

[0067] In formula (1-1), Rc 13 and Rc 14 Rc each independently represents a hydrogen atom or a substituent. 13 and Rc 14The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above.

[0068] In formula (1-2), Rc 21 and Rc 22 Rc each independently represents a substituent. 21 and Rc 22 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. Rc 21 and Rc 22 may be bonded to form a ring. 21 and Rc 22 The explanation, specific examples and preferred ranges for the ring formed by bonding are the same as those for ring X described above. Rc 21 and Rc 22 It is preferable that at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0069] In formula (1-2), B 21 represents a nitrogen atom or a carbon atom, and preferably represents a carbon atom. B 21 When represents a carbon atom, the carbon atom is 21 and Rc 22 In addition to the above, a hydrogen atom or a substituent ("substituent Y 2 ) may be bonded. 2 The explanation, specific examples and preferred ranges for are the same as those for the substituent Y described above. Substituent Y 2 is Rc 21 and Rc 22 The substituent Y may be bonded to at least one of the following: 2 and Rc 21 and Rc 22 The explanation, specific examples, and preferred ranges for the ring formed by bonding at least one of the above are the same as those for ring X.

[0070] In formula (1-2), A 21 represents an aromatic ring. 21 The aromatic ring represented by is condensed with the succinimide ring shown in formula (1-2). 21 The aromatic ring represented by may be an aromatic carbocyclic ring or an aromatic heterocyclic ring.

[0071] A 21 The case where the aromatic ring represented by is an aromatic carbocyclic ring will be described. The number of carbon atoms in the aromatic carbocyclic ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aromatic carbocyclic ring may be monocyclic or polycyclic. The aromatic carbocyclic ring is more preferably a benzene ring or a naphthalene ring. The aromatic carbocycle may be a fused ring having a structure in which an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene) is fused with at least one selected from the group consisting of a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), and a non-aromatic heterocyclic compound (for example, a five-membered non-aromatic heterocycle such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, or tetrahydrothiophene, or a six-membered non-aromatic heterocycle such as morpholine, piperidine, piperazine, or tetrahydropyran). The aromatic carbocyclic ring may have a substituent.

[0072] A 21 The case where the aromatic ring represented by is an aromatic heterocycle will be described. The aromatic heterocycle 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 heterocycle is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms in the aromatic heterocycle is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15. The aromatic heterocycle may be monocyclic or polycyclic. Examples of aromatic heterocycles include five-membered aromatic heterocycles such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The aromatic heterocycle may be any of the five-membered aromatic heterocycles or six-membered aromatic heterocycles, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms such as cyclohexene), non-aromatic heterocycles (e.g., pyrrolidine, pyrroline, 2-oxo-2-methyl ... and a fused ring (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of five-membered non-aromatic heterocycles such as sazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocycles such as morpholine, piperidine, piperazine, and tetrahydropyran. The aromatic heterocycle may have a substituent.

[0073] A 21 may have a substituent bonded thereto (i.e., A 21 A may have a substituent. 21 The explanation, specific examples, and preferred ranges of the substituents that may be bonded to are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. A 21 In one preferred embodiment, the aryl group has a substituent having at least one group selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0074] In formula (1-3), Rc 31 and Rc 32 Rc each independently represents a substituent. 31 and Rc 32 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. Rc 31 and Rc 32 may be bonded to form a ring. 31 and Rc 32 The explanation, specific examples and preferred ranges for the ring formed by bonding are the same as those for ring X described above. Rc 31 and Rc 32 In a preferred embodiment, at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0075] In formula (1-3), B 31 represents a nitrogen atom or a carbon atom, and preferably represents a carbon atom. B 31 When represents a carbon atom, the carbon atom is 31 and Rc 32 In addition to the above, a hydrogen atom or a substituent ("substituent Y 3 ) may be bonded. 3 The explanation, specific examples and preferred ranges for are the same as those for the substituent Y described above. Substituent Y 3 is Rc 31 and Rc 32 The substituent Y may be bonded to at least one of the following: 3 and Rc 31 and Rc 32 The explanation, specific examples, and preferred ranges for the ring formed by bonding at least one of the above are the same as those for ring X.

[0076] In formula (1-4), Rc 41 and Rc 42Rc each independently represents a substituent. 41 and Rc 42 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. Rc 41 and Rc 42 may be bonded to form a ring. 41 and Rc 42 The explanation, specific examples and preferred ranges for the ring formed by bonding are the same as those for ring X described above. Rc 41 and Rc 42 In a preferred embodiment, at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0077] In formula (1-4), B 41 represents a nitrogen atom or a carbon atom, and preferably represents a carbon atom. B 41 When represents a carbon atom, the carbon atom is 41 and Rc 42 In addition to the above, a hydrogen atom or a substituent ("substituent Y 4 ) may be bonded. 4 The explanation, specific examples and preferred ranges for are the same as those for the substituent Y described above. Substituent Y 4 is Rc 41 and Rc 42 The substituent Y may be bonded to at least one of the following: 4 and Rc 41 and Rc 42 The explanation, specific examples, and preferred ranges for the ring formed by bonding at least one of the above are the same as those for ring X.

[0078] In formula (1-4), A 41 represents an aromatic ring. 41 The aromatic ring represented by is condensed with the succinimide ring depicted in formula (1-4). 41The description, specific examples and preferred range of the aromatic ring represented by A in the above formula (1-2) are 21 It is the same as in A 41 may have a substituent bonded thereto (i.e., A 41 A may have a substituent. 41 The explanation, specific examples, and preferred ranges of the substituents that may be bonded to are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. A 41 In one preferred embodiment, the aryl group has a substituent having at least one group selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0079] In formula (1-4), L 41 represents a single bond or a divalent linking group. L 41 The divalent linking group represented by is not particularly limited, but is preferably at least one linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -COO-, -S-, -SO-, and -SO2-, and more preferably at least one linking group selected from the group consisting of an alkylene group, an arylene group, and -COO-. The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. The alkylene group, cycloalkylene group and arylene group may have a substituent, and examples of the substituent include the substituent T described above. L 41 preferably represents a single bond.

[0080] It is also preferable that the compound (T) is at least one selected from the group consisting of compounds represented by the following formula (1-5) and compounds represented by the following formula (1-6).

[0081] [ka]

[0082] In formula (1-5), Rc 51 and Rc 52 Rc each independently represents a substituent. 53 , Rc 54 and Rc 55 Rc each independently represents a hydrogen atom or a substituent. 51 , Rc 52 and Rc 55 At least two of these may be bonded to form a ring. In formula (1-6), Rc 61 and Rc 62 Rc each independently represents a substituent. 63 represents a hydrogen atom or a substituent. 61 , Rc 62 and Rc 63 At least two of these may be bonded to form a ring. A 61 represents an aromatic ring. 61 may have a substituent bonded to it.

[0083] In formula (1-5), Rc 51 and Rc 52 Rc each independently represents a substituent. 51 and Rc 52 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above.

[0084] In formula (1-5), Rc 53 , Rc 54 and Rc 55 Rc each independently represents a hydrogen atom or a substituent. 53 , Rc 54 and Rc 55The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above.

[0085] Rc 51 , Rc 52 and Rc 55 At least two of Rc may be bonded to form a ring. 51 , Rc 52 and Rc 55 The explanation, specific examples and preferred ranges for the ring formed by bonding at least two of the above are the same as those for ring X described above. Rc 51 , Rc 52 and Rc 55 It is preferable that at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0086] In formula (1-6), Rc 61 and Rc 62 Rc each independently represents a substituent. 61 and Rc 62 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above.

[0087] In formula (1-6), Rc 63 represents a hydrogen atom or a substituent. 63 The explanation, specific examples and preferred ranges of the substituents represented by are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above.

