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

Abstract

Provided are: an active ray-sensitive or radiation-sensitive resin composition containing a resin (A) comprising repeating units (i) represented by a specific general formula, repeating units (ii) that have a cyano group and a lactone structure, and repeating units (iii) that have a phenolic hydroxyl group, wherein the content of repeating units that have an acid-degradable group in resin (A) is at least 35 mol% with respect to all of the repeating units in resin (A); an active ray-sensitive or radiation-sensitive resin film formed from said active-ray-sensitive or radiation-sensitive resin composition; and a pattern formation method and electronic device production method that use said active ray-sensitive or radiation-sensitive resin composition. Based on the aforementioned, an active-ray-sensitive or radiation-sensitive resin composition, etc. are provided with which it is possible to inhibit the occurrence of defects in the formation of ultrafine patterns and which have excellent roughness performance.

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) lasers in addition to ArF excimer lasers during exposure, and the development of photosensitive or radiation-sensitive resin compositions suitable for EUV exposure has been undertaken.

[0003] In the formation of resist patterns using EUV (wavelength 13.5 nm) or electron beams for the purpose of creating fine patterns, the requirements for various performance aspects are more stringent than when using conventional ArF (wavelength 193 nm) light, etc.

[0004] For example, Patent Document 1 describes a photosensitive or radiation-sensitive resin composition comprising a resin containing repeating units that decompose upon irradiation with active light or radiation to generate acid anions in the side chains of the resin, and which contain at least two types of repeating units that decompose upon the action of an acid to generate alkali-soluble groups, and at least two types of repeating units that decompose upon the action of an acid to generate alkali-soluble groups. Patent Document 2 describes a photosensitive or radiation-sensitive resin composition comprising a resin containing specific repeating units that decompose upon the action of an acid and increase in polarity, and a compound having a specific structure that generates acid upon irradiation with active light or radiation. Patent Document 3 describes a resin having structural units with a specific structure, and a radiation-sensitive resin composition containing a radiation-sensitive acid generator. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2011-154216 [Patent Document 2] International Publication No. 2022 / 024929 [Patent Document 3] Japanese Patent Application Publication No. 2015-52769 [Overview of the project] [Problems that the invention aims to solve]

[0006] In recent years, with the miniaturization of patterns formed, such as those produced using EUV or electron beams, there has been a demand for further improvements in various performance aspects. In particular, there is room for improvement in defect suppression and roughness performance. In the case of line-and-space patterns, roughness performance includes, for example, line width roughness (LWR) performance.

[0007] The present invention aims to provide a photosensitive or radiation-sensitive resin composition that can suppress the occurrence of defects and has excellent roughness performance when forming extremely fine patterns (for example, line-and-space patterns with a line width of 35 nm or less, or hole patterns with a pore diameter of 35 nm or less), a photosensitive or radiation-sensitive resin film formed from the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. [Means for solving the problem]

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

[0009] [1] A photosensitive or radiation-sensitive resin composition containing a resin (A) comprising a repeating unit (i) represented by the following general formula (N-0), a repeating unit (ii) having a cyano group and a lactone structure, and a repeating unit (iii) having a phenolic hydroxyl group, A photosensitive or radiation-sensitive resin composition in which the content of the repeating unit having an acid-decomposable group in the resin (A) is 35 mol% or more based on all the repeating units in the resin (A).

[0010]

Chemical formula

[0011] In the general formula (N-0), X N1 represents a hydrogen atom, a halogen atom, a hydroxy group or an organic group. k represents 0 or 1. R N1 ~R N3 each independently represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. Two of R N1 ~R N3 may combine to form a ring. R N4 represents a halogen atom, a hydroxy group or an organic group. When a plurality of R N1 ~R N4 are present, the plurality of R N1 ~R N4 may be the same or different from each other. R N5 represents a hydrogen atom or an organic group. R N4 and R N5 may combine to form a ring. t1 represents an integer of 1 or more and (5 + 2k) or less. t2 represents an integer of 0 or more and (5 + 2k - t1) or less. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-1).

[0012]

Chemical formula

[0013] In general formula (N-1), X N1 , R N1 ~R N5 k, t1, and t2 are X in the general formula (N-0), respectively. N1 , R N1 ~R N5 , represents the same meaning as k, t1, and t2. [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-2).

[0014] [ka]

[0015] In general formula (N-2), X N1 , R N1 ~R N4 These are the X in the general formula (N-0), respectively. N1 , R N1 ~R N4 This has the same meaning. t3 represents an integer between 1 and 5 (inclusive). t4 represents an integer between 0 and 4 (inclusive). [4] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (ii) is a repeating unit represented by the following general formula (Q-1).

[0016] [ka]

[0017] In general formula (Q-1), X Q1 L represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. Q1 R represents a single bond or a divalent organic group. Q1 and R Q2 Each independently represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C1-C5 alkylthio group, or RQ1 and R Q2 The two are bonded together to represent a C1-C6 alkylene group, an ether bond, or a thioether bond, which may contain at least one oxygen atom and a sulfur atom. Q3 m1 represents a halogen atom, hydroxyl group, or organic group. m1 represents an integer from 1 to 6. m2 represents an integer from 0 to 5. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-3).

[0018] [ka]

[0019] In general formula (N-3), X N2 R represents a hydrogen atom, halogen atom, or methyl group. N6 represents a methyl group or an ethyl group. t5 represents 1 or 2. [6] The above resin (A) comprises a repeating unit represented by the following general formula (E-1) and is a photosensitive or radiation-sensitive resin composition according to any one of [1] to [5].

[0020] [ka]

[0021] In general formula (E-1), X E1 R represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. E1 ~R E3 Each of these independently represents a hydrocarbon group with 1 to 12 carbon atoms. E1 ~R E3 Two of them may combine to form a ring. E1 ~R E3 If the hydrocarbon group represented by includes an alkylene group, some of the alkylene groups may be replaced by an ether group, a thioether group, or a carbonyl group. [7] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the content of repeating units having acid-degradable groups in the resin (A) is 40 mol% or more relative to the total repeating units in the resin (A). [8] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the content of repeating units having acid-degradable groups in the resin (A) is 45 mol% or more relative to the total repeating units in the resin (A). [9] The above resin (A) comprises a repeating unit represented by the following general formula (E-2) and is a photosensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[0022] [ka]

[0023] In general formula (E-2), X E2 R represents a hydrogen atom, halogen atom, or methyl group. E4 represents a hydrocarbon group with 6 or fewer carbon atoms. u1 represents 1 or 2.

[10] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the molecular weight dispersion of the resin (A) is 1.70 or less.

[11] A photosensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , comprising an onium salt compound as a compound other than the resin (A) described above.

[12] A photosensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , containing a photoacid generator.

[13] The above R N1 ~R N3 A photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the total number of carbon atoms is 3 to 25.

[14] A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition described in any one of [1] to

[13] .

[15] 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

[13] , 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.

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

[15] . [Effects of the Invention]

[0024] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that can suppress the occurrence of defects in the formation of extremely fine patterns (for example, line-and-space patterns with a line width of 35 nm or less, or hole patterns with a pore diameter of 35 nm or less, etc.) and has excellent roughness performance, a photosensitive or radiation-sensitive resin film formed from the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. [Modes for carrying out the invention]

[0025] 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.

[0026] In this specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited 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:

[0027] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; and methyl Alkylsulfanil groups such as sulfanil groups and tert-butylsulfanil groups; arylsulfanil groups such as phenylsulfanil groups and p-tolylsulfanil groups; alkyl 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; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[0028] 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 and extreme ultraviolet light represented by excimer lasers, and X-rays, 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.

[0029] In this specification, the bonding direction of the divalent linking group 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-. The above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0030] 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 molecular weight dispersion (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).

[0031] 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).

[0032] pKa can also be determined by molecular orbital calculations. Specifically, based on the thermodynamic cycle, H in aqueous solution + 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.

[0033] 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. 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 (typically resist 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.

[0034] [Actinic ray-sensitive or radiation-sensitive resin composition] The following describes the photosensitive or radiation-sensitive resin compositions of the present invention. The photosensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is typically a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. It may also be a resist composition for alkaline development or a resist composition for organic solvent development. Furthermore, it may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is preferably a chemically amplified resist composition.

