Photosensitive or radiation-sensitive resin composition, photosensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic devices.

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing an acid decomposable resin (A) and a photoacid generator (B), the (A) having a repeating unit having a specific structure, the solubility parameter of which is greater than 20.31 MPa1 / 2, the content of the (B) being 15.0 mass% or greater with respect to the total solid content of the composition; an actinic ray-sensitive or radiation-sensitive film formed from said composition; a pattern-forming method using said composition, and an electronic device manufacturing method. The actinic ray-sensitive or radiation-sensitive resin composition, the actinic ray-sensitive or radiation-sensitive film, the pattern-forming method, and the electronic device manufacturing method thereby excel in resolution in the formation of an extremely fine pattern, even with the lapse of time after preparation.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device. [Background technology]

[0002] In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large-Scale Integrated Circuits), microfabrication is performed using lithography with photosensitive compositions. One lithography method involves forming a resist film using a photosensitive composition, exposing the resulting film to light, and then developing it. In particular, in recent years, studies have been conducted on using EB (Electron Beam) and EUV (Extreme Ultraviolet) in addition to ArF excimer lasers during exposure, and the development of photosensitive or radiation-sensitive resin compositions suitable for exposure using various light sources has been undertaken.

[0003] For example, Patent Documents 1 to 3 describe a resist composition comprising an acid-degradable resin having repeating units with an acenaphthylene skeleton and a photoacid generator. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-202974 [Patent Document 2] Japanese Patent Application Publication No. 2007-112898 [Patent Document 3] Japanese Patent Publication No. 2010-266842 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, the miniaturization of patterns formed using EUV (wavelength 13.5 nm) or electron beams has progressed, and the requirements for various performance aspects have become stricter than when using conventional ArF (wavelength 193 nm), etc. In particular, there is a need for photosensitive or radiation-sensitive resin compositions that can exhibit excellent resolution even after a certain period of time has elapsed since the preparation of the photosensitive or radiation-sensitive resin composition.

[0006] The present invention aims to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution in forming extremely fine patterns (for example, line and space patterns with a line width or space width of 25 nm or less, preferably 20 nm or less, or hole patterns with a pore diameter of 25 nm or less, preferably 20 nm or less) even after time has passed since preparation. Furthermore, the present invention aims to provide a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0007] The inventors have found that the above problems can be solved by the following configuration. <1> (A) A resin that decomposes and becomes more polar due to the action of an acid, (B) Compounds that generate acid upon irradiation with active light or radiation A photosensitive or radiation-sensitive resin composition containing, The above resin (A) has repeating units represented by the following general formula (N1), The solubility parameter of the repeating unit represented by the following general formula (N1) is 24.50 MPa. 1 / 2 That's all. Furthermore, the resin (A) has repeating units having acid-degradable groups, and the content of the repeating units having acid-degradable groups is 50 mol% or more relative to the total repeating units of the resin (A). A photosensitive or radiation-sensitive resin composition in which the content of compound (B) is 15.0% by mass or more relative to the total solid content of the photosensitive or radiation-sensitive resin composition. [ka] In general formula (N1), R N1 represents a substituent. k represents an integer between 1 and 6. If k represents an integer greater than or equal to 2, then multiple R N1 They may be the same or they may be different. If k represents an integer greater than or equal to 2, then multiple R N1 They may combine to form a ring. <2> The repeating unit represented by the above general formula (N1) is the same as the repeating unit represented by the following general formula (N2) or (N3). <1> The photosensitive or radiation-sensitive resin composition described above.

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[0008] [1] (A) A resin that decomposes and becomes more polar due to the action of an acid, (B) Compounds that generate acid upon irradiation with active light or radiation A photosensitive or radiation-sensitive resin composition containing, The above resin (A) has repeating units represented by the following general formula (N1), The solubility parameter of the repeating unit represented by the following general formula (N1) is 20.31 MPa. 1 / 2 Larger, Furthermore, the resin (A) has repeating units having acid-degradable groups, and the content of the repeating units having acid-degradable groups is 50 mol% or more relative to the total repeating units of the resin (A). A photosensitive or radiation-sensitive resin composition in which the content of compound (B) is 15.0% by mass or more relative to the total solid content of the photosensitive or radiation-sensitive resin composition.

[0009] [ka]

[0010] In general formula (N1), R N1 represents a substituent. k represents an integer between 1 and 6. If k represents an integer greater than or equal to 2, then multiple R N1 They may be the same or they may be different. If k represents an integer greater than or equal to 2, then multiple R N1 They may combine to form a ring. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit represented by the above general formula (N1) is a repeating unit represented by the following general formula (N2) or (N3).

[0011] [ka]

[0012] In general formula (N2), L N1 This represents a divalent linking group. L N2 This represents an alkylene group or single bond which may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group. R N2 represents a hydrogen atom or substituent. k1 represents an integer between 1 and 6. R N3 represents a substituent. k2 represents an integer between 0 and 5. However, the sum of k1 and k2 is 6 or less. If k1 represents an integer greater than or equal to 2, then multiple L N1 , multiple L N2 and multiple R N2 These may be the same or they may be different. If k2 represents an integer greater than or equal to 2, then multiple R N3 They may be the same or they may be different.

[0013] [ka]

[0014] In general formula (N3), L N3 and L N5 Each of these independently represents a divalent linking group. L N4 represents a single bond or a divalent linking group. k3 represents an integer between 1 and 3. R N4 represents a substituent. k4 represents an integer between 0 and 4. However, the sum of 2 × k3 and k4 is 6 or less. If k3 represents an integer greater than or equal to 2, then multiple L N3 , multiple L N4 and multiple L N5 These may be the same or they may be different. If k4 represents an integer greater than or equal to 2, then multiple R N4 They may be the same or they may be different. [3] In the above general formula (N2), L N1 , and also L in the above general formula (N3) N3 and L N5 The photosensitive or radiation-sensitive resin composition according to [2], wherein each of the following independently represents a carbonyl group, an ester group, an amide group, a sulfonyl group, an oxygen atom, an amino group, or a sulfur atom. [4] In the above general formula (N2), R N2 A photosensitive or radiation-sensitive resin composition according to [2] or [3], wherein the member comprises a hydrogen atom, a group represented by the following general formula (AL1), or a group represented by the following general formula (AL2).

[0015] [ka]

[0016] In general formula (AL1), L N6 k5 represents an alkyl group, cycloalkyl group, or aryl group. k5 represents an integer of 1 or more. * represents a bond position.

[0017] [ka]

[0018] In the general formula (AL2), L N7 k6 represents an alkyl group, cycloalkyl group, or aryl group. k6 represents an integer of 1 or more. * represents a bond position. [5] In the above general formula (N3), LN4 The photosensitive or radiation-sensitive resin composition according to [2] or [3], wherein the single bond, carbonyl group, oxygen atom, or amino group is represented. [6] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin (A) further comprises at least one of a repeating unit having a phenolic hydroxyl group and a repeating unit having a lactone structure, which are different from the repeating unit represented by the general formula (N1). [7] (C) A photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], comprising a compound that decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability. [8] The photosensitive or radiation-sensitive resin composition according to [7], wherein compound (B) is the same compound as compound (C), and is compound (D) that generates acid upon irradiation with active light or radiation and decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability. [9] Furthermore, the photosensitive or radiation-sensitive resin composition according to [8] further comprises at least one of the above compound (B) which is not compound (D) and the above compound (C) which is not compound (D).

[10] A photosensitive or radiation-sensitive film formed from any one of the photosensitive or radiation-sensitive resin compositions described in [1] to [9].

[11] A step of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of [1] to [9], A step of exposing the above-mentioned photosensitive or radiation-sensitive film, A pattern forming method comprising the steps of developing the exposed photosensitive or radiation-sensitive film using a developing solution to form a pattern.

[12] A method for manufacturing an electronic device, including the pattern formation method described in

[11] . [Effects of the Invention]

[0019] According to the present invention, even after time has passed since preparation, it is possible to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution in the formation of extremely fine patterns (for example, line and space patterns with a line width or space width of 25 nm or less, preferably 20 nm or less, or hole patterns with a pore diameter of 25 nm or less, preferably 20 nm or less). Furthermore, according to the present invention, it is possible to provide a photosensitive or radiation-sensitive film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. [Modes for carrying out the invention]

[0020] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred.

[0021] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0022] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0023] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0024] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0025] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0026] In this specification, pKa refers to a value calculated using software package 1, based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. Furthermore, in this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used. "Solid content" refers to components that form photosensitive or radiation-sensitive films, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered solid content, even if its state is liquid.

[0027] Furthermore, in this specification, there are no particular limitations on the type of substituent, the position of the substituent, or the number of substituents when we say "may have substituents." The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups excluding hydrogen atoms, and for example, substituents T can be selected from the following:

[0028] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acetyl, benzoyl, isobutyryl, Examples of substituents include acyl groups such as acryloyl, methacryloyl, and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; and so on. Furthermore, if these substituents can have one or more substituents, groups having one or more substituents selected from the substituents listed above as further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) are also included as examples of substituent T.

[0029] [Actinic ray-sensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is (A) A resin that decomposes and becomes more polar due to the action of an acid (also called "resin (A)"), (B) A photosensitive or radiation-sensitive resin composition containing a compound that generates acid upon irradiation with active light or radiation (also referred to as "compound (B)" or "photoacid generator (B)"), The resin (A) has repeating units represented by the following general formula (N1), The solubility parameter of the repeating unit represented by the following general formula (N1) is 20.31 MPa. 1 / 2 Larger, Furthermore, resin (A) has repeating units having acid-degradable groups, and the content of repeating units having acid-degradable groups is 50 mol% or more relative to the total repeating units of resin (A). The active photosensitive or radiation-sensitive resin composition is characterized in that the content of compound (B) is 15.0% by mass or more relative to the total solid content of the active photosensitive or radiation-sensitive resin composition.

[0030] [ka]

[0031] In general formula (N1), R N1 represents a substituent. k represents an integer between 1 and 6. If k represents an integer greater than or equal to 2, then multiple R N1 They may be the same or they may be different. If k represents an integer greater than or equal to 2, then multiple R N1 They may combine to form a ring.

[0032] The reason why the composition of the present invention exhibits excellent resolution in the formation of extremely fine patterns (for example, line and space patterns with a line width or space width of 25 nm or less, preferably 20 nm or less, or hole patterns with a pore diameter of 25 nm or less, preferably 20 nm or less) even after time has passed since preparation is not entirely clear, but the inventors believe it to be as follows.

[0033] The resin (A) contained in the composition of the present invention has an acenaphthylene skeleton within repeating units represented by general formula (N1), and this acenaphthylene skeleton has a high glass transition temperature (Tg). Therefore, it is believed that the resist film formed from the composition of the present invention has high rigidity. As a result, the resulting extremely fine patterns also have high rigidity, and defects such as pattern collapse are less likely to occur, thus improving resolution. Furthermore, the solubility parameter of the repeating unit represented by the general formula (N1) is 20.31 MPa. 1 / 2 It is larger. In this way, by imparting hydrophilicity to the hydrophobic acenaphthylene skeleton, the compatibility with the photoacid generator (B), which is typically an ionic compound, is improved, the uniformity of the distribution of the photoacid generator (B) in the resist film formed from the composition of the present invention is improved, the roughness of the pattern is improved, and thus the resolution is expected to be improved. Furthermore, resin (A) contains 50 mol% or more of repeating units having acid-degradable groups relative to the total number of repeating units in resin (A). This ensures that a sufficient amount of acidic groups remain in resin (A) after the decomposition of the acid-degradable groups, further improving interaction with the acid generated from the photoacid generator (B), suppressing acid diffusion, and thus improving resolution. Furthermore, by setting the content of the photoacid generator (B) to 15.0% by mass or more relative to the total solid content of the composition of the present invention, the uneven distribution of the photoacid generator (B) in the resist film formed from the composition of the present invention is eliminated, improving roughness and thus improving resolution. In particular, in conventional resist compositions, as described above, when the content of photoacid generator (B) is high (15.0% by mass or more relative to the total solid content of the composition), the photoacid generators (B) tend to aggregate and precipitate, causing a decrease in resolution. This problem becomes more pronounced when the resist composition is aged. However, in the present invention, precipitation is suppressed by the hydrophilic acenaphthylene group, so it is believed that the resolution remains good even when aged.