[0088] Rc 61 , Rc 62 and Rc 63 At least two of Rc may be bonded to form a ring. 61 , Rc 62 and Rc 63 The explanation, specific examples and preferred ranges for the ring formed by bonding at least two of the above are the same as those for ring X described above. Rc61 , Rc 62 and Rc 63 It is preferable that at least one of the groups represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0089] In formula (1-6), A 61 represents an aromatic ring. 61 The aromatic ring represented by is condensed with the succinimide ring depicted in formula (1-6). 61 The description, specific examples and preferred range of the aromatic ring represented by A in the above formula (1-2) are 21 It is the same as in A 61 may have a substituent bonded thereto (i.e., A 61 A may have a substituent. 61 The explanation, specific examples, and preferred ranges of the substituents that may be bonded to are the same as those of the substituents represented by Rc1 and Rc2 in formula (1) described above. A 61 In one preferred embodiment, the aryl group has a substituent having at least one group selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0090] In a preferred embodiment of the composition of the present invention, compound (T) is at least one selected from the group consisting of compounds represented by formula (1-1) and compounds represented by formula (1-2), Rc in formula (1-1) 11 and Rc 12 at least one of represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group; Rc in formula (1-2) 21 and Rc 22 represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

[0091] In a preferred embodiment of the composition of the present invention, compound (T) is at least one selected from the group consisting of compounds represented by formula (1-1) and compounds represented by formula (1-2), In this embodiment, compound (T) has only one structure represented by formula (1) in the same molecule.

[0092] In a preferred embodiment of the composition of the present invention, the compound (T) is at least one selected from the group consisting of a resin having a repeating unit represented by formula (1-3) and a resin having a repeating unit represented by formula (1-4), In this embodiment, the compound (T) is the resin (A).

[0093] In a preferred embodiment of the composition of the present invention, the compound (T) is a resin having a repeating unit represented by formula (1-4): L in formula (1-4) 41 represents a single bond.

[0094] Specific examples of the compound (TL) include Q-1 to Q-7 described below, but are not limited to these. Specific examples of the repeating unit having the structure represented by formula (1) in compound (TH) include, but are not limited to, a-1 to a-3 described below.

[0095] The content of repeating units having the structure represented by formula (1) in compound (TH) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the total repeating units in compound (TH). The content of repeating units having the structure represented by formula (1) in compound (TH) is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, based on the total repeating units in compound (TH).

[0096] The compound (TH) may have a repeating unit other than the repeating unit having the structure represented by formula (1). Examples of the repeating unit other than the repeating unit having the structure represented by formula (1) include repeating units that may be contained in the resin (A) described below.

[0097] The content of the compound (T) in the composition of the present invention is preferably from 0.5 to 99.9 mass %, more preferably from 1.0 to 95.0 mass %, based on the total solid content of the composition of the present invention. The compound (T) may be used alone or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range. When the composition of the present invention contains compound (TL), the content of compound (TL) is preferably 0.5 to 20.0 mass %, more preferably 1.0 to 10.0 mass %, based on the total solid content of the composition of the present invention. The compound (TL) may be used alone or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range. When the composition of the present invention contains compound (TH), the content of compound (TH) is preferably 40.0 to 99.9 mass %, more preferably 60.0 to 95.0 mass %, based on the total solid content of the composition of the present invention. The compound (TH) may be used alone or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range. The composition of the present invention may contain the compound (TL) and the compound (TH).

[0098] Compound (T) can be synthesized by referring to known methods. Generally, as shown below, it is obtained by reacting an imide compound or an N-hydroxyimide compound derived from an acid anhydride with an amine or a carboxylic acid using a condensing agent, but it can also be synthesized by methods other than these reaction examples. Details of synthesis examples will be shown in the Examples below.

[0099] [ka]

[0100] Resin (A) The resin (A) contained in the composition of the present invention is a resin having a repeating unit having an aromatic group. The resin (A) may or may not have a group that decomposes under the action of an acid to generate a polar group (also referred to as an "acid-decomposable group").

[0101] (Repeating unit having an acid group) The resin (A) preferably contains a repeating unit having an acid group. The acid group of the repeating unit having an acid group is preferably a phenolic hydroxyl group.The resin (A) preferably has a repeating unit having a phenolic hydroxyl group. The repeating unit containing a polar group is preferably a repeating unit represented by the following formula (N-1): That is, the resin (A) preferably has a repeating unit represented by the following formula (N-1).

[0102] [ka]

[0103] In formula (N-1), R 101 , R 102 and R 103 Each independently represents a hydrogen atom, a halogen atom, or an organic group. 102 Ar A may be bonded to form a ring, in which case R 102 represents a single bond or an alkylene group. A represents a single bond or a divalent linking group. A represents an aromatic group. 104 represents a hydroxyl group or a fluorinated alcohol group. 105 represents a halogen atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more.

[0104] R in formula (N-1) 101 , R 102 and R103 each independently represents a hydrogen atom, a halogen atom or an organic group. R 101 , R 102 and R 103 The organic group represented by the formula (I) is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a cyano group, or an alkoxycarbonyl group, and more preferably an alkyl group. R 101 , R 102 and R 103 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, but is preferably 1 to 5, and more preferably 1 to 3. R 101 , R 102 and R 103 The cycloalkyl group represented by the formula (I) 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 number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. In the cycloalkyl group, for example, one or more methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R 101 , R 102 and R 103 The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. R 101 , R 102 and R 103 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred.

[0105] L in formula (N-1)A represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited, but examples thereof include -COO-, -CONR 106 -, an alkylene group, or a group formed by combining two or more of these groups. 106 represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R 106 When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0106] Ar in formula (N-1) A represents an aromatic group, more specifically, a (k1+k2+1)-valent aromatic group. Ar A The aromatic group represented by may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Ar A When the aromatic group represented by is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably, for example, 6 to 20, and more preferably 6 to 14. The aromatic hydrocarbon group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. The aromatic hydrocarbon group may also be a group obtained by removing (k1+k2+1) hydrogen atoms from a fused ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is condensed with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.).

[0107] Ar AWhen the aromatic group represented by is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. 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 carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably, for example, 2 to 18, more preferably 3 to 12, and even more preferably 4 to 12. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but is, for example, preferably 5 to 20, and more preferably 6 to 15. Examples of aromatic heterocyclic groups include groups obtained by removing (k1 + k2 + 1) hydrogen atoms from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, and furan, and 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 (k1+k2+1) hydrogen atoms from a fused ring compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is fused 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., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, etc., and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.).

[0108] R in formula (N-1) 104 represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a group in which a hydroxyl group is bonded to a fluoroalkyl group. The fluorinated alcohol group may be a group represented by the following formula (FA1).

[0109] [ka]

[0110] In formula (FA1), Rq1, Rq2, and Rq3 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, or a hydroxyl group. However, at least one of Rq1, Rq2, and Rq3 represents a fluorine atom or a fluoroalkyl group. Furthermore, at least one of Rq1, Rq2, and Rq3 represents a hydroxyl group, an alkyl group having a hydroxyl group, or a fluoroalkyl group having a hydroxyl group. E1 represents an integer of 1 or greater. Two or more of Rq1, Rq2, and Rq3 may be bonded to form a ring. * represents a bonding position. The alkyl group represented by Rq1, Rq2, and Rq3 may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. The alkyl group may have a substituent other than a fluorine atom. The fluoroalkyl group represented by Rq1, Rq2, and Rq3 is a group in which at least one hydrogen atom of an alkyl group is substituted with a fluorine atom, and is preferably a group in which at least one hydrogen atom of the alkyl group represented by the above-mentioned Rq1, Rq2, and Rq3 is substituted with a fluorine atom. The fluoroalkyl group may be a perfluoroalkyl group. The fluoroalkyl group may have a substituent other than a fluorine atom.

[0111] R in formula (N-1) 105 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred.