[0035] The present invention is a photosensitive or radiation-sensitive resin composition containing a resin (A) comprising a repeating unit (i) represented by the following general formula (N-0), a repeating unit (ii) having a cyano group and a lactone structure, and a repeating unit (iii) having a phenolic hydroxyl group, This is a photosensitive or radiation-sensitive resin composition in which the content of repeating units having acid-degradable groups in resin (A) is 35 mol% or more relative to the total repeating units in resin (A).

[0036] [ka]

[0037] In general formula (N-0), X N1 k represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. k represents 0 or 1. N1 ~R N3 Each of these independently represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. N1 ~R N3 Two of them may combine to form a ring. N4 R represents a halogen atom, a hydroxyl group, or an organic group. N1 ~R N4 If multiple R N1 ~R N4 These can be the same or different. N5 R represents a hydrogen atom or an organic group. N4and R N5 These elements may be joined to form a ring. t1 represents an integer between 1 and (5+2k), and t2 represents an integer between 0 and (5+2k-t1), inclusive.

[0038] First, the various components of the composition of the present invention will be described in detail.

[0039] <Resin (A)> The composition of the present invention contains a resin (A) comprising a repeating unit (i) represented by general formula (N-0), a repeating unit (ii) having a cyano group and a lactone structure, and a repeating unit (iii) having a phenolic hydroxyl group. Resin (A) is a resin that decomposes and becomes more polar when exposed to acid (also known as an "acid-degradable resin"). Resin (A) contains repeating units having groups that decompose and increase in polarity due to the action of acid (also called "acid-degradable groups"). 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 (a 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. Since resin (A) is an acid-degradable resin, in the pattern-forming method using the composition 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 developer is used as the developer, a negative-type pattern is suitably formed.

[0040] In resin (A), it is preferable that repeating unit (i), repeating unit (ii), and repeating unit (iii) are all different repeating units.

[0041] (Repeating unit (i)) The resin (A) contains repeating units (i) represented by the general formula (N-0). Repeating unit (i) is a repeating unit having an acid-degradable group, which decomposes upon the action of an acid and produces a phenolic hydroxyl group. Repeating unit (i) has higher elimination reactivity compared to repeating units derived from (meth)acrylic acid esters, which are commonly used as repeating units with acid-degradable groups. High elimination reactivity of repeating units with acid-degradable groups makes it easier to suppress the occurrence of defects. Furthermore, high elimination reactivity of repeating units with acid-degradable groups reduces fluctuations in elimination (deprotection) and improves roughness performance. Normally, to improve elimination reactivity, it is thought that the size of the leaving group should be increased, but repeating unit (i) has high elimination reactivity not due to the size of the leaving group, but due to the skeleton represented by the general formula (N-0), so it is not necessary to increase the size of the leaving group to improve elimination reactivity. The smaller the molecular weight of the leaving group, the higher the volatility of the eliminated product, which suppresses the residue of the eliminated product in the photosensitive or radiation-sensitive film, and can suppress the decrease in the Tg (glass transition temperature) of the photosensitive or radiation-sensitive film. The higher the Tg of a photosensitive or radiation-sensitive film, the more effectively acid diffusion can be suppressed. This is thought to reduce defects when forming extremely fine patterns and improve roughness performance. Furthermore, as will be described later, the composition of the present invention preferably contains a photoacid generator. In the repeating unit (i), the polar group generated by the elimination reaction is a phenolic hydroxyl group, and it has high compatibility with the photoacid generator. Therefore, it is considered that when the composition of the present invention contains a photoacid generator, defects when forming an extremely fine pattern can be further suppressed, and the roughness performance can be further improved.

[0042] In general formula (N-0), X N1 represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. X N1 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. X N1 The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., with alkyl groups being preferred.N1 The number of carbon atoms in the organic group represented by is preferably 1 to 10, and more preferably 1 to 5. N1 The organic group represented is preferably a methyl group. X N1 It is preferably a hydrogen atom, a fluorine atom, or a methyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0043] In the general formula (N-0), k represents either 0 or 1, with 0 being preferred. The aromatic ring described in the general formula (N-0) represents a benzene ring when k is 0, and a naphthalene ring when k is 1.

[0044] In general formula (N-0), R N1 ~R N3 Each of these independently represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. R N1 ~R N3 The alkyl group represented by may be linear or branched, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. Specifically, preferred alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and the like.

[0045] R N1 ~R N3 The cycloalkyl group represented by may be monocyclic or polycyclic, with a preferred cycloalkyl group having 5 to 12 carbon atoms, more preferred a cycloalkyl group having 5 to 10 carbon atoms, and particularly preferred a cycloalkyl group having 5 to 8 carbon atoms. Specifically, preferred cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups.

[0046] R N1 ~R N3 Two of them may join together to form a ring. R N1 ~R N3The ring formed by the combination of two of them is preferably an alicyclic ring, and preferably a monocyclic or polycyclic cycloalkane ring. R N1 ~R N3 The number of carbon atoms in the ring formed by the combination of two of them is preferably 3 to 20, more preferably 4 to 15, and particularly preferably 5 to 12. Specifically, as the above ring, a cyclopentane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. are preferable.

[0047] R N1 ~R N3 The total number of carbon atoms is preferably 3 to 25, more preferably 3 to 20, and particularly preferably 3 to 15.

[0048] R N1 ~R N3 The alkyl group and cycloalkyl group represented by, and R N1 ~R N3 The ring formed by the combination of two of them may have a substituent. Examples of the substituent include the aforementioned substituent T. R N1 ~R N3 When representing an alkyl group or a cycloalkyl group having a substituent, the number of carbon atoms including the substituent is preferably within the above range. R N1 ~R N3 When the ring formed by the combination of two of them has a substituent, the number of carbon atoms including the substituent is preferably within the above range. <\(0000667\)><\(0000668\)>In the general formula (N-0), R <\(0000089\)>represents a halogen atom, a hydroxy group or an organic group. <\(0000669\)>R<\(0000090\)>The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable. <\(0000670\)>R<\(0000091\)>The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., and an alkyl group is preferable. R <\(0000092\)>The number of carbon atoms in the organic group represented by is preferably 1 to 10, and more preferably 1 to 5. <\(0000671\)>

[0050] In the general formula (N-0), R N5 represents a hydrogen atom or an organic group. The organic group represented by R N5 is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., and an alkyl group is preferred. The carbon number of the organic group represented by R N5 is preferably 1 to 10, more preferably 1 to 5. R N5 preferably represents a hydrogen atom. R N4 and R N5 may combine to form a ring.

[0051] In the general formula (N-0), t1 represents an integer of 1 or more and (5 + 2k) or less, preferably represents an integer of 1 or more and 5 or less, more preferably represents an integer of 1 or more and 3 or less, particularly preferably represents 1 or 2, and most preferably represents 1. t2 represents an integer of 0 or more and (5 + 2k - t1) or less, preferably represents an integer of 0 or more and 4 or less, more preferably represents an integer of 0 or more and 2 or less, particularly preferably represents 0 or 1, and most preferably represents 0.

[0052] The repeating unit (i) is preferably a repeating unit represented by the following general formula (N-1).

[0053]

Chemical formula

[0054] In the general formula (N-1), X N1 , R N1 ~R N5 , k, t1 and t2 respectively represent the same meanings as X N1 , R N1 ~R N5 in the general formula (N-0), k, t1 and t2.

[0055] In the general formula (N-1), X N1 , R N1 ~R N5k, t1, and t2 are X in the general formula (N-0), respectively. N1 , R N1 ~R N5 , k, t1 and t2 have the same meaning, and the preferred range and specific examples are also the same.

[0056] The repeating unit (i) is more preferably a repeating unit represented by the following general formula (N-2).

[0057] [ka]

[0058] In general formula (N-2), X N1 , R N1 ~R N4 These are the X in the general formula (N-0), respectively. N1 , R N1 ~R N4 This has the same meaning. t3 represents an integer between 1 and 5 (inclusive). t4 represents an integer between 0 and 4 (inclusive).

[0059] In general formula (N-2), X N1 , R N1 ~R N4 These are the X in the general formula (N-0), respectively. N1 , R N1 ~R N4 It expresses the same meaning, and the preferred range and specific examples are also the same. t3 represents an integer between 1 and 5, preferably between 1 and 3, more preferably between 1 and 2, and most preferably between 1. t4 represents an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1, and most preferably 0.

[0060] The repeating unit (i) is more preferably a repeating unit represented by the following general formula (N-3).