[0034] [Components of photosensitive or radiation-sensitive resin compositions] The components included in the composition of the present invention, and components that may be included, will be described in detail below. The compositions of the present invention are typically resist compositions, and may be either positive-type or negative-type resist compositions. They may also be resist compositions for alkaline development or resist compositions for organic solvent development. The compositions of the present invention are typically chemically amplified resist compositions.

[0035] <(A) Resin> The composition of the present invention contains a resin (A) that decomposes upon the action of an acid, thereby increasing its polarity. Resin (A) contains acid-degradable groups (groups that decompose and increase in polarity due to the action of acid), and is an acid-degradable resin that decomposes and increases in polarity due to the action of acid. In the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic-based developer is used as the developer, a negative-type pattern is suitably formed. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are also preferred as repeating units having acid-degradable groups.

[0036] (Repeating unit represented by general formula (N1)) The resin (A) has repeating units represented by the general formula (N1) (also called "repeating unit (a1)").

[0037] [ka]

[0038] In general formula (N1), R N1 represents a substituent. k represents an integer between 1 and 6. If k represents an integer greater than or equal to 2, then multiple R N1 They may be the same or they may be different. If k represents an integer greater than or equal to 2, then multiple R N1They may combine to form a ring.

[0039] R N1 An example of a substituent represented by is the substituent T mentioned above. The solubility parameter of the repeating unit represented by the general formula (N1) is 20.31 MPa. 1 / 2 It needs to be larger, therefore at least one R N1 It is preferable that the group is polar.

[0040] at least one R N1 The substituent is preferably an alkoxy group, a cycloalkyloxy group, an aryloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a sulfanyl group, a hydroxyl group, a carboxyl group, a formyl group, a sulfo group, an amino group, or a carbamoyl group. If these substituents can have one or more further substituents, they may be groups having one or more of the aforementioned substituent T as further substituents.

[0041] at least one R N1 It is more preferably a sulfanyl group, a hydroxyl group, a carboxyl group, or a sulfo group, even more preferably a hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group.

[0042] R N1 If R is an organic group, N1 The number of carbon atoms contained in is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.

[0043] R N1 This group may be an acid-degradable group. Acid-degradable groups will be discussed later.

[0044] k represents an integer from 1 to 6, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

[0045] The repeating unit represented by general formula (N1) is preferably the repeating unit represented by general formula (N2) or (N3) below. As will be explained later, L in the general formula (N2) N1 , and also L in general formula (N3) N3 and L N5 Preferably, each of these independently represents a carbonyl group, an ester group, an amide group, a sulfonyl group, an oxygen atom, an amino group, or a sulfur atom.

[0046] The repeating unit represented by the general formula (N2) will be explained.

[0047] [ka]

[0048] In general formula (N2), L N1 This represents a divalent linking group. L N2 This represents an alkylene group or single bond which may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group. R N2 represents a hydrogen atom or substituent. k1 represents an integer between 1 and 6. R N3 represents a substituent. k2 represents an integer between 0 and 5. However, the sum of k1 and k2 is 6 or less. If k1 represents an integer greater than or equal to 2, then multiple L N1 , multiple L N2 and multiple R N2 These may be the same or they may be different. If k2 represents an integer greater than or equal to 2, then multiple R N3 They may be the same or they may be different.

[0049] In general formula (N2), L N1 This represents a divalent linking group. L N1Preferably, represents a divalent linking group comprising at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, a sulfonyl group, an oxygen atom, an amino group, and a sulfur atom. L N1 It is preferable that represents a carbonyl group, ester group, amide group, sulfonyl group, oxygen atom, amino group, or sulfur atom; more preferably that it represents a carbonyl group, ester group, sulfonyl group, oxygen atom, or sulfur atom; even more preferably that it represents a carbonyl group, ester group, or oxygen atom; particularly preferably that it represents an ester group or oxygen atom; and most preferably that it represents an ester group. The ester group is "-COO-". The amide group is "-NRCO-", where R represents a hydrogen atom or a substituent. Preferred substituents are alkyl groups, cycloalkyl groups, or aryl groups. The amino group is "-NR-", where R represents a hydrogen atom or a substituent. Preferred substituents are alkyl groups, cycloalkyl groups, or aryl groups. The alkyl group R in "-NRCO-" and "-NR-" is not particularly limited, but examples include linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred. The cycloalkyl group R in "-NRCO-" and "-NR-" can be a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 17 carbon atoms, and more preferably a cycloalkyl group having 5 to 15 carbon atoms. The aryl group R in "-NRCO-" and "-NR-" is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples include a phenyl group, a naphthyl group, and anthryl group, with a phenyl group or a naphthyl group being preferred, and a phenyl group being more preferred. As mentioned above, the bonding direction of the ester group and amide group is not limited.

[0050] In general formula (N2), L N2represents an alkylene group or a single bond which may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group. L N2 The alkylene group of N2 is not particularly limited and may be linear or branched. The alkylene group 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, an octylene group, etc., more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms. The above alkylene group may have a substituent. The above alkylene group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group. For example, in the chain of the alkylene group, it may have a divalent linking group containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group, or at the end of the alkylene group, it may have a divalent linking group containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group (in this case, the above divalent linking group may be bonded to L N1 or R N2 ). Also, at least one hydrogen atom of the alkylene group may be substituted with a monovalent substituent containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group. Examples of the case where the end of the alkylene group has a divalent linking group containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a carbonyl group include an alkyleneoxy group, an alkylenecarbonyloxy group, an alkyleneoxycarbonyl group, etc.

[0051] In the general formula (N2), R N2 represents a hydrogen atom or a substituent. R N2 When R represents a substituent, the substituent is preferably a hydroxy group, a carboxyl group, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R N2The alkyl group is not particularly limited, but examples include linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred. The alkyl group may have substituents. R N2 The cycloalkyl group is not particularly limited, but examples include cycloalkyl groups having 3 to 20 carbon atoms, preferably cycloalkyl groups having 4 to 17 carbon atoms, and more preferably cycloalkyl groups having 5 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 above cycloalkyl group may have substituents. R N2 The aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples include a phenyl group, a naphthyl group, and anthryl group, with a phenyl group or a naphthyl group being preferred, and a phenyl group being particularly preferred. The above aryl group may have substituents. R N2 The heterocyclic group may be an aromatic heterocyclic group or a non-aromatic heterocyclic group. The heterocyclic group may have substituents. The heterocyclic group is preferably a five-membered ring group or a six-membered ring group. The heterocyclic group is also preferably a fused ring group consisting of a five-membered ring and a five-membered ring or a six-membered ring. The heterocyclic group is also preferably a fused ring group consisting of a six-membered ring and a five-membered ring or a six-membered ring. As the aromatic heterocyclic group (heteroaryl group), an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms is preferred. The carbon atoms included as ring members of the aromatic heterocyclic group may be substituted with oxo groups (=O). As the non-aromatic heterocyclic group (aliphatic heterocyclic group), a non-aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom is preferable. An oxo group (=O) may be substituted on the carbon atom contained as a ring member in the non-aromatic heterocyclic group.

[0052] R N2 preferably represents a hydrogen atom, a group represented by the following general formula (AL1) or a group represented by the following general formula (AL2).

[0053]

Chemical formula

[0054] In general formula (AL1), L N6 represents an alkyl group, a cycloalkyl group or an aryl group. k5 represents an integer of 1 or more. * represents the bonding position.

[0055]

Chemical formula

[0056] In general formula (AL2), L N7 represents an alkyl group, a cycloalkyl group or an aryl group. k6 represents an integer of 1 or more. * represents the bonding position.

[0057] L in general formula (AL1) N6 represents an alkyl group, a cycloalkyl group or an aryl group. However, k5 hydroxy groups are bonded to the alkyl group, cycloalkyl group or aryl group of L N6 . L[[ID=]] N6 For the description, specific examples and preferred ranges of the alkyl group, cycloalkyl group and aryl group of L N2 are the same as those described for the alkyl group, cycloalkyl group and aryl group of R described above.

[0058] In the general formula (AL1), k5 represents an integer of 1 or more, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0059] In the general formula (AL2), L N7 L represents an alkyl group, cycloalkyl group, or aryl group. N7 The alkyl, cycloalkyl, or aryl group has k6 carboxyl groups attached to it. L N7 The descriptions, specific examples, and preferred ranges of alkyl, cycloalkyl, and aryl groups are as described above in R N2 The same applies to alkyl groups, cycloalkyl groups, and aryl groups.

[0060] In the general formula (AL2), k6 represents an integer of 1 or more, preferably an integer between 1 and 6, more preferably an integer between 1 and 4, and even more preferably 1 or 2.

[0061] In general formula (N2), R N3 represents a substituent. R N3 Examples of these substituents are not particularly limited, but include halogen atoms, alkyl groups, cycloalkyl groups, and aryl groups. If these substituents can have one or more further substituents, they may have one or more substituents selected from the substituents listed above as further substituents. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or iodine atoms being preferred. R N3 When R represents an alkyl group, a cycloalkyl group, or an aryl group, the descriptions, specific examples, and preferred ranges of each group are as described above. N2 The same applies to alkyl groups, cycloalkyl groups, and aryl groups.

[0062] In the general formula (N2), k1 represents an integer from 1 to 6, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and even more preferably 1 or 2. In the general formula (N2), k2 represents an integer between 0 and 5, preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0.

[0063] The repeating unit represented by the general formula (N3) will be explained.

[0064] [ka]

[0065] In general formula (N3), L N3 and L N5 Each of these independently represents a divalent linking group. L N4 represents a single bond or a divalent linking group. k3 represents an integer between 1 and 3. R N4 represents a substituent. k4 represents an integer between 0 and 4. However, the sum of 2 × k3 and k4 is 6 or less. If k3 represents an integer greater than or equal to 2, then multiple L N3 , multiple L N4 and multiple L N5 These may be the same or they may be different. If k4 represents an integer greater than or equal to 2, then multiple R N4 They may be the same or they may be different.

[0066] In general formula (N3), L N3 and L N5 Each of these independently represents a divalent linking group. L N3 and L N5It is preferable that this represents a carbonyl group, ester group, amide group, sulfonyl group, oxygen atom, amino group, or sulfur atom; more preferably a carbonyl group, ester group, sulfonyl group, oxygen atom, or sulfur atom; even more preferably a carbonyl group, ester group, or oxygen atom; particularly preferably a carbonyl group or oxygen atom; and most preferably a carbonyl group. The explanations, specific examples, and preferred ranges for ester groups, amide groups, and amino groups are given in L of the general formula (N2), respectively. N1 The same applies when referring to ester groups, amide groups, and amino groups.

[0067] In general formula (N3), L N4 represents a single bond or a divalent linking group. L N4 It is preferable that represents a single bond, a carbonyl group, an oxygen atom, or an amino group. For an explanation of the amino group, specific examples, and preferred range, see L in the general formula (N2). N1 This is the same as the description when it represents an amino group.

[0068] In the general formula (N3), k3 represents an integer between 1 and 3, preferably 1 or 2, and more preferably 1.

[0069] In general formula (N3), R N4 represents a substituent. R N4 For an explanation, specific examples, and preferred range of R in general formula (N2), see R N3 This is similar to what was described earlier.

[0070] In the general formula (N3), k4 represents an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0.