[0112] Ar A The aromatic group represented by is R104 and R 105 The substituent may further have a substituent other than the above. The substituent is not particularly limited, but examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl groups.

[0113] In formula (N-1), k1 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. In formula (N-1), k2 represents an integer of 0 or more, preferably an integer of 0 to 4, and more preferably 0 or 1.

[0114] The repeating unit having an acid group is preferably represented by the following formula (N-2): That is, the resin (A) preferably has a repeating unit represented by the following formula (N-2).

[0115] [ka]

[0116] In formula (N-2), R 101 , R 102 and R 103 Each independently represents a hydrogen atom, an organic group, or a halogen atom. 102 Ar A may be bonded to form a ring, in which case R 102 represents a single bond or an alkylene group. A represents a single bond or a divalent linking group. A represents an aromatic group. k3 represents an integer of 1 to 5.

[0117] R in formula (N-2) 101 , R 102 , R 103 , L A and Ar AThe explanation, specific examples and preferred ranges of R in the above formula (N-1) are as follows: 101 , R 102 , R 103 , L A and Ar A It is the same as in In formula (N-2), k3 represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0118] Specific examples of repeating units having an acid group are shown below, but are not limited to these. 1 and G 2 each independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group. f1 represents an integer of 1 to 3.

[0119] [ka]

[0120] When the resin (A) has a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit having an acid group in the resin (A) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (A). The repeating unit having an acid group contained in the resin (A) may be one type or two or more types. When two or more types are contained, the total content thereof is preferably within the above-mentioned suitable content range.

[0121] (Repeating unit having an acid-decomposable group) In a preferred embodiment, the resin (A) has a repeating unit having an acid-decomposable group. When the resin (A) has a repeating unit having an acid-decomposable group, typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. When the resin (A) has a repeating unit having an acid-decomposable group, the resin (A) is an acid-decomposable resin. When the resin (A) is an acid-decomposable resin, typically, a positive pattern is preferably formed when an alkaline developer is used as the developer in a pattern formation method using the composition of the present invention, and a negative pattern is preferably formed when an organic developer is used as the developer.

[0122] The acid-decomposable group preferably has a structure in which a polar group is protected with a group that is eliminated by the action of an acid (a leaving group).

[0123] The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0124] Examples of the group that leaves when acted upon by an acid (leaving group) include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0125] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to each other to form a ring (which may be either a monocyclic ring or a polycyclic ring). The alkyl groups of Rx1 to Rx3 are preferably alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group, and more preferably alkyl groups having 1 to 5 carbon atoms. The number of carbon atoms in the cycloalkyl group of Rx1 to Rx3 is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have, for example, one methylene group constituting the ring replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, the cycloalkyl group may have one or more ethylene groups constituting the cycloalkane ring replaced with a vinylene group. That is, Rx1 to Rx3 may be a cycloalkenylene group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aralkyl group of Rx1 to Rx3 is preferably a group in which one hydrogen atom in the alkyl group of the above-mentioned Rx1 to Rx3 is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples thereof include a benzyl group. Examples of the alkenyl group of Rx1 to Rx3 include alkenyl groups having 2 to 20 carbon atoms, and alkenyl groups having 2 to 10 carbon atoms are preferred, such as vinyl and allyl groups. Examples of the alkynyl group of Rx1 to Rx3 include an alkynyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms is preferred, such as an ethynyl group. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0126] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. Also, R 38 may bond with another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0127] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0128] Resin (A) may contain at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3): The repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3) are repeating units containing an acid-decomposable group.

[0129] [ka]

[0130] In formula (M-1), R 11 , R 12 and R 13 L each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M1 represents a single bond or a divalent linking group. 14 , R 15 and R 16R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 14 , R 15 and R 16 Two of these may be bonded to form a ring. In formula (M-2), R 21 , R 22 and R 23 L each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M2 represents a single bond or a divalent linking group. 24 , R 25 and R 26 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 25 and R 26 may be bonded to form a ring. M2 The aromatic group contained in R 22 or R 24 may be bonded to form a ring. In formula (M-3), R 31 , R 32 and R 33 L each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M3 represents a single bond or a divalent linking group. 34 and R 35 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 35 and R 36 may be bonded to form a ring.

[0131] The repeating unit represented by formula (M-1) will be described below. R 11 , R 12 and R 13The 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, but is preferably 1 to 5, and more preferably 1 to 3. R 11 , R 12 and R 13 The cycloalkyl group represented by the formula (I) 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 number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R 11 , R 12 and R 13 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. R 11 , R 12 and R 13 The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0132] L M1 preferably represents a single bond or a divalent linking group containing an aromatic group. L M1 The aromatic group contained in may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group is preferably a divalent group.

[0133] L M1When the aromatic group contained in is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably, for example, 6 to 20, and more preferably 6 to 14. The aromatic hydrocarbon group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group. The aromatic hydrocarbon group may also be a group obtained by removing two hydrogen atoms from a fused ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is fused with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.).

[0134] L M1 When the aromatic group contained in is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. 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 carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably, for example, 2 to 18, more preferably 3 to 12, and even more preferably 4 to 12. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but is, for example, preferably 5 to 20, and more preferably 6 to 15. Examples of aromatic heterocyclic groups include groups obtained by removing two hydrogen atoms from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, and furan, 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 two hydrogen atoms from a fused ring compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the above-mentioned five-membered aromatic heterocyclic compound or the above-mentioned six-membered aromatic heterocyclic compound is fused with at least one selected from the group consisting of the above-mentioned five-membered aromatic heterocyclic compound, the above-mentioned 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., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, etc., and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.).

[0135] L M1 may contain other divalent groups in addition to the aromatic group. Examples of other divalent groups include -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, and groups in which a plurality of these groups are linked together. L M1 When contains another divalent group, the other divalent group is preferably located closer to the main chain of the resin (A) than the aromatic group.

[0136] R 14 , R 15 and R 16 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, but is preferably 1 to 5, and more preferably 1 to 3. R 14 , R 15 and R 16 In the alkyl group represented by the formula: the methylene group may be substituted with at least one of -CO- and -O-. R 14 , R 15 and R 16The cycloalkyl group represented by the formula (I) 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, an adamantyl group, etc. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. R 14 , R 15 and R 16 The number of carbon atoms in the aryl group represented by R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 14. 14 , R 15 and R 16 The aryl group represented by the formula (I) is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. R 14 , R 15 and R 16 The aralkyl group represented by the formula 14 , R 15 and R 16 One hydrogen atom in the alkyl group represented by the above-mentioned R 14 , R 15 and R 16 Preferred are groups substituted with an aryl group (preferably a phenyl group) represented by the following formula: and examples thereof include a benzyl group. R 14 , R 15 and R 16 The alkenyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 5, and more preferably 2 to 3. The alkenyl group is preferably a vinyl group.

[0137] R 14 , R 15 and R 16 Two of the R may be bonded to form a ring. 14 , R 15 and R 16The ring formed by combining two of these is preferably a cycloalkyl ring. The cycloalkane ring may be a monocyclic cycloalkane ring or a polycyclic cycloalkane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0138] Each of the above groups in formula (M-1) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0139] The repeating unit represented by formula (M-2) will be described below. R 21 , R 22 and R 23 The explanation, specific examples and preferred ranges of R in the above formula (M-1) are as follows: 11 , R 12 and R 13 is the same as L M2 The explanation, specific examples and preferred ranges of L in the above formula (M-1) M1 is the same as R 24 , R 25 and R 26 The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by the formula (M-1) are as follows: 14 , R 15 and R 16 is the same as R 25 and R 26 may be bonded to form a ring. 25 and R 26 The ring formed by bonding is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms. L M2 When L contains an aromatic group, M2The aromatic group contained in R 22 or R 24 may be bonded to form a ring. M2 Aromatic groups contained in R 22 or R 24 The ring formed by bonding is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms.