[0061] [ka]

[0062] In general formula (N-3), X N2 R represents a hydrogen atom, halogen atom, or methyl group. N6 represents a methyl group or an ethyl group. t5 represents 1 or 2.

[0063] X in general formula (N-3) N2 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. In the general formula (N-3), t5 represents either 1 or 2, and it is preferable that it represents 1.

[0064] Specific examples of monomers that provide a repeating unit (i) (monomers corresponding to repeating unit (i)) are shown below, but are not limited to these.

[0065] [ka]

[0066] The resin (A) may contain one or more types of repeating units (i).

[0067] The content of repeating unit (i) is not particularly limited. The content of repeating units (i) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units (i) is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less, relative to the total repeating units in resin (A).

[0068] (Repeating unit (ii)) The resin (A) contains repeating units (ii) having cyano groups and lactone structures. Since the repeating unit (ii) has a ring structure, the Tg of the photosensitive or radiation-sensitive film formed from the composition of the present invention can be increased. The higher the Tg of the photosensitive or radiation-sensitive film, the more the diffusion of acid can be suppressed, which is thought to suppress defects when forming extremely fine patterns and also improve roughness performance. Furthermore, as will be described later, the composition of the present invention preferably contains a photoacid generator, and since the repeating unit (ii) has a lactone structure which is a hydrophilic structure, it has high compatibility with the photoacid generator. Therefore, it is thought that when the composition of the present invention contains a photoacid generator, defects when forming an extremely fine pattern can be further suppressed and the roughness performance can be further improved. Furthermore, since the repeating unit (ii) has a cyano group, it is thought that the effect of increasing the Tg of the above-mentioned photosensitive or radiation-sensitive film and the effect of improving compatibility with the above-mentioned photoacid generator are enhanced, further suppressing defects when forming an extremely fine pattern and further improving roughness performance.

[0069] The repeating unit (ii) is preferably a repeating unit represented by the following general formula (Q-1).

[0070] [ka]

[0071] In general formula (Q-1), X Q1 L represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. Q1 R represents a single bond or a divalent organic group. Q1 and R Q2 Each independently represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C1-C5 alkylthio group, or R Q1 and R Q2 The two are bonded together to represent a C1-C6 alkylene group, an ether bond, or a thioether bond, which may contain at least one oxygen atom and a sulfur atom. Q3m1 represents a halogen atom, hydroxyl group, or organic group. m1 represents an integer from 1 to 6. m2 represents an integer from 0 to 5.

[0072] In general formula (Q-1), X Q1 represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. X Q1 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. X Q1 The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., with alkyl groups being preferred. Q1 The number of carbon atoms in the organic group represented by is preferably 1 to 10, and more preferably 1 to 5. N1 The organic group represented is preferably a methyl group. X Q1 It is preferably a hydrogen atom, a fluorine atom, or a methyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0073] In general formula (Q-1), L Q1 The symbol represents a single bond or a divalent organic group. L Q1 The divalent organic groups represented by include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and -Rt Q1 -COO-, -Rt Q1 -O- and others are examples. Rt Q1 Rt represents an alkylene group or a cycloalkylene group. Q1 The alkylene group having 1 to 5 carbon atoms is preferred, and -CH2-, -(CH2)2-, or -(CH2)3- is more preferred. L Q1 is a single bond or -Rt Q1 -COO- groups are preferred.

[0074] In general formula (Q-1), R Q1 and R Q2 Each independently represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C1-C5 alkylthio group, or RQ1 and R Q2 The two atoms are bonded together to represent a C1-C6 alkylene group, an ether bond, or a thioether bond, which may contain at least one oxygen atom and a sulfur atom. R Q1 and R Q2 The alkyl group having 1 to 5 carbon atoms represented by may be linear or branched, with alkyl groups having 1 to 3 carbon atoms being preferred, and methyl or ethyl groups being more preferred. Specifically, preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. R Q1 and R Q2 The alkoxy group having 1 to 5 carbon atoms represented by is preferably linear or branched, and a alkoxy group having 1 to 3 carbon atoms is preferred. Specific examples of alkoxy groups include methoxy groups and ethoxy groups. R Q1 and R Q2 The alkylthio group having 1 to 5 carbon atoms represented by is preferably linear or branched, and an alkylthio group having 1 to 3 carbon atoms is preferred. Specific examples of alkylthio groups include methylthio groups and ethylthio groups.

[0075] R Q1 and R Q2 When these groups combine to form an alkylene group, the alkylene group has 1 to 6 carbon atoms, preferably 1 to 5, and more preferably 1 to 3. Specific examples of alkylene groups include methylene groups and ethylene groups. R Q1 and R Q2 When these are combined to represent an alkylene group, the alkylene group may contain at least one of an oxygen atom and a sulfur atom. For example, the alkylene group may have an ether bond or a thioether bond in the chain or at its end. R Q1 and R Q2 These two elements may combine to form an ether bond or a thioether bond.

[0076] R Q1 and R Q2The alkyl group, alkoxy group and alkylthio group represented by, and R Q1 and R Q2 The alkylene group formed by the bonding of these two components may have substituents. Examples of substituents include the substituent T mentioned above. R Q1 and R Q2 When R represents a substituted alkyl group, a substituted alkoxy group, or a substituted alkylthio group, it is preferable that the number of carbon atoms, including the substituent, is within the above range. Q1 and R Q2 When the alkylene group formed by the bonding of these atoms has substituents, it is preferable that the number of carbon atoms, including the substituents, is within the above range.

[0077] In general formula (Q-1), R Q3 represents a halogen atom, a hydroxyl group, or an organic group. R Q3 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. R Q3 The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., with alkyl groups being preferred. Q3 The number of carbon atoms in the organic group represented by is preferably 1 to 10, and more preferably 1 to 5. Q3 The organic group represented is preferably a methyl group.

[0078] In the general formula (Q-1), m1 represents an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably 1 or 2. In the general formula (Q-1), m2 represents an integer between 0 and 5, preferably an integer between 0 and 3, and more preferably 0 or 1.

[0079] Specific examples of monomers that provide a repeating unit (ii) (monomers corresponding to repeating unit (ii)) are shown below, but are not limited to these.

[0080] [ka]

[0081] The resin (A) may contain one or more types of repeating units (ii).

[0082] The content of repeating units (ii) is not particularly limited. The content of repeating units (ii) is preferably 3 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 content of repeating units (ii) is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, and particularly preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0083] (Repeating unit (iii)) The resin (A) contains repeating units (iii) having phenolic hydroxyl groups. Since the repeating unit (iii) has a phenolic hydroxyl group, the Tg of the photosensitive or radiation-sensitive film formed from the composition of the present invention can be increased. The higher the Tg of the photosensitive or radiation-sensitive film, the more the diffusion of acid can be suppressed, which is thought to suppress defects when forming extremely fine patterns and also improve roughness performance. Furthermore, as will be described later, the composition of the present invention preferably contains a photoacid generator, and since the repeating unit (iii) has a phenolic hydroxyl group, it has high compatibility with the photoacid generator. Therefore, it is considered that when the composition of the present invention contains a photoacid generator, defects when forming extremely fine patterns can be further suppressed and roughness performance can be further improved. Furthermore, the phenolic hydroxyl group of the repeating unit (iii) is thought to enhance the elimination reactivity of the acid-degradable group due to its role as a proton source and its hydrophilic properties. Higher elimination reactivity of the acid-degradable group makes it easier to suppress the occurrence of defects. In addition, higher elimination reactivity of the acid-degradable group reduces fluctuations in elimination (deprotection), improving roughness performance.

[0084] As the repeating unit (iii), the repeating unit represented by the following general formula (G-1) is preferred.

[0085] [ka]

[0086] In general formula (G-1), X G1 represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. q represents 0 or 1. R G1 R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or aryloxycarbonyl group. G1 If multiple R G1 They can be the same or different. G2 L represents a hydrogen atom or an organic group. G1 represents a single bond or a divalent linking group. j1 represents an integer between 1 and (5+2q) inclusive. j2 represents an integer between 0 and (5+2q-j1) inclusive.

[0087] In general formula (G-1), X G1 The symbol represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. X G1 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. X G1 The alkyl group represented by may be linear or branched, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. X G1 The cycloalkyl group represented by may be monocyclic or polycyclic, with a preferred cycloalkyl group having 5 to 12 carbon atoms, a more preferred cycloalkyl group having 5 to 10 carbon atoms, and a particularly preferred cycloalkyl group having 5 to 8 carbon atoms. X G1It is preferably a hydrogen atom, a fluorine atom, or a methyl group, and more preferably a hydrogen atom or a methyl group.