[0071] The solubility parameter (also called the "SP value") of the repeating unit represented by the general formula (N1) is 20.31 MPa. 1 / 2 Larger, 20.33 MPa 1 / 2Preferably, the above is 21.36 MPa. 1 / 2 It is more preferable that the MPa is 23.15 MPa or higher. 1 / 2 It is even more preferable that the above is true, specifically 24.50 MPa. 1 / 2 It is especially preferable that the above conditions are met. The solubility parameter of the repeating unit represented by the general formula (N1) is 36.68 MPa. 1 / 2 Preferably, the following is true: 31.89 MPa 1 / 2 It is more preferable that the following conditions be met: 31.47 MPa 1 / 2 The following is even more preferable:

[0072] The solubility parameter of the repeating unit represented by general formula (N1) is the solubility parameter for the monomer represented by the following general formula (N1m), which corresponds to the repeating unit represented by general formula (N1).

[0073] [ka]

[0074] R in the general formula (N1m) N1 and k are R in general formula (N1), respectively. N1 It has the same meaning as k. R in the general formula (N1m) N1 The explanation, specific examples, and preferred ranges for and k are given by R in general formula (N1), respectively. N1 The same applies to k.

[0075] The SP value is calculated using the following software. HSPiP(Hansen Solubility Parameters in Practice) 5th Edition (5.1.02) More specifically, the above software calculates three components: the dispersion force term δd, the inter-dipole force term δp, and the hydrogen bonding force term δh, and the SP value is calculated using the following formula. (SP value) 2 =δd 2 +δp 2 +δh2

[0076] Specific examples of monomers corresponding to the repeating unit represented by general formula (N1) and their SP values ​​are shown in Tables 1-3 below, but the present invention is not limited to these. The units of the SP values ​​shown in Tables 1-3 below are MPa. 1 / 2 That is the case. By polymerizing the following monomers (M-1 to M-40), repeating units represented by the general formula (N1) can be obtained.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] The resin (A) may have one repeating unit represented by the general formula (N1), or it may have two or more repeating units.

[0081] The content of repeating units represented by general formula (N1) in resin (A) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 20 to 30 mol%, relative to the total repeating units of resin (A).

[0082] (Repeating unit having an acid-degradable group (a2)) The resin (A) preferably contains repeating units having acid-degradable groups (also referred to as "repeating units (a2)").

[0083] An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group that is released upon the action of an acid. In other words, resin (A) has repeating units that decompose upon the action of an acid to produce a polar group. Resins having these repeating units become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents. Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups (typically groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), as well as alcoholic hydroxyl groups.

[0084] Alcoholic hydroxyl groups refer to hydroxyl groups bonded to a hydrocarbon group, excluding hydroxyl groups directly bonded to an aromatic ring (phenolic hydroxyl groups), and exclude aliphatic alcohols (e.g., hexafluoroisopropanol groups) in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom. Preferably, the alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0085] Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0086] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (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)

[0087] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). 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 combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two 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 cycloalkyl groups formed by the bonding of two Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0088] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. Also, R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0089] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0090] [ka]

[0091] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0092] If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom (that is, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group). Furthermore, if the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and the group which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom which may contain a heteroatom.

[0093] 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 bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0094] From the standpoint of excellent acid decomposition properties of repeating units, in the case of a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0095] Other leaving groups that are removed by the action of an acid may include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0096] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0097] [ka]

[0098] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, L1 is preferably -CO-, an arylene group, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO-, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0099] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0100] R2 represents a leaving group that is eliminated by the action of an acid and may contain a fluorine atom or an iodine atom. Examples of leaving groups that may contain a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that contain a fluorine atom or an iodine atom.

[0101] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0102] [ka]

[0103] In formula (AI), Xa1 represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, if 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. Two of Rx1 to Rx3 may bond together to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0104] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0105] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0106] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The repeating unit represented by formula (AI) preferably has, for example, Rx1 being a methyl group or an ethyl group, and Rx2 and Rx3 being bonded to form the cycloalkyl group described above.

[0107] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0108] The repeating unit represented by formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0109] Specific examples of repeating units having acid-degradable groups are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] Resin (A) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0116] [ka]

[0117] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0118] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0119] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic group is preferred.

[0120] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. Ethynyl groups are preferred as the alkynyl groups of Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 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. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Rx3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0121] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0122] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0123] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0124] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''':R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, or monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof, and n and m represent integers of 0 or more.

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] Resin (A) may contain one type of repeating unit having an acid-degradable group, or two or more types in combination. Furthermore, if the repeating unit (a1) (the repeating unit represented by general formula (N1)) has an acid-degradable group, then repeating unit (a1) also corresponds to the repeating unit having an acid-degradable group (repeating unit (a2)).

[0130] The content of repeating units having acid-degradable groups is 50 mol% or more, and preferably 60 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having acid-degradable groups is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, relative to the total repeating units in resin (A). By setting the content of repeating units having acid-degradable groups within the above range, a sufficient amount of acid groups remains in the resin (A) after the decomposition of the acid-degradable groups. This further improves the interaction with the acid generated from the photoacid generator (B), suppresses acid diffusion, and allows the cross-sectional shape of the formed pattern to become more rectangular.

[0131] The total content of repeating units (a1) and repeating units (a2) contained in resin (A) (or the sum of any multiple repeating units (a1) and repeating units (a2)) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total repeating units of resin (A). Furthermore, if resin (A) contains only repeating units (a1) and (a2), the total amount of repeating units (a1) and (a2) contained in resin (A) will be 100 mol%.

[0132] The resin (A) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below, which is different from the repeating unit (a1) described above. Group A: A group consisting of the following repeating units (20) to (29). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom, a bromine atom, or an iodine atom, which are described later and do not have either an acid-degradable group or an acid group. (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having photoacid generators, as described later (24) Repeating units represented by formula (V-1), which will be described later (25) Repeating units represented by formula (A), as described later (26) Repeating units represented by formula (B), which will be described later (27) Repeating units represented by formula (C), as described later (28) Repeating units represented by formula (D), which will be described later (29) Repeating units represented by formula (E), which will be described later Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0133] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from the photoacid generator is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0134] When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group A. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that resin (A) contains at least one of a fluorine atom and an iodine atom. If resin (A) contains both a fluorine atom and an iodine atom, resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or resin (A) may contain two types of repeating units: one containing a fluorine atom and another containing an iodine atom. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is also preferable that the resin (A) has repeating units having aromatic groups. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. Furthermore, when the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have aromatic groups.

[0135] (Repeating units containing acidic groups) The resin (A) may have repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0136] Examples of repeating units having an acidic group include the following:

[0137] [ka]

[0138] As a repeating unit having an acid group, the repeating unit represented by the following formula (1) is preferred.

[0139] [ka]

[0140] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. If there are multiple Rs, they may cooperate to form a ring. A hydrogen atom is preferred as R. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0141] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] Of the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0147] [ka]

[0148] [ka]

[0149] The content of repeating units having acidic groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). The content of repeating units having acid groups is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0150] (A repeating unit that does not possess either an acid-degradable group or an acidic group, but has a fluorine atom, a bromine atom, or an iodine atom.) Resin (A) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. Furthermore, it is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0151] The repeating unit X is preferably represented by formula (C).

[0152] [ka]

[0153] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom. 10 This represents an alkyl group which may have a hydrogen atom, 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 thereof.

[0154] Examples of repeating units having fluorine or iodine atoms are shown below.

[0155] [ka]

[0156] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A).

[0157] The total content of repeating units in resin (A) that contain at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of resin (A). There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0158] (Repeating units having a lactone group, sultone group, or carbonate group) The resin (A) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0159] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferable. The resin (A) preferably has repeating units having lactone groups or sultone groups obtained by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3). Furthermore, lactone groups or sultone groups may be directly bonded to the main chain. For example, ring member atoms of lactone groups or sultone groups may constitute the main chain of resin (A).

[0160] [ka]

[0161] The above lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or greater, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0162] Examples of repeating units having a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3), include the repeating unit represented by the following formula (AI).

[0163] [ka]

[0164] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. 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, a carboxyl group, or a divalent group combining these. Among these, a single bond or a linking group represented as -Ab1-CO2- is preferred for Ab. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

[0165] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0166] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by the following formula (A-1) is preferred.

[0167] [ka]

[0168] In formula (A-1), R A 1 R represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0169] The unit Y is exemplified below. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0170] [ka]

[0171] [ka]

[0172] The content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). The content of unit Y is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A). In one embodiment of resin (A), it is preferable that resin (A) further comprises at least one of a repeating unit having a phenolic hydroxyl group and a repeating unit having a lactone structure, which are different from the repeating unit (a1) described above.

[0173] (Repeating unit with photoacid-generating group) The resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (hereinafter also referred to as a "photoacid generating group"). An example of a repeating unit having a photoacid-generating group is the repeating unit represented by formula (4).

[0174] [ka]

[0175] R 41 L represents a hydrogen atom or a methyl group. 41 L represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.

[0176] [ka]

[0177] Other examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327, and the repeating units described in paragraph

[0094] of International Publication No. 2018 / 193954.

[0178] The content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0179] (The repeating unit represented by equation (V-1)) The resin (A) may have repeating units represented by the following formula (V-1). The repeating unit represented by the following formula (V-1) is preferably a different repeating unit from the repeating unit described above.

[0180] [ka]

[0181] During the ceremony, Each R7 independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. Linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms are preferred as the alkyl group. n4 represents an integer between 0 and 4. X 4This is a methylene group, an oxygen atom, or a sulfur atom. The repeating units represented by equation (V-1) are exemplified below. Examples of repeating units represented by formula (V-1) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0182] (A repeating unit that reduces the mobility of the main chain) Resin (A) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 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 the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). Furthermore, the calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0183] To increase the Tg of resin (A) (preferably to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking of annular structures to the main chain Furthermore, it is preferable that resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher. Furthermore, there are no particular restrictions on the type of repeating units in which the homopolymer Tg is 130°C or higher; any repeating unit in which the homopolymer Tg calculated by the Bicerano method is 130°C or higher is acceptable. Note that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described later, some repeating units may be considered to have a homopolymer Tg of 130°C or higher.

[0184] One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into resin (A).

[0185] [ka]

[0186] Formula (A), R A R represents a group containing a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, which may or may not be condensed. Specific examples of repeating units represented by formula (A) are those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0187] One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into resin (A).

[0188] [ka]

[0189] In formula (B), R b1 ~R b4 Each of these independently represents a hydrogen atom or an organic group, and R b1 ~R b4 At least two of these represent organic groups. Furthermore, if at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited. Furthermore, if none of the organic groups are directly linked to the main chain in the repeating unit, then at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Specific examples of repeating units represented by formula (B) are those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0190] One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A).

[0191] [ka]

[0192] In formula (C), R c1 ~R c4 Each of these independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. In particular, it is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of resin (A). Specific examples of repeating units represented by formula (C) are those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0193] One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A).

[0194] [ka]

[0195] In formula (D), "cylic" represents a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Specific examples of repeating units represented by formula (D) are those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0196] One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A).

[0197] [ka]

[0198] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substitution mechanisms. A "cylic" is a cyclic group that contains carbon atoms in the main chain. There are no particular restrictions on the number of atoms that can be included in a cyclic group. Specific examples of repeating units represented by formula (E) are those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0199] (A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0200] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. 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. It is preferable that the repeating units having a hydroxyl group or a cyano group do not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0201] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bisulfonylimide groups, and aliphatic alcohols (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921.

[0202] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion solution during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0203] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0204] [ka]

[0205] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and 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 repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of Japanese Patent Publication No. 2014-098921.

[0206] (Other repeating units) Furthermore, resin (A) may have repeating units other than those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. Examples of such repeating units are shown below.

[0207] [ka]

[0208] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0209] As for resin (A), (especially when the composition is used as an active photosensitive or radiation-sensitive resin composition for ArF) it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. In this case, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0210] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0211] Resin (A) may contain impurities from the raw materials or generated during the synthesis process (such as impurities in the solvent, unreacted monomer raw materials, and by-products from the synthesis process), as well as other metallic impurities. It is preferable to reduce these impurities.

[0212] In the composition of the present invention, the content of resin (A) is preferably 35.0 to 99.9% by mass, more preferably 50.0 to 99.0% by mass, and even more preferably 65.0 to 98.0% by mass, based on the total solid content of the composition. The resin (A) contained in the composition of the present invention may be one type or two or more types.