[0140] Each of the above groups in formula (M-2) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0141] The repeating unit represented by formula (M-3) will be described below. R 31 , R 32 and R 33 The explanation, specific examples and preferred ranges of R in the above formula (M-1) are as follows: 11 , R 12 and R 13 is the same as L M3 The explanation, specific examples and preferred ranges of L in the above formula (M-1) M1 is the same as R 34 , R 35 and R 36 The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by the formula (M-1) are as follows: 14 , R 15 and R 16 is the same as R 35 and R 36 may be bonded to form a ring. 35 and R 36 The ring formed by bonding is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms.

[0142] Each of the above groups in formula (M-3) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0143] A preferred embodiment of the repeating unit having an acid-decomposable group is one having a halogen atom. In this embodiment, it is preferable that at least one of a fluorine atom and an iodine atom is contained, and it is more preferable that one repeating unit has 1 to 10 fluorine atoms and iodine atoms in total, and further more preferable that one to 5 fluorine atoms and iodine atoms in total. A preferred embodiment of the repeating unit having an acid-decomposable group is one that does not have a halogen atom. For repeating units having an acid-decomposable group, the descriptions in paragraphs

[0029] to

[0075] of WO 2022 / 024928 can be cited. The above descriptions are incorporated herein by reference.

[0144] Specific examples of repeating units having an acid-decomposable group are shown below, but are not limited to these.

[0145] [ka]

[0146] When the resin (A) has a repeating unit having an acid-decomposable group, the content of the repeating unit having an acid-decomposable group in the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit having an acid-decomposable group in the resin (A) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (A). The repeating unit having an acid-decomposable group contained in the resin (A) may be of one type or two or more types. When two or more types are contained, the total content thereof is preferably within the above-mentioned suitable content range.

[0147] (Repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the above-mentioned <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>, the resin (A) may also have a repeating unit (hereinafter also referred to as "unit X") that has neither an acid-decomposable group nor an acid group, but has a fluorine atom, a bromine atom, or an iodine atom. The <repeating unit that has neither an acid-decomposable group nor an acid group, but has a fluorine atom, a bromine atom, or an iodine atom> is preferably different from other types of repeating units such as the below-mentioned <repeating unit having a lactone group, a sultone group, or a carbonate group> and <repeating unit having a photoacid-generating group>.

[0148] The unit X is preferably a repeating unit represented by formula (C).

[0149] [ka]

[0150] L5 represents a single bond or an ester group. R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these. Specific examples of repeating units having a fluorine atom or an iodine atom include repeating units described in

[0116] to

[0117] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0151] When the resin (A) contains the unit X, the content of the unit X may be 5 mol % or more, or 10 mol % or more, based on all repeating units in the resin (A). The content of the unit X may be 50 mol % or less, or 40 mol % or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain any X units.

[0152] (Repeating units having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit having a lactone group, a sultone group, or a carbonate group (hereinafter also referred to as "unit Y"). It is also preferred that the unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0153] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among these, a 5- to 7-membered cyclic lactone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure, or a 5- to 7-membered cyclic sultone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure. The carbonate group is preferably a cyclic carbonate group. For repeating units having a cyclic carbonate group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928, the disclosures of which are incorporated herein by reference.

[0154] Resin (A) preferably has a repeating unit having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-22), a sultone structure represented by any one of the following formulae (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any one of the following formulae (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of Resin (A). The lactone group, sultone group, and carbonate group may have a substituent.

[0155] R in the following structural formula L represents a substituent. L If there are multiple R Lmay be the same or different. L Examples of the R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple R L may be the same or different, and multiple R L They may be bonded to each other to form a ring.

[0156] [ka]

[0157] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0158] [ka]

[0159] In formula (AI-2), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Examples of groups that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group combining these. Among these, Ab is preferably a single bond or a linking group represented by -Ab1-CO2-. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any one of formulas (CC1-1) to (CC1-2).

[0160] When the resin (A) contains the unit Y, the content of the unit Y may be 1 mol % or more, or 10 mol % or more, based on all repeating units in the resin (A), and the content of the unit Y may be 80 mol % or less, or 70 mol % or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain any Y units.

[0161] (Repeating unit having a photoacid generating group) The resin (A) may have a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid-generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0162] [ka]

[0163] R 41 represents a hydrogen atom or a methyl group. 41 and L 42 R each independently represents a single bond or a divalent linking group. 40 represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0164] L 41 represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).

[0165] L 42The divalent linking group represented by is preferably at least one linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -S-, -SO-, -SO2-, and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. The alkylene group, cycloalkylene group and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0166] R 40 is preferably a group represented by the following formula (S4-1).

[0167] [ka]

[0168] In equation (S4-1), Q - represents the residue of an acid, and M + represents a cation. * represents L 41 represents the bonding position with The acid residue is a group formed by dissociating a proton from an acid. Q - is a carboxylate anion group (COO - ), sulfonate anion group (SO3 - ), or a sulfonamide group (N - -SO2R N1 It is expressed as R N1represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. M + The explanation, specific examples and preferred ranges of M in the explanation of compound (B) to be described later. + is the same as

[0169] Specific examples of repeating units having a photoacid generating group include the repeating units described in

[0094] to

[0105] of JP 2014-041327 A, the repeating unit described in

[0094] of WO 2018 / 193954 A, and the repeating unit described in

[0138] of WO 2022 / 024928 A. The above descriptions are incorporated herein by reference.

[0170] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A and the repeating unit described in paragraph

[0094] of WO 2018 / 193954 A.

[0171] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 2 mol% or more, and particularly preferably 3 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (A). It is also preferred that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0172] (Repeating unit represented by formula (V-1) or formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). It is also preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the repeating units described above.

[0173] [ka]

[0174] In formulas (V-1) and (V-2), R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R represents an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X4 represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0175] (Repeating unit to reduce the mobility of the main chain) Resin (A) may have a high glass transition temperature (Tg) to prevent excessive diffusion of generated acid or pattern collapse during development. Tg may be higher than 90°C, higher than 100°C, higher than 110°C, or higher than 125°C. To improve the dissolution rate in the developer, Tg may be 400°C or lower, or 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of a repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg for each mass proportion is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to obtain the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0176] For repeating units for reducing the mobility of the main chain, the contents of

[0144] to

[0160] of WO 2022 / 024928 are incorporated by reference.

[0177] (a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>.

[0178] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves adhesion to the substrate and affinity for the developer. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0179] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) substituted at the α-position with an electron-withdrawing group, with carboxyl groups being preferred. Resin (A) containing a repeating unit having an alkali-soluble group improves resolution, particularly in contact hole applications. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0180] (Repeating units that have an alicyclic hydrocarbon structure and are not acid decomposable) Resin (A) may have an alicyclic hydrocarbon structure and a repeating unit that is not acid-decomposable. This reduces the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and are not acid-decomposable include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, and cyclohexyl(meth)acrylate.

[0181] (Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group) The resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.

[0182] [ka]

[0183] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP-A No. 2014-098921.

[0184] (Other repeating units) Furthermore, the resin (A) may have repeating units other than the repeating units described above. Resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in

[0170] of WO 2022 / 024928.

[0185] Regarding the resin (A), the contents of

[0171] to

[0172] of WO 2022 / 024928 can be further cited.

[0186] The resin (A) preferably has an aromatic group in any of the repeating units described above. The content of repeating units having an aromatic group in the resin (A) is not particularly limited, but is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, based on the total repeating units in the resin (A). The content of repeating units having an aromatic group in the resin (A) is 100 mol% or less, or may be 95 mol% or less, or may be 90 mol% or less, based on the total repeating units in the resin (A). The repeating unit having an aromatic group contained in the resin (A) may be one type or two or more types. When two or more types are contained, the total content thereof is preferably within the above-mentioned suitable content range.