[0088] In general formula (G-1), q represents 0 or 1, with 0 being preferred. The aromatic ring described in general formula (G-1) represents a benzene ring when q is 0, and a naphthalene ring when q is 1.

[0089] In general formula (G-1), R G1 represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or aryloxycarbonyl group. R G1 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine or iodine atoms being preferred. R G1 The alkyl group, alkoxy group, and alkylsulfonyloxy group represented by may be linear or branched, and preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. R G1 The alkenyl group, alkylcarbonyloxy group, and alkyloxycarbonyl group represented by may be linear or branched, and preferably have 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. R G1 The cycloalkyl group represented by may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 5 to 15. R G1 The aryl group, aralkyl group, and aryloxycarbonyl group represented by may be monocyclic or polycyclic, and preferably have 6 to 20 carbon atoms, more preferably 6 to 15.

[0090] In general formula (G-1), R G2 represents a hydrogen atom or an organic group. R G2The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., with alkyl groups being preferred. G2 The number of carbon atoms in the organic group represented is preferably 1 to 10, and more preferably 1 to 5. R G2 It is preferable that this represents a hydrogen atom.

[0091] In general formula (G-1), L G1 represents a single bond or a divalent linking group. L G1 The divalent linking groups represented by include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and -Rt G1 -COO-, -Rt G1 -O- and others are examples. Rt G1 Rt represents a single bond, an alkylene group, or a cycloalkylene group. G1 The material is preferably a single bond or an alkylene group having 1 to 5 carbon atoms. L G1 is a single bond or -Rt Q1 -COO- groups are preferred, and single bonds are more preferred.

[0092] In the general formula (G-1), j1 represents an integer between 1 and (5+2q), preferably an integer between 1 and 5, more preferably an integer between 1 and 3, particularly preferably 1 or 2, and most preferably 1. j2 represents an integer between 0 and (5 + 2q - j1), preferably between 0 and 4, more preferably between 0 and 2, particularly preferably between 0 and 1, and most preferably between 0.

[0093] The repeating unit (iii) is preferably a repeating unit represented by the following general formula (G-2).

[0094] [ka]

[0095] In general formula (G-2), X G1and R G1 each represents X in general formula (G-1) G1 and R G1 and have the same meanings. j3 represents an integer of 1 or more and 3 or less. j4 represents an integer of 0 or more and (5 - j3) or less.

[0096] In general formula (G-2), X G1 and R G1 each represents X in general formula (G-1) G1 and R G1 and have the same meanings, and the preferred ranges and specific examples are also the same. j3 represents an integer of 1 or more and 3 or less, more preferably represents 1 or 2, and most preferably represents 1. j4 represents an integer of 0 or more and (5 - j3) or less, more preferably represents 0 or 1, and most preferably represents 0.

[0097] Specific examples of the monomer (the monomer corresponding to repeating unit (iii)) that gives repeating unit (iii) are shown below, but are not limited thereto.

[0098]

Chemical formula

[0099] The type of repeating unit (iii) contained in resin (A) may be 1 type or 2 or more types.

[0100] The content of repeating unit (iii) is not particularly limited. The content of repeating unit (iii) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more with respect to all the repeating units in resin (A). Also, the content of repeating unit (iii) is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less with respect to all the repeating units in resin (A).

[0101] The resin (A) may contain, in addition to the repeating units (i), (ii), and (iii) described above, yet another repeating unit.

[0102] The aromatic ring of repeating unit (i), the phenolic hydroxyl group generated by the elimination reaction of repeating unit (i), the cyano group and lactone structure of repeating unit (ii), and the phenolic hydroxyl group of repeating unit (iii) interact to form a resin film that is resistant to acid diffusion. This is thought to suppress defects when forming extremely fine patterns and improve roughness performance. Furthermore, as mentioned above, the repeating units with acid-degradable groups in resin (A) also contribute to the interaction, and the effect is superior when the content of repeating units with acid-degradable groups is 35 mol% or more.

[0103] Furthermore, as will be described later, the composition of the present invention preferably contains a photoacid generator, and it is believed that the aromatic ring of repeating unit (i), the cyano group and lactone structure of repeating unit (ii), and the phenolic hydroxyl group of repeating unit (iii) interact with each other and become compatible with the photoacid generator. Therefore, it is believed that when the composition of the present invention contains a photoacid generator, defects when forming extremely fine patterns can be further suppressed and roughness performance can be further improved.

[0104] (Repeat unit (iv)) The resin (A) may contain repeating units having acid-degradable groups different from the repeating unit (i) described above (also called "repeating unit (iv)"). An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, an acid-degradable group has a structure in which the polar group is protected by a leaving group (a group that is eliminated by the action of an acid). 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, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0105] Examples of groups that are eliminated by the action of an acid include those 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)

[0106] 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 by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by 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 resist composition for EUV lithography, it is 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.

[0107] 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. 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 resist composition for EUV lithography, 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.

[0108] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0109] [ka]

[0110] 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 optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced by a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It is preferable that 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 combining an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5 - or 6 - membered ring). In terms of pattern miniaturization, it is preferable that L2 is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of the tertiary alkyl group include a tert - butyl group and an adamantane group. In these embodiments, since the Tg (glass transition temperature) and the activation energy are high, in addition to ensuring the film strength, it is possible to suppress blooming.

[0111] If the composition of the present invention is, for example, a resist composition for EUV lithography, then the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by L1 and L2 may further preferably have a fluorine atom or an iodine atom as a substituent. In addition to fluorine atoms and iodine atoms, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may also preferably contain heteroatoms such as oxygen atoms. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. If the composition of the present invention is, for example, an EUV lithography resist composition, then 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 in the groups which are combinations thereof, the heteroatom is preferably 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.

[0112] 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 resist composition for EUV lithography, 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.

[0113] 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.

[0114] Other groups that may be removed by the action of an acid 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.

[0115] As the repeating unit (iv), the repeating unit represented by formula (AI) is also preferred.

[0116] [ka]

[0117] 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).

[0118] 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. 11 R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. 11 Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. For Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0119] 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.

[0120] 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.

[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 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).

[0123] The repeating unit (iv) is preferably the repeating unit represented by the following general formula (E-1). A preferred embodiment of resin (A) is one which includes repeating units represented by the following general formula (E-1).

[0124] [ka]

[0125] In general formula (E-1), X E1 R represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. E1 ~R E3 Each of these independently represents a hydrocarbon group with 1 to 12 carbon atoms. E1 ~R E3 Two of them may combine to form a ring. E1 ~R E3 If the hydrocarbon group represented by includes an alkylene group, some of the alkylene groups may be replaced by an ether group, a thioether group, or a carbonyl group.

[0126] In general formula (E-1), X E1 represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. X E1 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. X E1 The organic group represented by is, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, etc., with alkyl groups being preferred. N1 The number of carbon atoms in the organic group represented by is preferably 1 to 10, and more preferably 1 to 6. E1 The organic group represented is preferably a methyl group. X E1 It is preferably a hydrogen atom, a fluorine atom, or a methyl group, and more preferably a hydrogen atom or a methyl group.

[0127] In general formula (E-1), R E1 ~R E3 Each of these independently represents a hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group is preferably 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). R E1 ~R E3 Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. R E1 ~R E3 Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. R E1 ~R E3 The preferred aryl group is one having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. R E1 ~R E3 A vinyl group is preferred as the alkenyl group.

[0128] R E1 ~RE3 Two of them may join together to form a ring. R E1 ~R E3 The ring formed by the bonding of two of these rings is preferably an alicyclic ring, and preferably a monocyclic or polycyclic cycloalkane ring. R E1 ~R E3 The number of carbon atoms in the ring formed by the bonding of two of these atoms is preferably 3 to 20, more preferably 4 to 15, and particularly preferably 5 to 12. Specifically, preferred rings include cyclopentane rings, cyclohexane rings, norbornane rings, adamantane rings, and the like.

[0129] R E1 ~R E3 The hydrocarbon group represented by, and R E1 ~R E3 The ring formed by the bonding of two of these elements may have substituents. Examples of substituents include the substituent T mentioned above. 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. R E1 ~R E3 When R represents a hydrocarbon group having substituents, it is preferable that the number of carbon atoms, including the substituents, is within the above range. E1 ~R E3 If the ring formed by the bonding of two of these atoms has substituents, it is preferable that the number of carbon atoms, including the substituents, is within the above range.