[0213] The composition of the present invention may contain, in addition to resin (A), a resin that does not have repeating units (a1) (also called resin (A')), to the extent that it does not impair the effects of the present invention. The resin (A') is not particularly limited as long as it is a resin that does not have repeating units (a1), but for example, a resin (A) that does not have repeating units (a1) can be given. If the composition of the present invention contains resin (A'), the ratio of the content of resin (A) to the content of resin (A') (content of resin (A): content of resin (A')) is preferably 9:1 to 8:2 by mass.

[0214] <(B) Compounds that generate acid upon irradiation with active light or radiation> The composition of the present invention contains a compound that generates acid upon irradiation with active light or radiation (also referred to as "compound (B)" or "photoacid generator (B)"). Photoacid generator (B) is a compound that generates acid upon exposure to light. The photoacid generator (B) and the aforementioned resin (A) are different compounds. The photoacid generator (B) may be the same compound as compound (C) described later. The molecular weight of the photoacid generator (B) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0215] The photoacid generator (B) is preferably an ionic compound. The photoacid generator (B) is preferably a photoacid generator having an anion and a cation.

[0216] The photoacid generator (B) is preferably an onium salt.

[0217] For example, the photoacid generator (B) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0218] The pKa of the acid generated from the photoacid generator (B) is preferably -20.00 to 2.00, more preferably -7.00 to 0.50, and even more preferably -5.00 to 0.00.

[0219] "M + X - In the compound represented by ", M + This represents an organic cation. The organic cation is not particularly limited. Furthermore, the valency of the organic cation may be 1 or 2 or higher. In particular, among the above organic cations, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0220] [ka]

[0221] In the above equation (ZaI), R201 , R 202 , and R 203 Each of these independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. Also, R 201 ~R 203 Two of these may bond 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 the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0222] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0223] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group. Aryl sulfonium cations are R 201 ~R 203 All of them may be aryl groups, or R 201 ~R 203 A portion of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of these may bond 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 the bonding of two of these include alkylene groups (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-) 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. Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0224] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. 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 or cycloalkyl group that the arylsulfonium cation may optionally have 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, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0225] R 201 ~R 203Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent, forming a halogenated alkyl group such as a trifluoromethyl group. Furthermore, it is preferable that the above substituents form an acid-degradable group in any combination. Furthermore, an acid-degradable group is defined as a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a leaving group that is removed upon the action of an acid. The polar group and leaving group are as described above.

[0226] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 However, each of these independently represents a cation that is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0227] R 201 ~R 203Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 This may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. Also, R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0228] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0229] [ka]

[0230] In the formula (ZaI-3b), R 1c ~R 5c Each of these 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 of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R yEach of these 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. Also, R 1c ~R 7c , and also, R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0231] 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 These elements may bond 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 above-mentioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0232] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of groups formed by the bonding of these atoms include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0233] R 1c ~R 5c , R 6c , R 7c , R x , R y , and also, 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 rings formed by the bonding of these elements to each other may have substituents.

[0234] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0235] [ka]

[0236] In the formula (ZaI-4b), l represents an integer between 0 and 2. r represents an integer between 0 and 8. R 13 This represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. R 14R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, 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 in part). These groups may have substituents. 14 If multiple instances exist, each independently represents one of the above-mentioned groups, such as a hydroxyl group. R 15 Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R 15 It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R 15 The ring formed by the bonding of these elements may have substituents.

[0237] In equation (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. Also, R 13 ~R 15 , and also, R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0238] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0239] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 and R 205 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0240] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0241] [ka]

[0242] [ka]

[0243] [ka]

[0244] "M + X - In the compound represented by ", X - This represents an organic anion. The organic anion is not particularly limited and can be any organic anion with one or more valents. As for the organic anion, anion with a remarkably low ability to undergo nucleophilic reactions is preferred, and non-nucleophilic anions are more preferred.

[0245] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0246] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group described above may be, for example, a fluoroalkyl group (which may have substituents other than a fluorine atom; it may also be a perfluoroalkyl group).

[0247] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0248] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0249] In aralkyl carboxylic acid anions, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0250] An example of a sulfonylimid anion is the saccharin anion.

[0251] For bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure. This increases the acid strength.

[0252] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4 - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0253] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably with 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred. Multiple non-nucleophilic anions may be bonded to each other via linking groups.

[0254] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0255] [ka]

[0256] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Furthermore, preferred non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0257] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0258] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0259] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0260] In formula (AN1-1), * a R in equation (AN1) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) 1 )(R 2)- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. 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 It represents. However, X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) 2a and R 2b If all of them are hydrogen atoms, then Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. * A R in equation (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0261] In formula (AN1), R 3 This represents an organic group. The above 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 above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0262] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0263] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0264] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0265] [ka]

[0266] In equation (AN2), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0267] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0268] R 4 and R 5 Each of these 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 instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred for R4 and R5.

[0269] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0270] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0271] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. Furthermore, the heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0272] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0273] 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 in equation (AN2). q' represents an integer from 0 to 10.

[0274] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0275] [ka]

[0276] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0277] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations of these.

[0278] B represents a hydrocarbon group. For B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group) is more preferred. Furthermore, examples of substituents that the aryl group may have include alkyloxycarbonyl groups (preferably having 1 to 10 carbon atoms) and cycloalkyloxycarbonyl groups. The cycloalkyl group in the cycloalkyloxycarbonyl group may have heteroatoms such as oxygen atoms and sulfur atoms as ring members.

[0279] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, R q R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. q They may be joined to each other to form a ring. Two R q The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0280] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0281] [ka]

[0282] [ka]

[0283] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have substituents (for example, a hydroxyl group).

[0284] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). Z 2c The hydrocarbon group in the above may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group, which may have substituents. The carbon atoms forming the norbornyl group may also be carbonyl carbons. Also, in equation (d1-2) "Z 2c -SO3 - It is preferable that the anion represented by the above formulas (AN1) to (AN3) is different from the anion. For example, Z 2c It is preferable that it is not an aryl group. Also, for example, Z 2c -SO3 - For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z 2c is, -SO3 - Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0285] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0286] In formula (d1-4), R 53 and R 54 Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). 53 and R 54 They may be joined to each other to form a ring.

[0287] Organic anions may be used individually or in combination of two or more.

[0288] Furthermore, the photoacid generator may be a betaine compound having a cationic and anionic portion, with the two portions covalently linked.

[0289] Furthermore, the following compounds are considered preferred specific examples. In the compounds below, the anion and cation can be arbitrarily exchanged.

[0290] [ka]

[0291] [ka]

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] [ka]

[0298] [ka]

[0299] [ka]

[0300] [ka]

[0301] The content of the photoacid generator (B) in the composition of the present invention (total content if the photoacid generator (B) includes two or more compounds) is 15.0% by mass or more, preferably 15.0 to 85.0% by mass, more preferably 20.0 to 70.0% by mass, even more preferably 25.0 to 60.0% by mass, and particularly preferably 30.0 to 60.0% by mass, based on the total solid content of the composition of the present invention. The photoacid generator (B) contained in the composition of the present invention may be one type or two or more types.

[0302] <(C) Compounds that decompose upon irradiation with active light or radiation, resulting in a decrease in acid-scavenging ability> The composition of the present invention may contain, as an acid diffusion control agent, (C) a compound that decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability (also referred to as "compound (C)" or "photodecayable quencher (C)"). Compound (C) acts as a quencher, trapping the acid generated from the photoacid generator (B) during exposure and suppressing the reaction of the resin (A) in the unexposed areas due to excess generated acid.

[0303] Compound (C) is preferably an ionic compound (C). Compound (C) is preferably a compound having an anion and a cation. Compound (C) is a compound that produces an acid that is relatively weaker than the acid produced by the photoacid generator (B). In other words, compound (C) is a compound that produces an acid with a higher pKa than the acid produced by the photoacid generator (B). The difference between the pKa of the acid generated from compound (C) and the pKa of the acid generated from the photoacid generator (B) (the value obtained by subtracting the pKa of the acid generated from the photoacid generator (B) from the pKa of the acid generated from compound (C)) is not particularly limited, but is preferably 1.00 or higher, preferably 1.00 to 10.00, more preferably 1.00 to 5.00, and even more preferably 1.00 to 3.00. Furthermore, the pKa of the acid generated from compound (C) varies depending on the type of photoacid generator (B) used, but for example, -4.00 to 14.00 is preferred, -2.00 to 12.00 is more preferred, and -1.00 to 5.00 is even more preferred.

[0304] In a preferred embodiment, compound (C) contains a halogen atom in the anion portion. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine atoms are preferred. Furthermore, the acid-scavenging group of compound (C) is preferably anionic. In a preferred embodiment, compound (C) may or may not have a non-anionic acid-scavenging group (e.g., an amino group).

[0305] Compound (C) is one of the compounds listed above as the photoacid generator (B) (preferably the above "M + X -Among the onium salts represented by ", a compound that generates an acid that is relatively weaker than the acid generated from the photoacid generator (B) used can be selected and used.

[0306] Compound (C) may or may not have a halogen atom in its cation region. In a preferred embodiment, it is preferable that compound (C) has a halogen atom in its cation region.

[0307] Compound (C) is preferably a compound represented by the following general formulas (C1) to (C3).

[0308] (Compounds represented by the general formula (C1))

[0309] [ka]

[0310] In general formula (C1), R C1 This represents a cycloalkyl group or an aryl group. L C1 This represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination of these. M C + This represents an organic cation.

[0311] In general formula (C1), R C1 This represents a cycloalkyl group or an aryl group. R C1 When represents a cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic. Examples of cycloalkyl groups include norbornyl, dekalinyl, and adamantyl groups, with adamantyl being preferred. One or more of the carbon atoms that are ring member atoms of the above cycloalkyl group may be replaced by carbonyl carbon atoms.

[0312] R C1 When represents an aryl group, an aryl group having 6 to 15 carbon atoms is preferred. Examples of aryl groups include phenyl groups and naphthyl groups, with phenyl groups being preferred.

[0313] R C1 It may have substituents. In one preferred embodiment, R C1 Examples of substituents that may be present include fluorine atoms, groups containing fluorine atoms, hydroxyl groups, alkyl groups, halogen atoms other than fluorine atoms, and the like. As the group having a fluorine atom, a fluorine-substituted alkyl group or a fluorine-substituted cycloalkyl group is preferred. As the fluorine-substituted alkyl group, a fluoride alkyl group having 1 to 5 carbon atoms is preferred. Specifically, examples include a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, etc., with a trifluoromethyl group being preferred. As the fluorine-substituted cycloalkyl group, a fluorinated cycloalkyl group having 3 to 15 carbon atoms is preferred. Specifically, examples include a fluorinated cyclohexyl group, a fluorinated cyclopentyl group, a fluorinated adamantyl group, etc., with a fluorinated cyclohexyl group being preferred. Examples of alkyl groups include linear or branched alkyl groups having 1 to 5 carbon atoms. Other halogen atoms besides fluorine include chlorine, bromine, and iodine.

[0314] In one preferred embodiment, R C1 , and L C1 At least one of them is substituted with a fluorine atom or a group having a fluorine atom. In one preferred embodiment, R C1 It is preferable that this is a polycyclic cycloalkyl group or aryl group substituted with a fluorine atom or a group having a fluorine atom.

[0315] In general formula (C1), L C1 This represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination of these.

[0316] L C1 Examples of alkylene groups when represents an alkylene group include linear or branched alkylene groups having 1 to 20 carbon atoms. Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, and n-pentylene groups, with methylene groups, ethylene groups, n-propylene groups, or n-butylene groups being preferred.

[0317] L C1 When represents a cycloalkylene group, examples of cycloalkylene groups include monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms. Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene, cyclohexylene, cyclopentylene, cycloheptylene, and norvonylene groups, with adamantylene, cyclohexylene, and norvonylene groups being preferred.