[0187] The resin (A) can be synthesized by a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 2,000 to 30,000, even more preferably 3,000 to 25,000, and particularly preferably 5,000 to 15,000, as determined by GPC in terms of polystyrene. The dispersity (also referred to as "molecular weight distribution," "Pd," or "Mw / Mn") of the resin (A) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0188] The content of the resin (A) in the composition of the present invention is preferably from 40.0 to 99.9 mass %, more preferably from 60.0 to 95.0 mass %, based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more resins are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0189] [Compound (B) that generates an acid upon exposure to actinic rays or radiation] The composition of the present invention may contain a compound (B) (also simply referred to as "compound (B)") that generates an acid upon irradiation with actinic rays or radiation. The compound (B) is a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation. The compound (B) is also referred to as a "photoacid generator." The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Alternatively, the photoacid generator may be in the form of a low molecular weight compound and the form of a low molecular weight compound incorporated into a part of a polymer. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferred. When the photoacid generator is incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). When the resin (A) does not have the photoacid-generating repeating unit described above, the composition of the present invention preferably contains a compound (B) that is a compound different from the resin (A). When the resin (A) has a photoacid-generating repeating unit, the composition of the present invention may or may not contain a separate compound (B). The photoacid generator is also preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of less than 0 upon irradiation with actinic rays or radiation, and more preferably a compound that generates an acid having a pKa of -15 or more and less than -1.

[0190] Examples of photoacid generators include "M + X - The compound is preferably an onium salt that generates an organic acid upon exposure to light. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0191] "M + X - In the compound represented by ", M + represents a cation, preferably an organic cation. The organic cation is not particularly limited, and the valence of the organic cation may be monovalent or divalent or higher. Among these, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0192] [ka]

[0193] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more 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 (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0194] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0195] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, wherein at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. R 201 ~R 203 one of which 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 groups formed by combining two of these include alkylene groups 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., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-). Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0196] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. 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 that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0197] R 201 ~R 203 The substituent that the aryl group, alkyl group, and cycloalkyl group may have is preferably 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 and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above substituents may further have a substituent, if possible, and 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. It is also preferred that the above substituents are combined in any manner to form an acid-decomposable group. The acid-decomposable group is intended to be a group that decomposes under the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that leaves under the action of an acid. The polar group and leaving group are as described above.

[0198] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 are each independently a cation representing an organic group having no aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. R 201 ~R 203 The organic group not having an aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. R 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.

[0199] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. R 201 ~R 203 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0200] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0201] [ka]

[0202] In formula (ZaI-3b), R 1c ~R 5ceach independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each 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. R 1c ~R 7c , and R x and R y It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0203] 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.

[0204] 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 include alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom. R 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.

[0205] 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 6c and R 7c , R 5c and R x , and R x and R y The ring formed by bonding together may have a substituent.

[0206] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0207] [ka]

[0208] In formula (ZaI-4b), l represents an integer of 0 to 2; r represents an integer of 0 to 8; R 13represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (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 groups are present, each independently represents the above group such as a hydroxyl group. R 15 Each of R 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 they are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R 15 are preferably alkylene groups and bond together to form a ring structure. 15 The ring formed by bonding together may have a substituent.

[0209] In formula (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. R 13 ~R 15 , and R x and R yIt is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0210] Next, formula (ZaII) will be explained. In formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 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 (for example, 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 (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0211] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 and R 205 Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0212] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0213] [ka]

[0214] [ka]

[0215] "M + X - In the compound represented by ", X - represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0216] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0217] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0218] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0219] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0220] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0221] An example of the sulfonylimide anion is a saccharin anion.

[0222] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0223] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are listed.

[0224] The non-nucleophilic anion is preferably an aliphatic sulfonate anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which an alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom. Among these, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferred, and a nonafluorobutanesulfonate anion, a perfluorooctane sulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferred.

[0225] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0226] [ka]

[0227] In formula (AN1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group, such as a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. The groups that are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', where R' is a monovalent hydrocarbon group.

[0228] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0229] L represents a divalent linking group. When a plurality of L's are present, each L may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these. Among these, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0230] L is preferably, for example, a group represented by the following formula (AN1-1). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0231] In formula (AN1-1), * a is R in formula (AN1) 3 represents the bonding position with * b is -C(R 1 )(R 2 )- represents the bonding position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, there are multiple instances of R 2a and R 2b may be the same or different. However, when Y is 1 or more, -C(R 1 )(R 2)- and CR 2b R in 2 2b is other than a fluorine atom. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. However, X+Y in formula (AN1-1) is 1 or more, and R in formula (AN1-1) 2a and R 2b are all hydrogen atoms, Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. * A is R in formula (AN1) 3 represents the bond position on the side, and * B is -SO3 in formula (AN1) - represents the bonding position on the side.

[0232] In formula (AN1), R 3 represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (e.g., an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0233] Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom), and the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group obtained by removing one hydrogen atom from a ring member atom constituting the lactone structure or sultone structure in any of the structures represented by the above formulae (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) is preferred.

[0234] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0235] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0236] [ka]

[0237] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0238] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and further preferably both Xf's are fluorine atoms.

[0239] R 4 and R 5 R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple 4 and R 5 may be the same or different. R 4 and R 5 The alkyl group represented by the following formula preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. R4 and R5 are preferably hydrogen atoms.

[0240] L represents a divalent linking group, and is defined as L in formula (AN1).

[0241] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0242] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, polycyclic heterocyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0243] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0244] The anion represented by formula (AN2) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0245] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0246] [ka]

[0247] In formula (AN3), Ar represents an aryl group (e.g., a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom or a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 or 3, and even more preferably 3.

[0248] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0249] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0250] The non-nucleophilic anion is also preferably a disulfonamide anion. Disulfonamide anions are, for example, N - (SO2-R q )2 is an anion. where R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. q may be bonded to each other to form a ring. q The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0251] It is also preferable that the compound (B) is at least one selected from the group consisting of the compounds (I) to (II).

[0252] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which, upon irradiation with actinic rays or radiation, 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: Structural site X: Anion site A1 - and cationic moiety M1+ and a structural moiety that forms a first acidic moiety represented by HA1 upon irradiation with actinic rays or radiation. Structural site Y: Anionic site A2 - and cationic moiety M2 + and a structural portion that forms a second acidic site represented by HA2 upon irradiation with actinic rays or radiation. The above compound (I) satisfies the following condition I.

[0253] Condition I: In the compound (I), the cation moiety M1 in the structural moiety X + and the cationic moiety M2 in the structural moiety Y. + H + The compound PI in which the cationic moiety M1 in the structural moiety X is replaced by + H + and the cationic moiety M2 in the structural moiety Y. + H + and an acid dissociation constant a2 derived from the acidic site represented by HA2 in which the acid dissociation constant a1 is replaced by the acid dissociation constant a2, which is greater than the acid dissociation constant a1.

[0254] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic moieties derived from the structural moiety X and one of the second acidic moieties derived from the structural moiety Y, compound PI corresponds to a "compound having HA1 and HA2." More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined by determining the acid dissociation constant of the compound PI. - The pKa at which the compound is formed is the acid dissociation constant a1, and the above "A1 - and HA2" is "A1 - and A2 - The pKa at which the compound becomes "a compound having the above formula" is the acid dissociation constant a2.