[0130] As the repeating unit (iv), the repeating unit represented by the following general formula (E-2) is also preferred. A preferred embodiment of resin (A) is one which includes repeating units represented by the following general formula (E-2).

[0131] [ka]

[0132] In general formula (E-2), X E2 R represents a hydrogen atom, halogen atom, or methyl group. E4 represents a hydrocarbon group with 6 or fewer carbon atoms. u1 represents 1 or 2.

[0133] In general formula (E-2), X E2 X represents a hydrogen atom, a halogen atom, or a methyl group. E2 The halogen atom represented by is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine being preferred. X E2 It is preferably a hydrogen atom, a fluorine atom, or a methyl group, and more preferably a hydrogen atom or a methyl group.

[0134] In general formula (E-2), R E4 represents a hydrocarbon group having 6 or fewer carbon atoms. The hydrocarbon group is preferably an alkyl group (linear or branched), a cycloalkyl group, an alkenyl group (linear or branched), or a phenyl group. R E4 Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. R E4 As the cycloalkyl group, a cyclopentyl group or a cyclohexyl group is preferred. R E4 A vinyl group is preferred as the alkenyl group.

[0135] R E4 The hydrocarbon group represented by may have substituents. Examples of substituents include the substituent T mentioned above. 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 5 carbon atoms). R E4 When R represents a hydrocarbon group having substituents, it is preferable that the number of carbon atoms, including the substituents, is within the above range. E1 ~R E3If the ring formed by the bonding of two of these atoms has substituents, it is preferable that the number of carbon atoms, including the substituents, is within the above range.

[0136] Specific examples of monomers that provide a repeating unit (iv) (monomers corresponding to repeating unit (iv)) are shown below, but are not limited to these.

[0137] [ka]

[0138] [ka]

[0139] If resin (A) contains repeating units (iv), the number of repeating units (iv) contained in resin (A) may be one or more.

[0140] If resin (A) contains repeating units (iv), the content of repeating units (iv) is not particularly limited. If the resin (A) contains repeating units (iv), the content of repeating units (iv) is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in the resin (A). Furthermore, if the resin (A) contains repeating units (iv), the content of repeating units (iv) is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less, relative to the total repeating units in the resin (A). The resin (A) does not have to contain repeating units (iv). That is, the content of repeating units (iv) may be 0 mol% relative to the total number of repeating units in the resin (A).

[0141] The content of repeating units having acid-degradable groups in resin (A) (total content of repeating units (i) and (iv)) is 35 mol% or more, preferably 40 mol% or more, and particularly preferably 45 mol% or more, relative to the total number of repeating units in resin (A). The solubility contrast increases as the content of repeating units with acid-degradable groups increases. Since repeating unit (i) tends to have relatively low solubility contrast during the elimination reaction, its content should be 35 mol% or more. In particular, when forming extremely fine patterns, a high solubility contrast is required, so the content of repeating unit (i) should be 35 mol% or more. Furthermore, resin (A) has a repeating unit (i) content of 35 mol% or more, and also contains repeating units (ii) having cyano groups and lactone structures, and repeating units (iii) having phenolic hydroxyl groups. This optimally adjusts the solubility before the elimination reaction, and the solubility changes significantly when the leaving group is eliminated, resulting in a high solubility contrast. The content of repeating units having acid-degradable groups in resin (A) is preferably 90% or less, and more preferably 80% or less, relative to the total number of repeating units in resin (A).

[0142] (Repeating units containing acidic groups) The resin (A) may further have repeating units (also called "repeating unit (v)") that have acid groups different from the repeating unit (iii) described above. 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 acidic groups include, for example, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. The hexafluoroisopropanol group described above may have one or more fluorine atoms (preferably one to two) 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 the polar group is protected by a group that is removed by the action of the aforementioned acid, 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.

[0143] Examples of repeating units having an acidic group include the following:

[0144] [ka]

[0145] If the resin (A) contains repeating units (v), the number of repeating units (v) contained in the resin (A) may be one or more.

[0146] If resin (A) contains repeating units (v), the content of repeating units (v) is not particularly limited. If the resin (A) contains repeating units (v), the content of repeating units (v) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the total repeating units in the resin (A). Furthermore, if the resin (A) contains repeating units (v), the content of repeating units (v) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in the resin (A). The resin (A) does not have to contain repeating units (v). That is, the content of repeating units (v) may be 0 mol% relative to the total number of repeating units in the resin (A).

[0147] (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) is a repeating unit different from the repeating units (i) to (v) described above, and may have a repeating unit (hereinafter also referred to as "unit X") that does not have either an acid-degradable group or an acid group, but has a fluorine atom, a bromine atom, or an iodine atom. The repeating unit referred to here, which does not have either an acid-degradable group or an acid group, but has a fluorine atom, a bromine atom, or an iodine atom, is preferably different from other types of repeating units such as the repeating units having a lactone group, a sultone group, or a carbonate group, and the repeating units having a photoacid-generating group, as described later.

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

[0149] [ka]

[0150] 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.

[0151] Examples of repeating units having fluorine or iodine atoms are shown below.

[0152] [ka]

[0153] 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).

[0154] 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.

[0155] (Repeating units having a lactone group, sultone group, or carbonate group) Resin (A) is a repeating unit different from the repeating unit (ii) described above, and may have a repeating unit (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 a hydroxyl group and a hexafluoropropanol group.

[0156] 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), and the lactone groups or sultone groups may be directly bonded to the main chain. For example, the ring member atoms of the lactone groups or sultone groups may constitute the main chain of the resin (A).

[0157] [ka]

[0158] 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, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0159] 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).

[0160] [ka]

[0161] 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 linking 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).

[0162] 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.

[0163] 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.

[0164] [ka]

[0165] 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 linking 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.

[0166] If resin (A) contains unit Y, 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). Furthermore, the upper limit 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). Resin (A) does not have to contain unit Y. That is, the content of unit Y may be 0 mol% relative to the total repeating units in resin (A).

[0167] (Repeating unit having a 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 (also called a "photoacid generating group"). An example of a repeating unit having a photoacid-generating group is the repeating unit represented by formula (4).

[0168] [ka]

[0169] R 41L 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.

[0170] [ka]

[0171] 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.

[0172] When resin (A) contains repeating units having photoacid generating groups, 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). Resin (A) does not have to contain repeating units having photoacid generating groups. That is, the content of repeating units having photoacid generating groups may be 0 mol% relative to the total repeating units in resin (A).

[0173] (The repeating unit is represented by formula (V-1) or formula (V-2) below) The resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formulas (V-1) and (V-2) are preferably different from the repeating units described above.

[0174] [ka]

[0175] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R 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. n3 represents an integer between 0 and 6. n4 represents an integer between 0 and 4. X4 is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

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

[0176] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (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 are those described in paragraphs

[0085] and

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

[0177] (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 liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0178] (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.

[0179] [ka]

[0180] 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.

[0181] (Other repeating units) Furthermore, resin (A) may have other repeating units besides 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.

[0182] 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.

[0183] 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.

[0184] The molecular weight dispersion (Mw / Mn) of resin (A) is preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.70 or less, and particularly preferably 1.60 or less. When the molecular weight dispersion of resin (A) is 1.70 or less, variations in the solubility of resin (A) are suppressed, which can suppress defects, especially when forming extremely fine patterns, and also improve roughness performance. Furthermore, the molecular weight dispersion of resin (A) is usually 1.0 or higher, but may be 1.2 or higher.

[0185] The resin (A) contained in the composition of the present invention may be one type or two or more types. The content of resin (A) in the composition of the present invention is preferably 20.0 to 99.9% by mass, and more preferably 30.0 to 90.0% by mass, based on the total solid content of the composition of the present invention.

[0186] <Onium salt compounds> The composition of the present invention preferably contains an onium salt compound. A preferred embodiment of the composition of the present invention is one which contains an onium salt compound as a compound other than the resin (A) described above. Examples of onium salt compounds include photoacid generators and acid diffusion controllers, which will be discussed later.