[0318] L C1 It may have substituents. In one preferred embodiment, L C1 If it has substituents, the substituents are as follows: C1 Examples of substituents include those that have substituents.

[0319] L C1 It is preferably a single bond, an alkylene group, or a divalent linking group formed by a combination of an alkylene group, -O-, and -C(=O)-, and more preferably a single bond or a methylene group.

[0320] In general formula (C1), M C + This represents an organic cation. MC + It is preferable that this is a cation represented by the following formula (ZcI) or formula (ZcII).

[0321] [ka]

[0322] In the formula (ZcI), R C01 , R C02 , and R C03 Each of these independently represents an organic group.

[0323] [ka]

[0324] In the formula (ZcII), R C04 , and R C05 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group.

[0325] In the above formula (ZcI), R C01 , R C02 , and R C03 Each of these independently represents an organic group. R C01 , R C02 , and R C03 The number of carbon atoms in the organic group is usually 1 to 30, and preferably 1 to 20. Also, R C01 ~R C03 Two of these may bond together 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. C01 ~R C03 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene groups, pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0326] Examples of cations in formula (ZcI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) in the above-mentioned photoacid generator (B).

[0327] In the general formula (ZcII), R C04 , and R C05 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R C04 , and R C05 The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. C04 , and R C05 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R C04 , and R C05 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0328] R C04 , and R C05 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. C04 , and R C05 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C15), alkoxy groups (e.g., C1-C15), halogen atoms, hydroxyl groups, and phenylthio groups.C04 and R C05 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0329] In a preferred embodiment, the cation represented by formula (ZcI) and the cation represented by formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. The acid-degradable group is the same as the acid-degradable group described in resin (A) above. The compound represented by general formula (C1) may or may not have a halogen atom in the cation region.

[0330] (Compounds represented by the general formula (C2))

[0331] [ka]

[0332] In general formula (C2), R C2 This represents a cycloalkyl group or an aryl group. L C2 This represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination of these. M C + This represents an organic cation.

[0333] In general formula (C2), R C2 This represents a cycloalkyl group or an aryl group. R C2 When represents a cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic. Examples of cycloalkyl groups include norbornyl, dekalinyl, and adamantyl groups, with adamantyl being preferred.

[0334] R C2 When represents an aryl group, an aryl group having 6 to 15 carbon atoms is preferred. Examples of aryl groups include phenyl groups and naphthyl groups, with phenyl groups being preferred.

[0335] R C2 It may have substituents. In one preferred embodiment, R C2 If the substituent has substituents, the substituent is R in the general formula (C1) as a preferred embodiment. C1 Examples of substituents include those that have substituents. In one preferred embodiment, R C2 When the compound has substituents, the substituents are not particularly limited, but include alkyl groups (preferably having 1 to 6 carbon atoms), alkylcarbonylamino groups (preferably having 1 to 6 carbon atoms), hydroxyl groups, or halogen atoms. C2 It may have multiple substituents. The alkyl group may have further substituents.

[0336] In one preferred embodiment, R C2 The group is preferably a polycyclic cycloalkyl group, a polycyclic cycloalkyl group substituted with a fluorine atom or a group having a fluorine atom, or an aryl group substituted with a fluorine atom or a group having a fluorine atom, and more preferably an adamantyl group, or a phenyl group substituted with a fluorine atom or a group having a fluorine atom.

[0337] In general formula (C2), L C2 This represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination of these.

[0338] L C2Examples of alkylene groups when represents an alkylene group include linear or branched alkylene groups having 1 to 20 carbon atoms. Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, and n-pentylene groups, with methylene groups, ethylene groups, n-propylene groups, or n-butylene groups being preferred.

[0339] L C2 When represents a cycloalkylene group, examples of cycloalkylene groups include monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms. Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene, cyclohexylene, cyclopentylene, cycloheptylene, and norvonylene groups, with adamantylene, cyclohexylene, and norvonylene groups being preferred.

[0340] L C2 It may have substituents. In one preferred embodiment, L C2 If the substituent has substituents, then R is one preferred embodiment of the above. C2 Examples of substituents include those that have substituents.

[0341] The above R C2 When L represents an aryl group, C2 It is preferable that the bond is a single bond. The above R C2 When L represents a cycloalkyl group, C2 It is preferably an alkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination thereof, and it is even more preferable that it is an alkylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination thereof, substituted with a fluorine atom or a group containing a fluorine atom. In one preferred embodiment, R C2 , and L C2 At least one of the components is substituted with a fluorine atom or a group containing a fluorine atom. The groups containing a fluorine atom are as described above.

[0342] M C + This represents an organic cation. M C + It is preferable that this is a cation represented by the above formula (ZcI) or the above formula (ZcII). In a preferred embodiment, the cation represented by formula (ZcI) and the cation represented by formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. The acid-degradable group is the same as the acid-degradable group described in resin (A) above. Compounds represented by the general formula (C2) may or may not have a halogen atom in the cation region.

[0343] (Compounds represented by the general formula (C3))

[0344] [ka]

[0345] In general formula (C3), A C31 , and A C32 These are, independently, -SO2-R PC1 , or -CO-R PC2 It represents. R PC1 , and R PC2 This represents an organic group. M C + This represents an organic cation.

[0346] In general formula (C3), A C31 and A C32 These are, independently, -SO2-R PC1 , or -CO-R PC2 It represents. R PC1 , and R PC2 This represents an organic group. R PC1 , and RPC2 These are -L C31 -R C31 , and -L C32 -R C32 It is preferable that it be represented as follows:

[0347] R C31 , and R C32 Each of these independently represents an alkyl group or a cycloalkyl group. R C31 , or R C32 When represents an alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups, with methyl or ethyl groups being preferred, and methyl groups being more preferred.

[0348] R C31 , or R C32 When represents a cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic. Examples of cycloalkyl groups include cyclohexyl, norbornyl, dekalinyl, and adamantyl groups, with cyclohexyl or adamantyl being preferred. One or more of the carbon atoms that are ring member atoms of the above cycloalkyl group may be replaced by carbonyl carbon atoms. Furthermore, one or more of the carbon atoms that are ring member atoms of the above cycloalkyl group may be replaced by oxygen atoms.

[0349] R C31 , or R C32 It may have substituents. In one preferred embodiment, R C31 , or R C32 If the substituent has substituents, the substituent is R in the general formula (C1) as a preferred embodiment. C1Examples of substituents include those that have substituents.

[0350] R C31 , and R C32 Each of these is preferably an alkyl group, a fluorine atom, or an alkyl group substituted with a group having a fluorine atom, or a cycloalkyl group, and more preferably a methyl group, a trifluoromethyl group, a cyclohexyl group, or an adamantyl group.

[0351] L C31 , and L C32 Each of these independently represents a single bond or a divalent linking group. L C31 , and L C32 Preferably, each of these independently represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, -S(=O)2-, or a divalent linking group formed by a combination thereof.

[0352] L C31 or L C32 Examples of alkylene groups when represents an alkylene group include linear or branched alkylene groups having 1 to 20 carbon atoms. Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, and n-pentylene groups, with methylene groups, ethylene groups, n-propylene groups, or n-butylene groups being preferred.

[0353] L C31 or L C32 When represents a cycloalkylene group, examples of cycloalkylene groups include monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms. Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene, cyclohexylene, cyclopentylene, cycloheptylene, and norvonylene groups, with adamantylene, cyclohexylene, and norvonylene groups being preferred. One or more of the carbon atoms that are ring members of the cycloalkylene group may be replaced by heteroatoms (e.g., oxygen atoms, nitrogen atoms).

[0354] L C31 , or L C32 It may have substituents. In one preferred embodiment, L C31 , or L C32 If the substituent has substituents, the substituent is R as a preferred embodiment described above. C31 , or R C32 Examples of substituents include those that have substituents.

[0355] L C31 , and L C32 Preferably, each of these is independently a single bond, an alkylene group, a cycloalkylene group, a fluorine-substituted alkylene group, -S(=O)2-, or a divalent linking group formed by a combination thereof. In a preferred embodiment, A C31 , and A C32 At least one of them is substituted with a fluorine atom or a group having a fluorine atom.

[0356] In general formula (C3), M C + This represents an organic cation. M C + It is preferable that this is a cation represented by the above formula (ZcI) or formula (ZcII).

[0357] In a preferred embodiment, the cation represented by formula (ZcI) and the cation represented by formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. The acid-degradable group is the same as the acid-degradable group described in resin (A) above. Compounds represented by the general formula (C3) may or may not have a halogen atom in the cation region.

[0358] Furthermore, compound (C) may be a betaine compound having a cationic and anionic moiety, with the two moieties covalently linked.

[0359] The following compounds are preferred examples of compound (C). In the following compounds, the anion and cation can be arbitrarily exchanged.

[0360] [ka]

[0361] [ka]

[0362] [ka]

[0363] [ka]

[0364] [ka]

[0365] [ka]

[0366] [ka]

[0367] [ka]

[0368] If the composition of the present invention contains compound (C), the content of compound (C) is not particularly limited, but is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 5.0% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the content of compound (C) is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 50.0% by mass or less. If the composition of the present invention contains compound (C), compound (C) may be used alone or in combination of two or more types.

[0369] <A compound (D) that generates acid upon irradiation with active light or radiation, and decomposes upon irradiation with active light or radiation, resulting in a decrease in its acid-scavenging ability.> As mentioned above, compound (B) and compound (C) may be the same compound. In this case, the compound may be compound (D) (also called "compound (D)" or "photoacid generator linked quencher (D)") which generates acid upon irradiation with active light or radiation and decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability. In other words, compound (D) is a compound that possesses a structure having the function equivalent to that of photoacid generator (B) and a structure having the function equivalent to that of compound (C). Compound (D) is a preferred embodiment of the photoacid generator (B), and is also a preferred embodiment of compound (C). Compound (D) is preferably an ionic compound. Compound (D) is preferably a compound having an anion and a cation.

[0370] As mentioned above, compound (C) is a compound that generates an acid that is relatively weaker than the acid generated by the photoacid generator (B). In other words, compound (C) is a compound that generates an acid with a pKa greater than the acid generated by the photoacid generator (B). If the photoacid generator (B) and compound (C) are the same compound (D), then the pKa of the acid generated from the structure in compound (D) that has the function equivalent to compound (C) shall be greater than the pKa of the acid generated from the structure that has the function equivalent to the photoacid generator (B).

[0371] (Compounds represented by the general formula (PD)) Compound (D) is not particularly limited, but is preferably a compound represented by the following general formula (PD).

[0372] [ka]

[0373] In the general formula (PD), M D1 + , and M D2 + Each of these independently represents an organic cation. L D This represents a divalent organic group. A D1 - , and B D1 - Each of these independently represents an acid anion group. However, the M of compounds represented by the general formula (PD) D1 + and M D2 + Each of these is HA substituted with a hydrogen atom. D1 -L D -B D1 In a compound represented by H, HA D1 The pKa of the group represented by B D1 It is lower than the pKa of the group represented by H.

[0374] Compounds represented by the general formula (PD) have a structure ("M") that has a function equivalent to that of a photoacid generator (B). D1 + A D1 - The part corresponding to "-" and the structure having a function corresponding to compound (C) ("-B" D1 - M D2 + Since it contains both the part corresponding to " and in a single molecule, the relative abundance of each of the above structures can be kept constant in the resist film. Therefore, the inventors speculate that when the resist film is exposed, the amount and diffusion of acid generated within the resist film tend to be uniform, resulting in a stable pattern width after development.

[0375] In the general formula (PD), M D1 + and M D2 + Each of these independently represents an organic cation. M D1 + and M D2 + The organic cations are preferably each independently represented by the above formula (ZcI) or formula (ZcII).

[0376] In the general formula (PD), L D This represents a divalent organic group. Examples of the above-mentioned divalent organic groups include -COO-, -CONH-, -CO-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. One or more methylene groups constituting the cycloalkane ring of the above cycloalkylene group may be replaced by a carbonyl carbon and / or oxygen atom. These divalent linking groups may further preferably have a group selected from the group consisting of -O-, -S-, -SO-, and -SO2-.