[0255] When the compound (I) is a compound that generates an acid having, for example, two of the above-mentioned first acidic sites derived from the above structural site X and one of the above-mentioned second acidic sites derived from the above structural site Y, the compound PI corresponds to a "compound having two HA1s and one HA2". When the acid dissociation constant of the compound PI is determined, when the compound PI becomes a "compound having one A1 - and one HA1 and one HA2", the acid dissociation constant, and "one A1 - and one HA1 and one HA2" becomes "two A1s - and one HA2" corresponds to the above-mentioned acid dissociation constant a1. "Two A1s - and one HA2" becomes "two A1s - and A2 - When the acid dissociation constant when it becomes a "compound having" corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 in which the cation site M1 + in the above structural site X is replaced by H + , the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. When the acid dissociation constant when the compound PI becomes a "compound having one A1 - and one HA1 and one HA2" is aa, and "one A1 - and one HA1 and one HA2" becomes "two A1s - and one HA2" When the acid dissociation constant is ab, the relationship between aa and ab satisfies aa < ab.

[0256] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-described method for measuring the acid dissociation constant. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1s - , and two or more of the above M1s +may be the same or different. In compound (I), the above A1 - and A2 above - , and the above M1 + and M2 above + may be the same or different, but - and A2 above - are preferably different from each other.

[0257] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0258] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0259] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0260] Anionic site A1 - and anionic site A2 - is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. Anionic site A1 - As the acid group, those capable of forming an acidic site with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. In addition, the anionic site A2 - As the anion moiety A1- Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R A represents a monovalent organic group. A The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0261] [ka]

[0262] [ka]

[0263] Cationic moiety M1 + and cationic moiety M2 + is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. + Examples of the organic cation include those represented by the following formula:

[0264] (Compound (II)) Compound (II) is a compound having two or more of the structural moieties X described above and one or more of the structural moieties Z described below, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation. Structural site Z: a non-ionic site capable of neutralizing acids

[0265] In compound (II), the definition of the structural moiety X and A1 - and M1 + The definition of the structural moiety X in the compound (I) and A1- and M1 + The definition and preferred embodiments are also the same as those given above.

[0266] In the compound (II), the cation moiety M1 in the structural moiety X + H + In the compound PII, the cationic moiety M1 in the structural moiety X is replaced by + H + The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the following is replaced by is the same as the acid dissociation constant a1 in the compound PI. In addition, when compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, it is considered that compound PII has "one A1 - and one HA1" and the acid dissociation constant when "a compound having one A1" - and one HA1" is "a compound with two A1 - The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0267] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. - , and two or more of the above M1 + may be the same or different.

[0268] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having an electron. Examples of the group capable of electrostatically interacting with a proton or the functional group having an electron include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group 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:

[0269] [ka]

[0270] Examples of the partial structure of a 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 to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary to tertiary amine structure is preferred.

[0271] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0272] [ka]

[0273] [ka]

[0274] Specific examples of compound (B) include the compounds described in

[0320] to

[0321] of WO 2022 / 172715. The above descriptions are incorporated herein by reference.

[0275] The composition of the present invention may or may not contain compound (B). When the composition of the present invention contains compound (B), the content of compound (B) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total solid content of the composition of the present invention. When the composition of the present invention contains compound (B), the content of compound (B) is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total solid content of the composition of the present invention. The compound (B) may be used alone or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0276] [Acid diffusion controller] The composition of the present invention may further contain an acid diffusion controller (also referred to as "compound (C)"). The compound (C) may be a compound different from the compound (T), the resin (A) and the compound (B). The acid diffusion controller can act as a quencher that traps the acid generated from the photoacid generator or the like upon exposure and suppresses the reaction of the resin, which becomes more polar due to the action of excess acid generated in the unexposed area. The type of compound (C) is not particularly limited, and examples thereof include a basic compound (CA), a low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) that is a weak acid relative to the photoacid generator, and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824. Specific examples of basic compounds (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824 and those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is released by the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of onium salt compounds (CD) that are relatively weak acids compared to photoacid generators include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0277] In addition to the above, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

[0664] , U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0095] to

[0187] , U.S. Patent Application Publication No. 2016 / 0237190A1, paragraphs

[0403] to

[0423] , and U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0259] to

[0328] can be suitably used as the acid diffusion controller.

[0278] The composition of the present invention may or may not contain compound (C). When the composition of the present invention contains compound (C), the content of compound (C) is preferably 0.01 to 30 mass%, more preferably 0.05 to 20 mass%, and even more preferably 0.1 to 15 mass%, based on the total solid content of the composition of the present invention. The compound (C) may be used alone or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0279] [Hydrophobic resin] The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin") different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike 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. The effects of adding a hydrophobic resin include control of the static and dynamic contact angle of water on the surface of the resist film and suppression of outgassing.

[0280] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin, and more preferably has two or more of these. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0281] The composition of the present invention may or may not contain a hydrophobic resin. When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, based on the total solid content of the composition of the present invention. The hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0282] [Surfactants] The composition of the present invention may contain a surfactant. When the composition contains a surfactant, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0283] The surfactant may be used alone or in combination of two or more.

[0284] The composition of the present invention may or may not contain a surfactant. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0285] [solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0286] The combination of the above-mentioned solvent and the above-mentioned resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0287] When the solvent 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 % relative to the total amount of the solvent.

[0288] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass %, more preferably 1 to 20 mass %, which further improves the coatability of the composition of the present invention.

[0289] [Other additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0290] The "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0291] The content of fluorine atoms in the total solid content of the composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0292] The composition of the present invention can also be suitably used as a photosensitive composition for EUV exposure.

[0293] <Actinic ray- or radiation-sensitive film and pattern formation method> The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The procedure for the pattern formation method using the composition of the present invention is not particularly limited, but it is preferable that the method comprises the following steps. Step 1: Forming a resist film on a substrate using the composition of the present invention Step 2: Step of exposing the resist film Step 3: Developing the exposed resist film using a developer The procedures for each of the above steps will be described in detail below.

[0294] (Step 1: Resist film formation step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0295] An example of a method for forming a resist film on a substrate using the composition of the present invention is a method in which the composition of the present invention is applied onto a substrate. The composition of the present invention is preferably filtered as needed before application. 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.

[0296] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated silicon) used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spinning using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After coating the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic films, organic films, anti-reflective films) may be formed under the resist film.

[0297] 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, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0298] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm in order to form a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. 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.

[0299] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP-A-2013-61648 on the resist film. Specific examples of the basic compound that the top coat may contain include the basic compounds that may be contained in the composition of the present invention. The top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0300] (Step 2: Exposure step) Step 2 is a step of exposing the resist film. The exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams, preferably having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet rays having a wavelength of 1 to 200 nm, and specifically including KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0301] After exposure, it is preferable to bake (heat) the film before developing, as this promotes the reaction of the exposed areas, 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 from 10 to 1000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. This step is also called post-exposure baking.

[0302] (Process 3: Development process) 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 (also called an "organic developer").

[0303] 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 the substrate by surface tension and left to stand 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 dispensing nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as 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 from 0 to 50°C, more preferably from 15 to 35°C.

[0304] 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 preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.

[0305] 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.

[0306] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0307] The developer may contain other components in addition to the components described above. Examples of other components include surfactants, antioxidants, basic compounds, etc. The content of other components in the developer is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, even more preferably 0% by mass or more and 0.5% by mass or less, with the total amount of the developer being 100% by mass, and particularly preferably 0% by mass (i.e., no other components are contained).

[0308] (Other processes) The pattern formation method preferably includes, after step 3, a step of washing with a rinse liquid.

[0309] The rinse liquid used in the rinse step after the development step using an alkaline developer is, for example, pure water, to which an appropriate amount of surfactant may be added. A suitable amount of surfactant may be added to the rinse solution.

[0310] 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.

[0311] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing liquid 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 a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method). The pattern formation method 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 due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0312] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlying 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 preferred method is to form 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. The dry etching is preferably oxygen plasma etching.

[0313] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, 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 or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. 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.

[0314] 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.

[0315] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as the 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).

[0316] In addition to filtration, impurities may be removed using an adsorbent, or a combination of 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 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferred.