[0187] <Photoacid Generator> The composition of the present invention preferably contains a photoacid generator (also referred to as "photoacid generator (B)" or "compound (B)"). Photoacid generators are compounds that generate acid upon irradiation with active light or radiation. The pKa of the acid generated from the photoacid generator (B) is not particularly limited, but is preferably -12 to 1, and more preferably -12 to -2. The acid generated from the photoacid generator (B) typically reacts with the acid-degradable groups of the resin (A). The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Alternatively, both the low molecular weight compound form and the polymer-integrated form may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, 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. The lower limit is not particularly limited, but may be, for example, 100 or more. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). The photoacid generator (B) is preferably a different compound from the resin (A). The photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0188] The photoacid generator (B) is preferably an onium salt compound, for example, "M + X - Examples include compounds represented by '' (onium salt compounds), 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.

[0189] "M + X -In the compound represented by ", M + This represents an organic cation. The organic cation is not particularly limited. The valency of the organic cation may be 1 or 2 or more. 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.

[0190] [ka]

[0191] In the above equation (ZaI), R 201 , 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. 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-.

[0192] A preferred embodiment of the organic cation in formula (ZaI) is the cation (ZaI-1), which will be described later.

[0193] 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 R201 ~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. 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.

[0194] 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.

[0195] R 201 ~R 203 Preferred 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. The above substituents may also preferably 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 group that is eliminated by the action of an acid. The polar group and leaving group are as described above.

[0196] 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 205The 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).

[0197] 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.

[0198] "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.

[0199] 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.

[0200] 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).

[0201] 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.

[0202] 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).

[0203] 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.

[0204] An example of a sulfonylimid anion is the saccharin anion.

[0205] 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.

[0206] The photoacid generator is preferably at least one selected from the group consisting of compounds (I) to (II).

[0207] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural part X: Anion part A1 - and cation site M1 + It consists of the above, and upon irradiation with active light or radiation, it forms a structural site that forms a first acidic site represented by HA1. Structural site Y: Anionic site A2 -and cation site M2 + It consists of the above, and upon irradiation with active light or radiation, a structural site which forms a second acidic site represented by HA2. The above compound (I) satisfies the following condition I.

[0208] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation portion M2 in the structural portion Y + to H + The compound PI obtained by replacing the above structural site X is the above cation site M1 + to H + The acid dissociation constant a1 derived from the acidic site represented by HA1, which is replaced by the above-mentioned cation site M2 in the above-mentioned structural site Y + to H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, which is replaced by the above acid dissociation constant a1, and the above acid dissociation constant a2 is greater than the above acid dissociation constant a1.

[0209] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having HA1 and HA2". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of the compound having the above characteristics is the acid dissociation constant a2.

[0210] When the compound (I) is a compound that generates an acid having, for example, two of the above-mentioned first acidic sites derived from the above structural site X and one of the above-mentioned second acidic sites derived from the above structural site Y, the compound PI corresponds to "a compound having two HA1s and one HA2". When the acid dissociation constant of the compound PI is determined, when the compound PI becomes "a compound having one A1 - and one HA1 and one HA2", the acid dissociation constant, and "one A1 - and one HA1 and one HA2" becomes "two A1s - and one HA2", the acid dissociation constant corresponds to the above-mentioned acid dissociation constant a1. "Two A1s - and one HA2" becomes "two A1s - and A2 - When the acid dissociation constant when it becomes "a compound having" corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 in which the cation site M1 + [[ID=1 or 16]]in the above structural site X is replaced by H + , the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. Incidentally, when the acid dissociation constant when the compound PI becomes "a compound having one A1 - and one HA1 and one HA2" is aa, and "one A1 - and one HA1 and one HA2" becomes "two A1s - and one HA2", when the acid dissociation constant is ab, the relationship between aa and ab satisfies aa <ab.

[0211] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-described method for measuring the acid dissociation constant. [[ID=()]] The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1s - , and two or more of the above M1s +These may be the same or different. In compound (I), the above A1 - and A2 above - , and the above M1 + and M2 above + These may be the same or different, but as mentioned above, A1 - and A2 above - It is preferable that they are all different.

[0212] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or greater, more preferably 0.5 or greater, and even more preferably 1.0 or greater. There is no particular upper limit to the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2, but for example, it is 16 or less.

[0213] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0214] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0215] Anion part A1 - and anion part A2 - This refers to a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion part A1 - Preferably, the acidic site can form an acidic site with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion part A2 - For example, Anion part A1- It is preferable that the material can form an acidic site with a larger acid dissociation constant than the other material, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), R A R represents a monovalent organic group. A The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0216] [ka]

[0217] [ka]

[0218] Cation site M1 + and cation site M2 + This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. + Examples of organic cations represented by the following are given.

[0219] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids.

[0220] Definition of structural site X in compound (II), and A1 - and M1 + The definition is the definition of structural site X in compound (I) described above, and A1- and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0221] In the above compound (II), the above cation moiety M1 in the above structural moiety X + to H + In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic moiety represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII corresponds to "one A1 - The acid dissociation constant when a compound having "one HA1" is formed, and "one A1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0222] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. - , and two or more of the above M1 + These may be the same or different.

[0223] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably, for example, a site that can electrostatically interact with a proton or a site that contains an electron-containing functional group. Examples of functional groups that can electrostatically interact with protons, or that have electrons, include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0224] [ka]

[0225] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0226] Specific examples of photoacid generators (B) are shown below, but are not limited to these.

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] [ka]

[0234] [ka]

[0235] [ka]

[0236] If the composition of the present invention contains a photoacid generator (B), the composition of the present invention may contain one type of photoacid generator (B) or two or more types. When the composition of the present invention contains a photoacid generator (B), the content of the photoacid generator (B) is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the composition of the present invention, on the grounds that the cross-sectional shape of the formed pattern becomes more rectangular. The content of the photoacid generator is preferably 50.0% by mass or less, and more preferably 40% by mass or less, relative to the total solid content of the composition of the present invention.

[0237] <Acid diffusion control agent> The composition of the present invention may contain an acid diffusion control agent (also referred to as "acid diffusion control agent (C)" or "compound (C)"). The acid diffusion control agent may also be an onium salt compound. The acid diffusion control agent is preferably a compound different from resin (A). Furthermore, the acid diffusion control agent (C) may be the same compound as the photoacid generator (B) mentioned above, or it may be a different compound. The acid diffusion control agent (C) can act as a quencher to trap the acid generated from photoacid generators, etc., during exposure, and to suppress the reaction of acid-degradable resins in unexposed areas due to excess generated acid. The type of acid diffusion control agent (C) is not particularly limited and includes, for example, basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation. Specific examples of basic compounds (CA) include, for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (CE) whose basicity is reduced or lost upon irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824 and those described in paragraph

[0164] of International Publication No. 2020 / 066824; and specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824. Specific examples of onium salt compounds (CDs) that are relatively weak acids with respect to photoacid generators include, for example, those described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337.

[0238] In addition to the above, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents.

[0239] Among acid diffusion control agents, the above compound (CC) is also called a photodecaying quencher. Acid diffusion control agents other than the above compound (CC) are also called non-photodecaying quenchers. The acid diffusion control agent (C) may be a photodecaying quencher or a non-photodecaying quencher. Alternatively, a combination of a photodecaying quencher and a non-photodecaying quencher may be used as the acid diffusion control agent (C).

[0240] If the composition of the present invention contains an acid diffusion control agent (C), the composition of the present invention may contain one type of acid diffusion control agent (C) or two or more types. When the composition of the present invention contains an acid diffusion control agent (C), the content of the acid diffusion control agent (C) is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass, relative to the total solid content of the composition of the present invention.

[0241] <Hydrophobic resin> The composition of the present invention may further contain a hydrophobic resin different from resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the photosensitive or radiation-sensitive film (preferably a resist film) formed from the composition of the present invention. However, unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does 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.

[0242] 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. 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.

[0243] Hydrophobic resins may be used individually or in combination of two or more types. 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 of the present invention.

[0244] <Surfactants> The composition of the present invention may contain a surfactant. The inclusion of a surfactant allows for 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 / 193954. Surfactants may be used individually or in combination of two or more types. 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, relative to the total solid content of the composition of the present invention.

[0245] <Solvent> The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, 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).

[0246] 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.

[0247] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0248] 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.

[0249] <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).

[0250] The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developing solutions.

[0251] The composition of the present invention is suitably used as a photosensitive composition for EUV exposure. 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.

[0252] [Method for forming patterns on photosensitive or radiation-sensitive films] The procedure for a pattern formation method using the composition of the present invention is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition. Step 2: Exposing the above-mentioned photosensitive or radiation-sensitive film. Step 3: Developing the exposed photosensitive or radiation-sensitive film using a developer. The following details the steps for each of the above processes.