[0377] Among them, L D It is preferable that the group is represented by the following general formula (LD). *A D -L D AL D BL D CL D DL D E-*B D (LD)

[0378] In the general formula (LD), *A D A in the general formula (PD)D1 - This indicates the connection point with [the other element]. In the general formula (LD), *B D In the general formula (PD), B D1 - This indicates the connection point with [the other element].

[0379] In the general formula (LD), L D A is -(C(R D LA1 )(R D LA2 )) XA D - or represents an arylene group. The above XA D represents an integer greater than or equal to 1, preferably between 1 and 10, and more preferably between 1 and 3. R D LA1 and R D LA2 Each of these independently represents a hydrogen atom or a substituent. R D LA1 and R D LA2 Each substituent is preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and even more preferably a fluorine atom or a perfluoromethyl group. XA D If it is 2 or more, XA D There are R D LA1 These may be the same or different. XA D If it is 2 or more, XA D There are R D LA2 These may be the same or different. -(C(R D LA1 )(R D LA2 ))- is preferably -CH2-, -CHF-, -CH(CF3)-, or -CF2-. In particular, A in the general formula (PD) D1 - It directly bonds with -(C(R DLA1 )(R D LA2 ))- is preferably -CH2-, -CHF-, -CH(CF3)-, or -CF2-. A in the general formula (PD) D1 - It directly bonds with -(C(R D LA1 )(R D LA2 ))-other-(C(R D LA1 )(R D LA2 Each of the following is preferably independently -CH2-, -CHF-, or -CF2-. L D The arylene group of A is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred. The arylene group may have substituents. The substituents are not particularly limited, but halogen atoms are preferred, and fluorine atoms are more preferred.

[0380] In the general formula (LD), L D B represents a single bond, an ether group (-O-), an ester group (-COO-), a sulfonyl group (-SO2-), or a group formed by a combination of these.

[0381] In the general formula (LD), L D C represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, or a group formed by a combination of these (e.g., "-alkylene group-cycloalkylene group-"). The alkylene group described above may be linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. The number of carbon atoms in the cycloalkylene group is preferably 3 to 15, and more preferably 5 to 10. The alkylene group may have substituents. The above cycloalkylene group may be monocyclic or polycyclic. Examples of the cycloalkylene groups mentioned above include norbornanediyl and adamantanediyl groups. The above cycloalkylene group may have substituents. Preferred substituents on the above cycloalkylene group are alkyl groups (which may be linear or branched; preferably having 1 to 5 carbon atoms). One or more methylene groups constituting the cycloalkane ring of the above-mentioned cycloalkylene group may be replaced by a carbonyl carbon and / or a heteroatom (such as a nitrogen atom or an oxygen atom). L D If C is "-alkylene group-cycloalkylene group-", the alkylene group portion is L D It is preferable that it be located on side B. L D The arylene group of C is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred. The arylene group may have substituents. In a preferred embodiment, the arylene group may have C as a substituent. D1 - -L D AL D It is acceptable to have a B- rating. C D1 - represents an acid anionic group. Examples of acid anionic groups include the above A. D1 - Examples similar to the acid anionic group can be given. L D A, L D B is L in the above formula (LD) D A, L D This is synonymous with B. Note that the arylene group has C as a substituent. D1 - -L D AL D If B- is present, the above general formula (PD) is M D3 + It has M D3 + is an organic cation, and as mentioned above, M D1 + and M D2 + Examples of organic cations similar to the above can be given. LD If B is a single bond, L D C is preferably a single bond or a cycloalkylene group.

[0382] In the general formula (LD), L D D represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

[0383] In the general formula (LD), L D E is a single bond, -N(R)-, -(C(R) D LE1 )(R D LE2 )) XE D -, or a combination of these, represents a base. In the above -N(R)-, R represents a hydrogen atom or a substituent. The substituent of R is preferably an alkyl group (preferably a linear or branched group with 1 to 6 carbon atoms) or a cycloalkyl group (preferably with 3 to 12 carbon atoms). The above - (C(R D LE1 )(R D LE2 )) XE D - in XE D represents an integer greater than or equal to 1, preferably between 1 and 10, and more preferably between 1 and 3. R D LE1 and R D LE2 Each of these independently represents a hydrogen atom or a substituent. R D LE1 and R D LE2 Each substituent is preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and even more preferably a fluorine atom or a perfluoromethyl group. XE D If it is 2 or more, XE D There are R D LE1 These may be the same or different. XE DIf it is 2 or more, XE D There are R D LE2 These may be the same or different. Among them, -(C(R D LE1 )(R D LE2 ))- is preferred to be -CH2-. General formula (L D ) Medium, L D B, L D C and L D If D is a single bond, L D It is preferable that E is also a single bond.

[0384] In the general formula (PD), A D1 - This represents an acid anionic group. An acid anionic group is a group that contains an anionic atom. A D1 - Specifically, it is preferable that the group is represented by one of the general formulas (AD-1) to (AD-3).

[0385] [ka]

[0386] In the general formulas (AD-1) to (AD-3), * represents the bond position. In general formula (AD-2), R AD This represents an organic group. In general formula (AD-3), R AE Each of these independently represents an organic group. R AD While not particularly limited, alkyl groups or aryl groups are preferred. The alkyl group mentioned above may be linear or branched. The alkyl group has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The alkyl group described above may have substituents. While not particularly limited, fluorine atoms are preferred as substituents. The alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.

[0387] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, or perfluoroalkyl groups being more preferred. R AE The organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0388] In the general formula (PD), B D1 - This represents an acid anionic group. B D1 - Specifically, it is preferable that the group is represented by one of the general formulas (BD-1) to (BD-7). B D1 - The group is preferably represented by any of the general formulas (BD-1) to (BD-3), and more preferably by any of the general formulas (BD-1) to (BD-2).

[0389] [ka]

[0390] In the general formulas (BD-1) to (BD-7), R BD Each of these independently represents an organic group. L BD Each of these independently represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, -O-, -C(=O)-, -SO2-, or a divalent linking group formed by a combination of these. * indicates the connection position.

[0391] R BD The group is preferably an alkyl group, a cycloalkyl group, or an aryl group. R BD When represents an alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups, with methyl or ethyl groups being preferred, and methyl groups being more preferred.

[0392] R BD When represents a cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic. Examples of cycloalkyl groups include cyclopentyl, norbornyl, dekalinyl, and adamantyl groups. One or more methylene groups constituting the cycloalkane ring of the above cycloalkyl group may be replaced by a carbonyl carbon and / or a heteroatom (such as a nitrogen atom or an oxygen atom).

[0393] R BD When represents an aryl group, an aryl group having 6 to 15 carbon atoms is preferred. Examples of aryl groups include phenyl groups and naphthyl groups, with phenyl groups being preferred.

[0394] R BD It may have substituents. In one preferred embodiment, R BD If the substituent has substituents, the substituent is R in the general formula (C1) as a preferred embodiment. C1 Examples of substituents include those that have substituents. In one preferred embodiment, R BDIf the substituent has substituents, the substituents may be alkyl groups, cycloalkyl groups, alkoxy groups, alkyloxyalkyloxy groups, alkoxycarbonyl groups, cyano groups, halogen atoms, or SO3 - We can list some examples. The alkyl group is not particularly limited, but a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. The cycloalkyl group is not particularly limited, but cycloalkyl groups having 3 to 15 carbon atoms are preferred, and cycloalkyl groups having 5 to 10 carbon atoms are more preferred. The cycloalkyl group may be monocyclic or polycyclic. The alkoxy group is not particularly limited, but an alkoxy group having 1 to 12 carbon atoms is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred. The alkyloxyalkyloxy group is not particularly limited, but a straight alkyloxyalkyloxy having 2 to 12 carbon atoms (which may be linear or branched) is preferred. The alkyl group in the alkoxycarbonyl group is not particularly limited, but a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. R BD The alkyl group may have multiple substituents. The alkyl group, cycloalkyl group, alkoxy group, alkyloxyalkyloxy group, and alkoxycarbonyl group may have further substituents.

[0395] Note, R BD However, SO3 is used as a substituent. - If it has, then the above general formula (PD) is M D4 + It has M D4 + is an organic cation, and as mentioned above, M D1 + and M D2 + Examples of organic cations similar to the above can be given.

[0396] R BD It is preferable that it has an acid-degradable group. Acid-degradable groups are groups that decompose under the action of acid to produce polar groups. The acid-degradable groups are the same as those described in resin (A) above.

[0397] L BD This represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, -O-, -C(=O)-, -SO2-, or a divalent linking group formed by a combination of these.

[0398] L BD Examples of alkylene groups when represents an alkylene group include linear or branched alkylene groups having 1 to 20 carbon atoms. Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, and n-pentylene groups, with methylene groups, ethylene groups, n-propylene groups, or n-butylene groups being preferred.

[0399] L BD When represents a cycloalkylene group, examples of cycloalkylene groups include monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms. Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene, cyclohexylene, cyclopentylene, cycloheptylene, and norvonylene groups, with adamantylene, cyclohexylene, and norvonylene groups being preferred. L BD When represents an arylene group, the arylene group is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred.

[0400] L BD It may have substituents. In one preferred embodiment, L BD If the substituent has substituents, the substituent is R as a preferred embodiment described above. BD Examples of substituents include those that have substituents. In addition, as a preferred embodiment, L BDExamples of substituents that may be present include alkyl groups, alkoxy groups, and alkoxycarbonyl groups. The alkyl group is not particularly limited, but a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. The alkoxy group is not particularly limited, but an alkoxy group having 1 to 12 carbon atoms is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred. The alkyl group in the alkoxycarbonyl group is not particularly limited, but a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. L BD It is preferable that it has an acid-degradable group. Acid-degradable groups are groups that decompose under the action of acid to produce polar groups. The acid-degradable groups are the same as those described in resin (A) above.

[0401] L BD It is preferable that the linking group is a single bond, a methylene group, -O-, -C(=O)-, or a divalent linking group formed by a combination thereof, and more preferably a single bond or a methylene group.

[0402] M of compounds represented by the general formula (PD) D1 + and M D2 + Each of these is HA substituted with a hydrogen atom. D1 -L D -B D1 In a compound represented by H, HA D1 The pKa of the group represented by B D1 It is lower than the pKa of the group represented by H. More specifically, HA D1 -L D -B D1 When the acid dissociation constant is determined for a compound represented by H, "HA D1 -L D -B D1 H is A D1 - -L D -B D1When pKa becomes "H", the pKa is "HA D1 Let the pKa of the group represented by "A" be the acid dissociation constant a1, and further, "A D1 - -L D -B D1 H is A D1 - -L D -B D1 - The pKa when this occurs is "B D1 Let the pKa of the group represented by H be the acid dissociation constant a². "HA D1 The pKa of the group represented by "B D1 The pKa of the group represented by H can be determined by the acid dissociation constant measurement method described above. Among them, HA D1 The pKa of the group represented by is preferably -20.00 to 2.00, more preferably -7.00 to 0.50, and even more preferably -5.00 to 0.00. B D1 The pKa of the group represented by H is preferably -4.00 to 20.00, more preferably -4.00 to 14.00, even more preferably -2.00 to 12.00, and particularly preferably -1.00 to 5.00. B D1 pKa of the group represented by H and HA D1 The difference from the pKa of the group represented by ("B D1 "pKa of the group represented by H" - "HA D1 The pKa of the group represented by is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, and even more preferably 1.00 to 15.00.

[0403] Furthermore, as a preferred embodiment, "M" is listed as the photoacid generator (B). + X - The onium salt represented by " and the compound represented by any of the general formulas (C1) to (C3) listed as compound (C) may be bonded to each other by a single bond or by a linking group. For example, "M" listed as a photoacid generator (B) + X - X of the onium salt represented by " -The anionic portions of the compounds represented by any of the general formulas (C1) to (C3) listed as compound (C) may be bonded to each other by single bonds or by linking groups.