[0317] A conductive compound may be added to an organic processing liquid such as a rinse liquid to prevent breakdown of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing properties, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For example, SUS (stainless steel), or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used as the chemical liquid pipe. Similarly, antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the filter and O-ring.

[0318] <Electronic device manufacturing method> The present invention also relates to a method for manufacturing an electronic device, which includes the above-described pattern formation method, and an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present invention is one that is installed in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0319] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed 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 following examples.

[0320] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0321] <Resin (A)> As the resin (A), AT-1 to AT-5 and A-6 to A-11 were used. Table 1 below shows the type and content (molar ratio) of repeating units contained in each resin, as well as the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin. In Table 1, the content of repeating units in each resin is separated by " / " and listed in the order corresponding to the order of the repeating unit types (i.e., "repeating unit 1 / repeating unit 2 / repeating unit 3 / repeating unit 4." However, if the type of repeating unit is "-," this indicates that the repeating unit is not contained, and the content of that repeating unit is not listed.) The repeating unit content is the ratio of each repeating unit to all repeating units contained in each resin (unit: mol %). The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). 13 Measurement was performed by C-NMR (nuclear magnetic resonance).

[0322] [Table 1]

[0323] The structures of the repeating units listed in Table 1 are shown below. a-1 to a-3 have a structure represented by formula (1). AT-1 to AT-5 have any of a-1 to a-3 and have a molecular weight of 400 or more, and therefore correspond to compound (T) (compound (TH)). d-1, d-2, d-4, d-7, and d-11 are repeating units having a group that decomposes under the action of an acid to generate a polar group, and AT-2, AT-4, and A-6 to A-9 having any of these are acid-decomposable resins.

[0324] [ka]

[0325] [ka]

[0326] [ka]

[0327] [ka]

[0328] <Compound (TL)> Q-1 to Q-7 were used as compounds (TL) (compounds (T) that are not resins). The structures and molecular weights (MW) of Q-1 to Q-7 are shown below. Me represents a methyl group.

[0329] [ka]

[0330] Furthermore, the following QX-1 was used in a comparative example. QX-1 has a molecular weight of less than 400 and does not fall under the category of compound (T), but for convenience it is listed in the column for compound (TL) in the table below.

[0331] [ka]

[0332] <Photoacid generator> The photoacid generators used were B-1 to B-3, whose structures are shown below.

[0333] [ka]

[0334] <Acid diffusion control agent> The acid diffusion controllers used were C-1 to C-8, whose structures are shown below.

[0335] [ka]

[0336] <Surfactant> The surfactants used are shown below. W-1: Megafac R08 (DIC Corporation; fluorine and silicone type) W-2: Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troisol S-366 (manufactured by Trois Chemical Co., Ltd.; fluorine-based) W-4: PolyFox PF-6320 (OMNOVA Solutions Inc.; fluorine-based)

[0337] <Solvent> The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Diacetone alcohol (DAA) S-3: Propylene glycol monomethyl ether (PGME) S-4: Ethyl lactate (EL) S-5: Ethyl 3-ethoxypropionate (EEP) S-6: 2-heptanone (MAK) S-7: Methyl 3-methoxypropionate (MMP) S-8: 3-Methoxybutyl acetate

[0338] A synthesis example of the compound (T) is shown below.

[0339] (Synthesis of Q-1)

[0340] [ka]

[0341] Four molar equivalents of cesium carbonate and 10 parts by mass of dimethylformamide (DMF) were added to 1 molar equivalent of 3,4-dihydroxybenzoic acid and heated to 70°C. Four molar equivalents of tetrahydrofurfuryl bromide were added dropwise and stirred for 4 hours. After the reaction, the reaction mixture was cooled to room temperature (23°C), the organic phase was extracted with ethyl acetate, washed with pure water, and the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / methanol = 99 / 1 by mass) to obtain intermediate (q-1-1). To 1 molar equivalent of intermediate (q-1-1), 1.2 molar equivalents of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC HCl), 0.2 molar equivalents of N,N-dimethylaminopyridine (DMAP), 1 molar equivalent of 4-hydroxypiperidine, and 10 parts by mass of dichloromethane were added and stirred at room temperature for 4 hours. After the reaction, the organic phase was washed with pure water, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain intermediate (q-1-2). Under nitrogen, 1 molar equivalent of intermediate (q-1-2), 1 molar equivalent of carbonyldiimidazole, and 10 parts by mass of tetrahydrofuran (THF) were added and stirred at room temperature for 10 hours. Then, 1 molar equivalent of N-hydroxyphthalimide was added and stirred for an additional 7 hours. After the reaction, the organic phase was extracted with ethyl acetate, washed with pure water, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain Q-1.

[0342] (Synthesis of Q-2)

[0343] [ka]

[0344] Four molar equivalents of cesium carbonate and 10 parts by mass of dimethylformamide were added to 1 molar equivalent of 4-hydroxycyclohexanecarboxylic acid and heated to 70°C. Four molar equivalents of 5-(2-bromoethyl)-2,3-dihydrobenzofuran were added dropwise and stirred for 4 hours. After the reaction, the reaction mixture was cooled to room temperature, the organic phase was extracted with ethyl acetate, washed with pure water, and the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / methanol = 99 / 1 by mass) to obtain intermediate (q-2-1). To 1 molar equivalent of intermediate (q-2-1), 1.2 molar equivalents of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.2 molar equivalents of N,N-dimethylaminopyridine, 1 molar equivalent of N-hydroxyphthalimide, and 10 parts by mass of dichloromethane were added and stirred at room temperature for 4 hours. After the reaction, the organic phase was washed with pure water, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / methanol = 99 / 1 by mass) to obtain Q-2.

[0345] (Synthesis of AT-1)

[0346] [ka]

[0347] Under nitrogen, 4-bromophthalic anhydride, 2 molar equivalents of hydroxylamine hydrochloride, and 5 parts by mass of pyridine were charged, heated to 80°C, and stirred for 6 hours. After the reaction, the reaction mixture was cooled to room temperature, poured into pure water, neutralized with hydrochloric acid, and the precipitate was filtered and recrystallized from ethanol to obtain intermediate (pa-1). To 1 molar equivalent of intermediate (pa-1), 1.2 molar equivalents of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC HCl), 0.2 molar equivalents of N,N-dimethylaminopyridine (DMAP), 1 molar equivalent of N-hydroxyphthalimidocyclohexanecarboxylic acid, and 10 parts by mass of dichloromethane were added and stirred at room temperature for 4 hours. After the reaction, the organic phase was washed with pure water, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / methanol = 99 hexane = 1 / 1 by mass) to obtain intermediate (pa-2). Under nitrogen, 1.3 molar equivalents of potassium vinyltrifluoroborate, 0.05 molar equivalents of palladium acetate, 0.2 molar equivalents of triphenylphosphine, and 5 molar equivalents of tetrahydrofuran were added to 1 molar equivalent of intermediate (pa-1), and the mixture was stirred at boiling point reflux for 6 hours. After extraction with ethyl acetate and washing with pure water, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1 / 1 mass ratio) to obtain Ma-1.

[0348] [ka]

[0349] The monomers used were Ma-1, Mb-2, and Mc-1. The monomers were mixed in a molar ratio of Ma-1:Mb-2:Mc-1 = 30 / 69 / 1. Cyclohexanone was added to a solution with a monomer concentration of 30% by mass. 7 mol% of dimethyl 2,2'-azobis(2-methylpropionate) was added as an initiator to prepare a monomer solution. Under a nitrogen atmosphere, 0.1 times the mass of cyclohexanone was heated to 85°C, and the monomer solution was added dropwise over 2 hours. The reaction was then continued for another 2 hours at 85°C. The resulting resin solution was added dropwise to a 1:9 ethyl acetate:n-heptane (mass ratio) mixed solvent, and the resin was precipitated. It was then filtered, collected, and vacuum-dried to obtain resin (AT-1) in a 68% yield.