[0253] (Step 1: Actinic ray-sensitive or radiation-sensitive film formation step) Step 1 is a step of forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition.

[0254] One method for forming a photosensitive or radiation-sensitive film (preferably a resist film) on a substrate using a photosensitive or radiation-sensitive resin composition is, for example, a method of coating the composition of the present invention onto a substrate. Furthermore, it is preferable to filter the composition of the present invention 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.

[0255] The composition of the present invention 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 (rotations per minute). After applying the composition of the present invention, the substrate may be dried to form a photosensitive or radiation-sensitive film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed beneath the photosensitive or radiation-sensitive film.

[0256] 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.

[0257] The thickness of the photosensitive or radiation-sensitive film is not particularly limited, but 10 to 120 nm is preferred in order to form finer patterns with higher precision. In particular, when using EUV exposure, 10 to 65 nm is more preferred for the thickness of the photosensitive or radiation-sensitive film, and 15 to 50 nm is even more preferred. When using ArF immersion exposure, 10 to 120 nm is more preferred for the thickness of the photosensitive or radiation-sensitive film, and 15 to 90 nm is even more preferred.

[0258] Furthermore, a topcoat may be formed on the upper layer of the photosensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition is not mixed with the photosensitive or radiation-sensitive film and can be uniformly applied to the upper layer of the photosensitive or radiation-sensitive film. The topcoat is not particularly limited, and conventionally known topcoats 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 photosensitive or radiation-sensitive film. Specific examples of basic compounds that the topcoat may contain include the basic compounds that may be included in the compositions of the present invention described above. The top coat may also preferably contain 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.

[0259] (Step 2: Exposure process) Step 2 is the step of exposing a photosensitive or radiation-sensitive film. One method of exposure is to irradiate the formed photosensitive or radiation-sensitive film with active 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, with wavelengths of 250 nm or less being preferred, more preferably 220 nm or less, and far ultraviolet light with wavelengths of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams being particularly preferred.

[0260] 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.

[0261] (Process 3: Development process) Step 3 is the process of developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0262] 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 letting it stand for a certain period of time (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.

[0263] 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 preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0264] 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.

[0265] 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.

[0266] (Other processes) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0267] 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 be added to the rinse solution.

[0268] 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 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.

[0269] The rinsing process is not particularly limited and can be performed in any way, for example, by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), by immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or by spraying rinsing solution onto the surface of the substrate (spray method). Furthermore, the pattern formation method may include a heating step (Post Bake) after the rinsing step. This step removes any developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of smoothing 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).

[0270] 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.

[0271] The compositions and various materials used in the pattern-forming methods of this specification (e.g., solvents, developers, rinses, anti-reflective coating compositions, topcoat 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.

[0272] 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.

[0273] 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 constituent materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0274] 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.

[0275] 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 polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating can be used.

[0276] [Manufacturing methods for electronic devices] This specification also relates to a method for manufacturing an electronic device, including the pattern forming method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic devices described herein include those mounted in electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0277] 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.

[0278] <Components of the resist composition> The components contained in the resist compositions used in the examples and comparative examples are shown below.

[0279] [Resin (A)] The resins A-1 to A-71 (acid-degradable resins) used in the preparation of the resist composition are shown in Tables 1 to 3 below. Resin A-1 was synthesized using the synthesis method described later (Synthesis Example 1). Resins A-2 to A-4 were synthesized using the synthesis methods described later (synthesis Examples 2 to 4). Other resins (A) were synthesized according to Synthesis Example 1. However, for resins (A) containing repeating units with some phenolic hydroxyl groups (Mb-2 to Mb-7, Mb-12 to Mb-15, Mb-17), resins were synthesized using precursors with protected phenolic hydroxyl groups, according to the synthesis methods for resins A-2 to A-4 (Synthesis Examples 2 to 4). As precursors for Mb-3 to Mb-7, Mb-12 to Mb-15, and Mb-17, Mb-3-i to Mb-7-i, Mb-12-i to Mb-15-i, and Mb-17-i were used. As a precursor for Mb-2, either Mb-2-i or Mb-2-ii was used. Furthermore, the resins A-1R to A-8R (acid-degradable resins) used in the preparation of the comparative resist compositions are shown in Table 3 below. Although resins A-1R to A-8R are not resin (A), they are listed in the resin (A) column in Table 7 below for convenience. In Tables 1-3, the molar ratio of each repeating unit indicates the content (mol%) of each repeating unit relative to the total number of repeating units. Each repeating unit is indicated by the structure of the monomer corresponding to that unit. In Tables 1-3, the "Mw" column indicates the weight-average molecular weight. In Tables 1-3, the "Mw / Mn" column indicates the degree of molecular weight dispersion. The weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The composition ratio (molar ratio) of the resin was also determined. 13 The measurement was performed using 1C-NMR (Nuclear Magnetic Resonance). In Tables 1-3, the "Total Molar Ratio of Acid-Degradable Groups (mol%)" column indicates the content of repeating units containing acid-degradable groups in each resin (the total content of repeating units (i) and (iv)).

[0280] [Table 1]

[0281] [Table 2]

[0282] [Table 3]

[0283] M-1 to M-13 are examples of monomers that provide the repeating unit (i), as previously listed. Ma-1 to Ma-3 are examples of monomers that provide the repeating unit (ii), as previously listed. Mb-1 to Mb-17 are examples of monomers that provide the repeating unit (iii), as previously listed. Mc-1 to Mc-36 are examples of monomers that provide a repeating unit (iv), as previously mentioned. The structures of Md-1 to Md-28 and Me-1 to Me-4 are shown below.

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] The structures of Mb-2-i, Mb-2-ii, Mb-3-i to Mb-7-i, Mb-12-i to Mb-15-i, and Mb-17-i are shown below.

[0288] [ka]

[0289] <Synthesis Example 1: Synthesis of Resin A-1> Cyclohexanone (39 g) was heated to 85°C under a nitrogen stream. To this solution, a mixed solution of cyclohexanone (7.5 g) and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (0.84 g) was added and stirred for 5 minutes. While stirring this solution, a mixed solution of monomer represented by the following formula M-1 (27.5 g), monomer represented by the following formula Ma-1 (32.2 g), monomer represented by the following formula Mb-1 (14 g), monomer represented by the following formula Mc-1 (26.3 g), cyclohexanone (187 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (8.4 g) was added dropwise over 6 hours to obtain the reaction solution. After the dropwise addition was complete, the reaction solution was stirred for a further 2 hours at 85°C. After the resulting reaction solution was allowed to cool, it was diluted with 167 g of ethyl acetate, reprecipitated with a large amount of n-heptane, filtered, and the resulting solid was vacuum-dried to obtain 75 g of resin A-1.

[0290] [ka]

[0291] The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-1, determined from the GPC (carrier: tetrahydrofuran (THF)), was 6500, and the degree of dispersion (Mw / Mn) was 1.60. 13 The composition ratio measured by 13C-NMR was 30 / 25 / 15 / 30 in molar ratio (ratio of repeating units, corresponding from left to right).

[0292] <Synthesis Example 2: Synthesis of Resin A-2> 44 g of cyclohexanone was heated to 85°C under a nitrogen stream. To this solution, a mixed solution of 3.1 g of cyclohexanone and 0.8 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added and stirred for 5 minutes. While stirring this solution, a mixed solution of 17 g of monomer represented by formula M-1, 17 g of monomer represented by formula Ma-1, 41 g of monomer represented by formula Mb-2-ii, 25 g of monomer represented by formula Mc-1, 187 g of cyclohexanone, and 7.9 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain the reaction solution. After the dropwise addition was complete, the reaction solution was stirred at 85°C for a further 2 hours to obtain resin A-2' solution.

[0293] [ka]

[0294] 3.6 g of 0.3 mol / L hydrochloric acid aqueous solution (HClaq) was added to resin A-2' solution and stirred at 40°C for 1 hour. 1560 g of ethyl acetate was added to the resulting reaction mixture, and liquid-liquid purification was performed five times with 1 L of distilled water. The organic layer was reprecipitated with a large amount of n-heptane / ethyl acetate mixed solution (mass ratio 9 / 1), filtered, and the resulting solid was vacuum-dried to obtain 78 g of resin A-2.