[0404] The following are preferred specific examples of compounds that fall under compound (D).

[0405] [ka]

[0406] [ka]

[0407] [ka]

[0408] [ka]

[0409] [ka]

[0410] [ka]

[0411] [ka]

[0412] [ka]

[0413] When the composition of the present invention contains compound (D), the content of compound (D) is not particularly limited, but is preferably 5.0% by mass or more, more preferably 9.0% by mass or more, and even more preferably 15.0% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the above content is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 50.0% by mass or less. Compound (D) may be used alone or in combination of two or more types.

[0414] The composition of the present invention contains compound (D), and more preferably contains at least one of compound (B) that is not compound (D) (a compound from compound (B) that does not correspond to compound (D)) and compound (C) that is not compound (D) (a compound from compound (C) that does not correspond to compound (D)).

[0415] The following are specific examples of the forms in which the compound corresponding to the photoacid generator (B) or compound (C) in the composition of the present invention can be contained.

[0416] (i) Photoacid generators other than compound (D) (B) (ii) Photoacid generator (B) other than compound (D) + compound (C) other than compound (D) (iii) Compound (D) (iv) Compound (D) + Photoacid generator (B) other than Compound (D) (v) Compound (D) + Compound (C) other than Compound (D) (vi) Compound (D) + Photoacid generator other than compound (D) (B) + Compound (C) other than compound (D)

[0417] <Hydrophobic resin> The composition of the present invention may further contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0418] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. Furthermore, the hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0419] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition.

[0420] <Solvent> The composition of the present invention may contain 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, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0421] The inventors have found that when such solvents are used in combination with the resins described above, the coatability of the composition is improved, and patterns with fewer development defects can be formed. Although the reason for this is not entirely clear, the inventors believe that these solvents have a good balance of solubility, boiling point, and viscosity with the resins described above, which suppresses unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein by reference.

[0422] As described above, the solvent may further contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0423] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the applicability of the composition of the present invention. Furthermore, "solid content" refers to all components other than the solvent, and as mentioned above, it refers to the components that form a photosensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the mass of the components other than the solvent, relative to the total mass of the composition of the present invention. "Total solids" refers to the total mass of the components of the composition of the present invention, excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent, as described above, and may be solid or liquid at 25°C, for example.

[0424] <Surfactants> The composition of the present invention may contain a surfactant. The inclusion of a surfactant results in superior adhesion and the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 19395.

[0425] These surfactants may be used individually or in combination of two or more types.

[0426] If the composition of the present invention contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition.

[0427] <Other additives> The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0428] The composition of the present invention may further contain a dissolution-inhibiting compound. Here, a "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer.

[0429] The composition of the present invention is suitably used as a photosensitive composition for EUV. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0430] A high A value, calculated using the following formula (1), indicates that the EUV and electron beam absorption efficiency of the resist film formed from the composition of the present invention is high, which is effective in reducing photon shot noise. The A value represents the EUV and electron beam absorption efficiency of the mass percentage of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value of 0.120 or higher is preferred. There is no particular upper limit, but if the A value is too high, the EUV and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result it becomes difficult to obtain a good pattern shape. Therefore, 0.240 or lower is preferred, and 0.220 or lower is more preferred.

[0431] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from the total solids in the photosensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition. For example, if the resist composition contains an acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-degradable resin, the photoacid generator, and the acid diffusion control agent constitute the solid content. In other words, the total atoms of the total solid content refer to the sum of the total atoms derived from the resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the total hydrogen atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent to the sum of the total atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent.

[0432] The A value can be calculated by determining the atomic ratio of the constituent components if the structure and content of the total solid components in the resist composition are known. Even if the constituent components are unknown, the atomic ratio can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.

[0433] [Application] The present invention relates to a photosensitive or radiation-sensitive resin composition whose properties change upon irradiation with active light or radiation. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or manufacturing of lithographic printing plates or acid-curable compositions. The patterns formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0434] [Actinic ray-sensitive or radiation-sensitive film] The present invention also relates to photosensitive or radiation-sensitive films (typically "resist films") formed by the photosensitive or radiation-sensitive composition of the present invention. Such films are formed, for example, by coating the composition of the present invention onto a support such as a substrate. The thickness of the film is preferably 0.01 to 0.15 μm. The coating is applied to the substrate by various methods, including spin coating, roll coating, flow coating, dip coating, spray coating, and doctor coating. Spin coating is preferred, with a preferred rotation speed of 1000 to 3000 rpm (rotations per minute). The coated film is pre-baked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes, to form a thin film. The materials constituting the substrate to be processed and its outermost layer can, for example, be silicon wafers in the case of semiconductor wafers. Examples of materials for the outermost layer include Si, SiO2, SiN, SiON, TiN, WSi, BPSG (Boron Phosphorus Silicon Glass), SOG (spin-on-glass), and organic anti-reflective coatings.

[0435] [Pattern formation method] The procedure for a pattern-forming method using the above-mentioned photosensitive or radiation-sensitive resin composition is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition. Step 2: Exposure of a photosensitive or radiation-sensitive film. Step 3: A process of developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern. The following details the steps for each of the above processes.

[0436] <Step 1: Actinic ray- or radiation-sensitive film formation step> Step 1 is a step of forming an activated light-sensitive or radiation-sensitive film on a substrate using an activated light-sensitive or radiation-sensitive resin composition.

[0437] One method for forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive light or a radiation-sensitive resin composition is to apply the photosensitive light or radiation-sensitive resin composition onto the substrate. Furthermore, it is preferable to filter the reactive light or radiation-sensitive resin composition before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0438] The light-sensitive or radiation-sensitive resin composition can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the reactive light or radiation-sensitive resin composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic film, organic film, anti-reflective film) may be formed beneath the resist film.

[0439] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out 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.

[0440] The thickness of the light-sensitive or radiation-sensitive film is not particularly limited, but 10 to 120 nm is preferred because it allows for the formation of more precise fine patterns. In particular, when using EUV exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0441] Furthermore, a topcoat may be formed on the upper layer of the light-sensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition can be applied uniformly to the top layer of the light-sensitive or radiation-sensitive film without being mixed with the light-sensitive or radiation-sensitive film. The topcoat is not particularly limited, and any conventionally known topcoat can be formed by conventionally known methods. For example, a topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Publication No. 2013-61648, on a light-sensitive or radiation-sensitive film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be included in the aforementioned light-sensitive or radiation-sensitive resin composition. Furthermore, it is preferable that the top coat contains a compound comprising at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0442] <Step 2: Exposure Process> Step 2 is the step of exposing the reactive light or radiation-sensitive film. One method of exposure is to irradiate the formed reactive light or radiation-sensitive film with reactive light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV, X-rays, and electron beams.

[0443] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in 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 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also called post-exposure baking.

[0444] <Process 3: Development process> Step 3 is the process of developing the exposed light-sensitive or radiation-sensitive film using a developer solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0445] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and leaving it still for a certain period of time for development (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0446] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

[0447] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0448] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, based on the total amount of the developer.

[0449] <Other processes> The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0450] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may also be added to the rinsing solution.

[0451] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0452] The rinsing process is not particularly limited and can be performed by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or spraying rinsing solution onto the substrate surface (spray method). Furthermore, the pattern formation method of the present invention may include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of softening 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 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0453] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask. Dry etching is preferably performed using oxygen plasma etching.

[0454] The compositions of the present invention and the various materials used in the pattern forming method of the present invention (e.g., solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred. Examples of metallic 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.

[0455] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0456] Furthermore, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0457] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction 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 in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0458] In organic processing solutions such as rinsing solutions, a conductive compound may be added to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. For chemical piping, various types of piping can be used, such as SUS (stainless steel), or piping coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.). Similarly, for filters and O-rings, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) can be used.

[0459] <Method of manufacturing electronic devices> Furthermore, the present invention relates to a method for manufacturing an electronic device, including the pattern formation method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present invention include those mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0460] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0461] [Various components of photosensitive or radiation-sensitive resin compositions] [Resin (A)] Resins A-1 to A-42 were used as resin (A). In addition, resins A-1C to A-5C were used as resins other than resin (A). Tables 4-6 below show the types and content (mol%) of each repeating unit contained in each resin, the weight-average molecular weight (Mw), and the degree of dispersion (Mw / Mn). The content of each repeating unit is the ratio (molar ratio) of each repeating unit to the total number of repeating units contained in each resin. The type of each repeating unit is indicated by the structure of the corresponding monomer. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The repeating unit content was also determined. 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance). Resins A-7 and A-30 each contain 30 mol% of repeating units corresponding to MA-2 and MA-8, respectively, as acid-degradable repeating units, for a total of 60 mol%. Note that resins A-1C to A-5C are not resins (A), but for convenience, they are listed in the resin (A) column of Table 6. Also, the repeating unit corresponding to M-41 is not a repeating unit represented by general formula (N1), but for convenience, it is listed in the repeating unit represented by general formula (N1) column of Table 6.

[0462] [Table 4]

[0463] [Table 5]

[0464] [Table 6]

[0465] Of the monomers corresponding to each repeating unit that constitutes each resin shown in Tables 4-6, the structures of M-1 to M-40 are as shown in Tables 1-3 above. The structure and SP values ​​of M-41 are shown in Table 7 below. The unit of the SP values ​​shown in Table 7 below is MPa. 1 / 2 That is the case.

[0466] [Table 7]

[0467] The structure of MA-1 to MA-20 is shown below.

[0468] [ka]

[0469] The structures of MB-1 to MB-30 are shown below.

[0470] [ka]

[0471] Examples of the synthesis of M-3 and M-4 are shown below.

[0472] <Synthesis Example 1: Synthesis of Monomer M-3> 120 g of acenaphthene bromide and 720 g of tetrahydrofuran (THF) were mixed and the mixture was cooled to -78°C. 320 mL of 1.6 mol / L nBuLi (hexane solution) was added dropwise and the mixture was stirred for 1 hour. Next, dry ice was added and the mixture was stirred at room temperature for 2 hours. 1 mol / L sodium hydroxide solution was added to stop the reaction, and 83 g of the carboxylic acid compound of acenaphthene was obtained by liquid-liquid purification. Next, 30 g of the obtained carboxylic acid derivative of acenaphthene was mixed with 720 mL of dichloroethane (DCE), and under a nitrogen atmosphere, 57 g of N-bromosuccinimide (NBS) and 56 g of azobisisobutyronitrile (AIBN) were added to the mixture and heated under reflux. After the reaction was complete, the crude product obtained by liquid-liquid purification was mixed with 1600 mL of dimethylformamide (DMF), 39 g of lithium bromide was added, and the mixture was heated at 115°C for 2 hours. The reaction mixture was poured into ice water to stop the reaction, and 4.5 g of M-3 was obtained by column purification.

[0473] [ka]

[0474] <Synthesis Example 2: Synthesis of Monomer M-4> 20 g of M-3 and 23 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (WSC)·HCl hydrochloride were added to 786 mL of dichloromethane and heated at 45°C for 1 hour. To this solution, 19 g of 5-hydroxyisophthalic acid and 2.5 g of 4-dimethylaminopyridine (DMAP) were added and the mixture was stirred at 60°C for 3 hours. The reaction was stopped by adding pure water, and the precipitated solid was purified by recrystallization to obtain 4.2 g of M-4.

[0475] [ka]

[0476] Other monomers were also synthesized using the same method as described above, or by referring to known methods.

[0477] The resin (A) used was synthesized using each monomer by a known method. An example of the synthesis of resin A-4 is shown below.