[0350] <Preparation of Resist Composition> The components shown in Table 2 below were mixed to obtain a mixed liquid. The resulting mixed liquid was passed through a polyethylene filter with a pore size of 0.02 μm and filtered to prepare resist compositions (R-1 to R-20, RX-1 to RX-3). The solid content concentration of each resist composition is shown in Table 2. "Solid content" refers to components other than the solvent. In Table 2, "content (mass%)" indicates the content (mass%) of each solid component relative to the total solid content of the resist composition. However, when a surfactant was used, the surfactant content was set to 0.01 mass%. When multiple types of resin (A), compound (TH), photoacid generator, and acid diffusion controller were used, the table was divided into multiple rows. Furthermore, for the solvents, the content (mass%) of each solvent component relative to the total solvent is shown.

[0351] [Table 2]

[0352] <Coating of resist composition> The prepared resist composition was applied to a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and then dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate.

[0353] <Pattern formation method (1): EB exposure, alkaline development (positive)> The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (Advantest Corporation; F7000S, acceleration voltage 50 keV). The lithography was performed to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0354] <Patterning method (2): EUV exposure, alkaline development (positive)> The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure system (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line:space = 1:1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0355] <Evaluation of resist pattern> The resulting patterns were evaluated by the following method.

[0356] The irradiation energy required to resolve a 1:1 line and space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

[0357] (resolution) The limiting resolving power (the minimum line width at which a line and a space (line:space = 1:1) are resolved separately) at the exposure dose that shows the above sensitivity (Eop) was defined as the resolution (nm). The results of the resolution (nm) are shown in Tables 3 and 4.

[0358] (development defects) A 1:1 line and space pattern with a line width of 100 nm formed at the above sensitivity (Eop) was inspected using a defect inspection system KLA2360 (product name) manufactured by KLA Tencor Corporation. The pixel size of the defect inspection system was set to 0.16 μm and the threshold value was set to 20. The number of defects (number / cm) extracted from the difference caused by overlaying the comparison image and pixel unit was measured. 2 ) and count the number of defects per unit area (pcs / cm 2 After that, a defect review was performed to classify and extract development defects from all defects, and the number of development defects per unit area (number / cm 2 The smaller the number of development defects, the more the occurrence of development defects is suppressed, which is preferable. The number of development defects was rated as A when it was less than 0.3, B when it was 0.3 or more and less than 0.8, and C when it was 0.8 or more and less than 3.0. The smaller the value, the better the performance. The results of the number of development defects are shown in Tables 3 and 4.

[0359] The resist compositions used and the evaluation results for the patterns formed by the above pattern forming method (1) are shown in Table 3 below.

[0360] [Table 3]

[0361] The resist compositions used and the evaluation results for the patterns formed by the above pattern forming method (2) are shown in Table 4 below.

[0362] [Table 4]

[0363] The results in Tables 3 and 4 show that the resist compositions of the examples, when used in pattern formation, were able to suppress the occurrence of development defects and provided excellent resolution.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) having a repeating unit having an aromatic group and an organic solvent, An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (T) having a structure represented by the following formula (1) and having a molecular weight of 400 or more: 【Chemical 1】 In formula (1), Rc １ and Rc ２ Rc each independently represents a substituent. １ and Rc ２ may be bonded to form a ring. １ represents a nitrogen atom or a carbon atom. １ represents a carbon atom, said carbon atom may be １ and Rc ２ In addition to the above, a hydrogen atom or a substituent may be bonded. * indicates the bonding position.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (T) is at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a resin having a repeating unit represented by the following formula (1-3), and a resin having a repeating unit represented by the following formula (1-4): 【Chemistry 2】 In formula (1-1), Rc １１ and Rc １２ Rc each independently represents a substituent. １１ and Rc １２ may be bonded to form a ring. １１ represents a nitrogen atom or a carbon atom. １１ represents a carbon atom, said carbon atom may be １１ and Rc １２ In addition to Rc, a hydrogen atom or a substituent may be bonded. １３ and Rc １４ each independently represents a hydrogen atom or a substituent. In formula (1-2), Rc ２１ and Rc ２２ Rc each independently represents a substituent. ２１ and Rc ２２ may be bonded to form a ring. ２１ represents a nitrogen atom or a carbon atom. ２１ represents a carbon atom, said carbon atom may be ２１ and Rc ２２ In addition to the above, a hydrogen atom or a substituent may be bonded. ２１ represents an aromatic ring. ２１ may have a substituent bonded thereto. In formula (1-3), Rc ３１ and Rc ３２ Rc each independently represents a substituent. ３１ and Rc ３２ may be bonded to form a ring. ３１ represents a nitrogen atom or a carbon atom. ３１ represents a carbon atom, said carbon atom may be ３１ and Rc ３２ In addition, a hydrogen atom or a substituent may be bonded. In formula (1-4), Rc ４１ and Rc ４２ Rc each independently represents a substituent. ４１ and Rc ４２ may be bonded to form a ring. ４１ represents a nitrogen atom or a carbon atom. ４１ represents a carbon atom, said carbon atom may be ４１ and Rc ４２ In addition to the above, a hydrogen atom or a substituent may be bonded. ４１ represents an aromatic ring. ４１ A substituent may be bonded to L. ４１ represents a single bond or a divalent linking group.

3. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit having a phenolic hydroxyl group.

4. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit represented by the following formula (N-1): 【Chemistry 3】 In formula (N-1), R １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, a halogen atom, or an organic group. １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic group. １０４ represents a hydroxyl group or a fluorinated alcohol group. １０５ represents a halogen atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more.

5. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit represented by the following formula (N-2): 【Chemistry 4】 In formula (N-2), R １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic group; k3 represents an integer of 1 to 5;

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (T) is at least one selected from the group consisting of compounds represented by the following formula (1-5) and compounds represented by the following formula (1-6): 【Chemistry 5】 In formula (1-5), Rc ５１ and Rc ５２ Rc each independently represents a substituent. ５３ , Rc ５４ and Rc ５５ Rc each independently represents a hydrogen atom or a substituent. ５１ , Rc ５２ and Rc ５５ At least two of these may be bonded to form a ring. In formula (1-6), Rc ６１ and Rc ６２ Rc each independently represents a substituent. ６３ represents a hydrogen atom or a substituent. ６１ , Rc ６２ and Rc ６３ At least two of these may be bonded to form a ring. ６１ represents an aromatic ring. ６１ may have a substituent bonded to it.

7. the compound (T) is at least one selected from the group consisting of compounds represented by formula (1-1) and compounds represented by formula (1-2), Rc in the formula (1-1) １１ and Rc １２ at least one of represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group; Rc in the formula (1-2) ２１ and Rc ２２ 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein at least one of the groups represented by the formula (I) represents a substituent having at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, and an acetal group.

8. the compound (T) is at least one selected from the group consisting of compounds represented by formula (1-1) and compounds represented by formula (1-2), 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the compound (T) has only one structure represented by the formula (1) in the same molecule.

9. the compound (T) is at least one selected from the group consisting of a resin having a repeating unit represented by formula (1-3) and a resin having a repeating unit represented by formula (1-4), The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2 , wherein the resin (A) is the compound (T).

10. the compound (T) is a resin having a repeating unit represented by the formula (1-4), L in the formula (1-4) ４１ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2 , wherein represents a single bond.

11. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a group that decomposes under the action of an acid to generate a polar group.

12. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a compound (B) that generates an acid upon irradiation with actinic rays or radiation.

13. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein the resin (A) has a repeating unit having a photoacid-generating group.

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

15. A pattern forming method comprising: a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13; an exposure step of exposing the resist film to light; and a development step of developing the exposed resist film using a developer.

16. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 15.

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