[0478] <Synthesis Example 3: Synthesis of Resin A-4> 8.3 parts by mass of propylene glycol 1-monomethyl ether 2-acetate (PGMEA) was heated to 85°C under a nitrogen stream. To this solution, while stirring, a mixed solution consisting of 13.6 parts by mass of monomer represented by structural formula M-4, 6.3 parts by mass of monomer represented by structural formula MB-5, 3.6 parts by mass of monomer represented by structural formula MB-12, 13.6 parts by mass of monomer represented by structural formula MA-15, 77.7 parts by mass of cyclohexanone, and 1.1 parts by mass of 2,2'-aziobisisobutyrate dimethyl [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain a reaction solution. After the dropwise addition was complete, the reaction solution was stirred for a further 2 hours at 85°C. After the reaction solution was allowed to cool, it was reprecipitated with a large amount of methanol / water (mass ratio 9 / 1), filtered, and the resulting solid was vacuum dried to obtain resin A-4. The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-4, determined from the GPC (solvent: tetrahydrofuran (THF)), was 12,000, and the degree of dispersion (Mw / Mn) was 1.80. 13 The composition ratio of repeating units derived from M-4, MB-5, MB-12, and MA-15, as measured by 13C-NMR (nuclear magnetic resonance), was 25 / 15 / 10 / 50 in molar ratio.

[0479] Other resins were synthesized in the same manner.

[0480] [Photoacid Generator (B)] The structure of the compound used as the photoacid generator (B) is shown below. Please note that compounds B-1 to B-29 listed below belong to compound (D) (and also to compound (C)). Compounds C-1 to C-12 listed below are compounds (B) that are not compound (D).

[0481] [ka]

[0482] [ka]

[0483] [ka]

[0484] [ka]

[0485] [Compound (C)] The structure of the compound used as compound (C) is shown below. Compounds D-1 to D-9 listed below are compounds (C) that are not compounds (D).

[0486] [ka]

[0487] [Hydrophobic resin] The hydrophobic resins (resins E-1 to E-12) shown in Table 8 below are listed below. Resins E-1 to E-12 were synthesized according to the synthesis method of resin A-4 described above. Table 8 below shows the type and content (mol%) of each repeating unit contained in each resin, the weight-average molecular weight (Mw), and the degree of dispersion (Mw / Mn). The content of each repeating unit is the ratio (molar ratio) of each repeating unit to the total number of repeating units contained in each resin. The type of each repeating unit is indicated by the structure of the corresponding monomer. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The repeating unit content was also determined. 13The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0488] [Table 8]

[0489] The structures of monomers ME-1 to ME-21, which correspond to each repeating unit constituting resins E-1 to E-12 shown in Table 8, are shown below.

[0490] [ka]

[0491] [Surfactants] The surfactants used are listed below. H-1: Megafuck F176 (manufactured by DIC Corporation, fluorine-based surfactant) H-2: Megafuck R08 (manufactured by DIC Corporation, containing fluorine and silicone-based surfactants) H-3: PF656 (manufactured by OMNOVA, a fluorine-based surfactant)

[0492] 〔solvent〕 The solvents used are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene Carbonate F-10: Diacetone alcohol

[0493] <Preparation of the resist composition> The components shown in Tables 9-11 were dissolved in the solvents shown in Tables 9-11 to prepare a solution with a solid content concentration of 2.3% by mass. This solution was then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare a resist composition. Note that "solids" refers to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples. In Tables 9-11, the "Quantity" column indicates the content (mass%) of each component relative to the total solids in the resist composition. In Example 13, 1.0 mass% of C-7 and 5.0 mass% of C-10 were used as photoacid generators (B) that were not compound (D). Tables 9-11 also list the types of solvents used and their mixing ratios (mass ratios).

[0494] [Table 9]

[0495] [Table 10]

[0496] [Table 11]

[0497] Examples 1-40, 47-52, and Comparative Examples 1-6 were patterned using pattern formation method (1) and their performance was evaluated.

[0498] <Pattern formation method (1): EUV exposure, organic solvent development (negative)> A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer film with a thickness of 20 nm. A resist composition was applied on top of the base layer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 40 nm. A silicon wafer containing the obtained resist film was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 50 nm and a line-to-space ratio of 1:1 was used as the reticle. After exposure, the resist film was baked at 90°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative-type pattern. The resist composition used was prepared by storing it in a constant temperature bath at 35°C for 6 months.

[0499] <Performance Evaluation> [Resolution over time] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (EUV irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure levels that exhibit the above sensitivity was defined as L / S resolution (nm). A smaller value indicates better resolution.

[0500] Examples 41 and 42 and Comparative Example 7 were patterned using pattern formation method (2), and their performance was evaluated.

[0501] <Pattern formation method (2): EUV exposure, alkaline development (positive)> A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer film with a thickness of 20 nm. A resist composition was applied on top of the base layer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 40 nm. A silicon wafer containing the obtained resist film was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 50 nm and a line-to-space ratio of 1:1 was used as the reticle. The resist film after exposure was baked at 90°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. Afterward, it was spin-dried to obtain a positive-type pattern. The resist composition used was prepared by storing it in a constant temperature bath at 35°C for 6 months.

[0502] <Performance Evaluation> [Resolution over time] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (EUV irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure levels that exhibit the above sensitivity was defined as L / S resolution (nm). A smaller value indicates better resolution.

[0503] Examples 43 and 44 and Comparative Example 8 were patterned using pattern formation method (3), and their performance was evaluated.

[0504] <Pattern formation method (3): EB exposure, organic solvent development (negative)> The resist composition was applied to a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 40 nm. Furthermore, similar results can be obtained by changing the Si wafer to a chromium substrate.

[0505] The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam lithography system (HL750, Hitachi, Ltd., accelerating voltage 50 keV). During this process, the pattern was drawn to form a 1:1 line-and-space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with n-butyl acetate for 30 seconds, spin-dried, and heated at 95°C for 60 seconds to obtain a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm. The resist composition used was prepared by storing it in a constant temperature bath at 35°C for 6 months.

[0506] <Performance Evaluation> [Resolution over time] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure levels that exhibit the above sensitivity was defined as L / S resolution (nm). A smaller value indicates better resolution.

[0507] Examples 45 and 46 and Comparative Example 9 were patterned using pattern formation method (4), and their performance was evaluated.

[0508] <Pattern formation method (4): EB exposure, alkaline development (positive)> The resist composition was applied to a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 40 nm. Here, 1 inch is equal to 0.0254 m. Furthermore, similar results can be obtained by changing the Si wafer to a chromium substrate.

[0509] The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam lithography system (HL750, Hitachi, Ltd., accelerating voltage 50 keV). During this process, the pattern was drawn to form a 1:1 line-and-space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm. The resist composition used was prepared by storing it in a constant temperature bath at 35°C for 6 months.

[0510] <Performance Evaluation> [Resolution over time] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure levels that exhibit the above sensitivity was defined as L / S resolution (nm). A smaller value indicates better resolution.

[0511] The evaluation results obtained are shown in Tables 12 and 13.

[0512] [Table 12]

[0513] [Table 13]

[0514] As shown in Tables 12 and 13, the resist compositions of the examples were confirmed to exhibit extremely excellent resolution even after a certain period of time had elapsed since preparation, when subjected to EUV or EB exposure and then developed with alkaline or organic solvent to form extremely fine patterns. On the other hand, the resist compositions of the comparative examples exhibited insufficient performance in this regard. [Industrial applicability]

[0515] According to the present invention, even after time has passed since preparation, it is possible to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution in the formation of extremely fine patterns (for example, line and space patterns with a line width or space width of 25 nm or less, preferably 20 nm or less, or hole patterns with a pore diameter of 25 nm or less, preferably 20 nm or less). Furthermore, according to the present invention, it is possible to provide a photosensitive or radiation-sensitive film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[0516] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-160153 filed on September 29, 2021, the contents of which are incorporated herein by reference.

Claims

1. (A) A resin that decomposes and becomes more polar due to the action of an acid, (B) Compounds that generate acid upon irradiation with active light or radiation A photosensitive or radiation-sensitive resin composition containing, The resin (A) has repeating units represented by the following general formula (N1), The solubility parameter of the repeating unit represented by the following general formula (N1) is 24.50 MPa 1 / 2 or higher. Furthermore, the resin (A) has repeating units having acid-degradable groups, and the content of the repeating units having acid-degradable groups is 50 mol% or more relative to the total repeating units of the resin (A). A photosensitive or radiation-sensitive resin composition in which the content of compound (B) is 15.0% by mass or more relative to the total solid content of the photosensitive or radiation-sensitive resin composition. 【Chemistry 1】 In general formula (N1), R Ｎ１ represents a substituent. k represents an integer between 1 and 6. If k represents an integer greater than or equal to 2, then multiple R Ｎ１ They may be the same or they may be different. If k represents an integer greater than or equal to 2, then multiple R Ｎ１ They may combine to form a ring.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (N1) is a repeating unit represented by the following general formula (N2) or (N3). 【Chemistry 2】 In general formula (N2), L Ｎ１ This represents a divalent linking group. L Ｎ２ This represents an alkylene group or single bond which may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a carbonyl group. R Ｎ２ represents a hydrogen atom or substituent. k1 represents an integer between 1 and 6. R Ｎ３ represents a substituent. k2 represents an integer between 0 and 5. However, the sum of k1 and k2 is 6 or less. When k1 represents an integer of 2 or more, a plurality of Ls Ｎ１ , a plurality of Ls Ｎ２ and a plurality of Rs Ｎ２ may be the same as each other or may be different from each other. If k2 represents an integer greater than or equal to 2, then multiple R Ｎ３ They may be the same or they may be different. 【Transformation 3】 In general formula (N3), L Ｎ３ and L Ｎ５ Each of these independently represents a divalent linking group. L Ｎ４ represents a single bond or a divalent linking group. k3 represents an integer between 1 and 3. R Ｎ４ represents a substituent. k4 represents an integer between 0 and 4. However, the sum of 2 × k3 and k4 is 6 or less. If k3 represents an integer greater than or equal to 2, then multiple L Ｎ３ , multiple L Ｎ４ and multiple L Ｎ５ These may be the same or they may be different. If k4 represents an integer greater than or equal to 2, then multiple R Ｎ４ They may be the same or they may be different.

3. L in the above general formula (N2) Ｎ１ , and L in the general formula (N3) Ｎ３ and L Ｎ５ The photosensitive or radiation-sensitive resin composition according to claim 2, wherein each of the following independently represents a carbonyl group, an ester group, an amide group, a sulfonyl group, an oxygen atom, an amino group, or a sulfur atom.

4. In the above general formula (N2), R Ｎ２ The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the group represents a hydrogen atom, a group represented by the following general formula (AL1), or a group represented by the following general formula (AL2). 【Chemistry 4】 In the general formula (AL1), L Ｎ６ k5 represents an alkyl group, cycloalkyl group, or aryl group. k5 represents an integer of 1 or more. * represents a bond position. 【Transformation 5】 In the general formula (AL2), L Ｎ７ k6 represents an alkyl group, cycloalkyl group, or aryl group. k6 represents an integer of 1 or more. * represents a bond position.

5. L in the above general formula (N3) Ｎ４ The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the single bond represents a carbonyl group, an oxygen atom, or an amino group.

6. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) further comprises at least one of a repeating unit having a phenolic hydroxyl group and a repeating unit having a lactone structure, which are different from the repeating unit represented by the general formula (N1).

7. (C) The photosensitive or radiation-sensitive resin composition according to claim 1, comprising a compound that decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability.

8. The photosensitive or radiation-sensitive resin composition according to claim 7, wherein compound (B) is the same compound as compound (C), and is compound (D) that generates acid upon irradiation with active light or radiation and decomposes upon irradiation with active light or radiation, thereby reducing its acid-scavenging ability.

9. Furthermore, the photosensitive or radiation-sensitive resin composition according to claim 8, further comprising at least one of the compound (B) other than compound (D) and the compound (C) other than compound (D).

10. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 9.

11. A step of forming a photosensitive or radiation-sensitive film on a substrate using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 9, A step of exposing the aforementioned photosensitive or radiation-sensitive film, A pattern forming method comprising the steps of developing the exposed photosensitive or radiation-sensitive film using a developing solution to form a pattern.

12. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 11.

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