[0295] [ka]

[0296] The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-2, calculated from the GPC (carrier: tetrahydrofuran (THF)), was 7200, and the degree of dispersion (Mw / Mn) was 1.59. 13 The composition ratios measured by 13C-NMR were 18 / 13 / 40 / 29 in molar ratio (ratio of repeating units, corresponding from left to right).

[0297] <Synthesis Example 3: Synthesis of Resin A-3> 43 g of cyclohexanone was heated to 85°C under a nitrogen stream. To this solution, a mixed solution of 4.0 g of cyclohexanone and 0.4 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added and stirred for 5 minutes. While stirring this solution, a mixed solution of monomers represented by the following formula M-1 (17 g), monomers represented by the following formula Ma-1 (12.5 g), monomers represented by the following formula Mb-2-i (40 g), monomers represented by the following formula Mc-3 (30.5 g), 187 g of cyclohexanone, and 8.8 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain the reaction solution. After the dropwise addition was complete, the reaction solution was stirred at 85°C for a further 2 hours to obtain resin A-3' solution.

[0298] [ka]

[0299] Triethylamine (N(Et)3) (67g) and methanol (MeOH) (158g) were added to resin A-3' solution, and the mixture was stirred at 80°C for 15 hours under a nitrogen stream. After the resulting reaction mixture was allowed to cool, 0.2 mol / L hydrochloric acid aqueous solution (4L) was added and stirred, and then ethyl acetate (1570g) was added and stirred. After extracting the organic layer, liquid-liquid purification was performed once with 0.2 mol / L hydrochloric acid aqueous solution (0.5L) and five times with distilled water (1L). The obtained organic layer was reprecipitated with a large amount of n-heptane / ethyl acetate mixed solution (mass ratio 9 / 1), filtered, and the resulting solid was vacuum-dried to obtain 82g of resin A-3.

[0300] [ka]

[0301] The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-3, determined from the GPC (carrier: tetrahydrofuran (THF)), was 7000, and the degree of dispersion (Mw / Mn) was 1.58. 13The composition ratios measured by 13C-NMR were 18 / 9 / 45 / 28 in molar ratio (ratio of repeating units, corresponding from left to right).

[0302] <Synthesis Example 4: Synthesis of Resin A-4> 44 g of cyclohexanone was heated to 85°C under a nitrogen stream. To this solution, a mixed solution of 2.4 g of cyclohexanone and 0.58 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added and stirred for 5 minutes. While stirring this solution, a mixed solution of 14.9 g of monomer represented by the following formula M-1, 36.5 g of monomer represented by the following formula Ma-1, 25.8 g of monomer represented by the following formula Mb-6-i, 22.9 g of monomer represented by the following formula Mc-2, 187 g of cyclohexanone, and 5.8 g of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours to obtain the reaction solution. After the dropwise addition was complete, the reaction mixture was stirred at 85°C for a further 2 hours to obtain resin A-4' solution.

[0303] [ka]

[0304] Triethylamine (60 g) and methanol (94.5 g) were added to resin A-4' solution, and the mixture was stirred at 80°C for 3 hours under a nitrogen stream. After the resulting reaction solution was allowed to cool, 0.2 mol / L hydrochloric acid aqueous solution (3.6 L) was added and stirred, and then ethyl acetate (1570 g) was added and stirred. After extracting the organic layer, liquid-liquid purification was performed once with 0.2 mol / L hydrochloric acid aqueous solution (0.5 L) and five times with distilled water (1 L). The obtained organic layer was reprecipitated with a large amount of n-heptane / ethyl acetate mixed solution (mass ratio 9 / 1), filtered, and the resulting solid was vacuum-dried to obtain 75 g of resin A-4.

[0305] [ka]

[0306] The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-4, determined from the GPC (carrier: tetrahydrofuran (THF)), was 7500, and the degree of dispersion (Mw / Mn) was 1.55. 13 The composition ratios measured by 13C-NMR were 20 / 35 / 15 / 30 in molar ratio (ratio of repeating units, corresponding from left to right).

[0307] [Photoacid Generator (B)] Compounds B-1 to B-75 listed above were used as the photoacid generator (B).

[0308] [Photodisintegrating Quencher] The following compounds C-1 to C-26 were used as photodecayable quenchers.

[0309] [ka]

[0310] [ka]

[0311] [ka]

[0312] [Non-photodisintegrating quencher] The following compounds G-1 to G-5 were used as non-photodecaying quenchers.

[0313] [ka]

[0314] [Hydrophobic resin] The structures of resins I-1 to I-8, which were used as hydrophobic resins, are shown below.

[0315] [ka]

[0316] Resins I-1 to I-8 were synthesized according to the synthesis method for resin A-1 described above (synthesis example 1). Table 4 shows the composition ratio (mass ratio; corresponding from left to right), weight-average molecular weight (Mw), and molecular weight dispersion (Mw / Mn) of each repeating unit. The weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) of resins I-1 to I-8 were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). Furthermore, the composition ratio (mass ratio) of the resins was determined as follows: 13 It was measured by 13C-NMR.

[0317] [Table 4]

[0318] [Surfactants] The surfactants used (H-1 to H-3) 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)

[0319] [solvent] The solvents used (F-1 to F-9) 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

[0320] <Preparation of the resist composition> Each component shown in Tables 5-8 below was mixed to achieve a solid content concentration of 2.0% by mass. The resulting mixture was then filtered by passing it through a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, in that order to prepare resist compositions (Re-1 to Re-96, Re-1R to Re-8R). Solids refer to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples. In the table, the "Quantity" column indicates the content (mass %) of each component relative to the total solids in the resist composition.

[0321] [Table 5]

[0322] [Table 6]

[0323] [Table 7]

[0324] [Table 8]

[0325] <Examples 1-1 to 1-96, Comparative Examples 1-1 to 1-8> [Pattern formation method (1): EUV exposure and organic solvent development] A 12-inch diameter silicon wafer was coated with the underlayer film formation composition AL412 (manufactured by Brewer Science), and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. On top of the underlayer film, the resist compositions shown in Tables 9-10 below were coated and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), a silicon wafer with the obtained resist film was patterned so that the average line width of the resulting pattern was 14 nm. A mask with a line size of 14 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.

[0326] [Evaluation Item 1: Defect Evaluation (Defect Prevention)] The patterns obtained using the method described above were evaluated by counting the number of defects per silicon wafer using UVision5 (AMAT) and SEMVisionG4 (AMAT), according to the following evaluation criteria. A lower number of defects indicates better defect suppression, and an "F" rating or higher is considered acceptable. A: Number of defects is 50 or less B: Number of defects is between 50 and 100. C: Number of defects is between 100 and 200. D: Number of defects is between 200 and 300. E: Number of defects is between 300 and 400. F: Number of defects: more than 400 but less than or equal to 500 G: Number of defects exceeds 500

[0327] [Evaluation Item 2: Line With Sloughness Performance (LWR Performance, nm)] The pattern obtained by the method described above was observed from above using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at 250 locations, and its standard deviation (σ) was calculated. The measurement variability of the line width was evaluated using 3σ, and the value of 3σ was defined as LWR (nm). A smaller LWR value indicates better LWR performance. The LWR performance (nm) is preferably 4.5 nm or less, more preferably 4.2 nm or less, even more preferably 3.9 nm or less, still preferably 3.6 nm or less, particularly preferably 3.3 nm, and most preferably 3.0 nm or less.

[0328] The results are shown in Tables 9-10 below.

[0329] [Table 9]

[0330] [Table 10]

[0331] As shown in Tables 9-10 above, the resist composition of the present invention was confirmed to exhibit excellent defect performance (defect suppression) and LWR performance when forming extremely fine patterns by organic solvent development. On the other hand, the resist composition of the comparative example exhibited insufficient performance in these areas.

[0332] <Examples 2-1 to 2-96, Comparative Examples 2-1 to 2-8> [Pattern formation method (2): EUV exposure and alkaline aqueous solution development] A 20 nm thick underlayer film was formed by coating a 12-inch diameter silicon wafer with the underlayer film formation composition AL412 (manufactured by Brewer Science) and baking it at 205°C for 60 seconds. On top of the underlayer film, the resist compositions shown in Tables 11-12 below were coated and baked at 100°C for 60 seconds to form a 30 nm thick resist film. Using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), a silicon wafer with the obtained resist film was patterned so that the average line width of the resulting pattern was 14 nm. A mask with a line size of 14 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 resulting positive-type patterns were evaluated for defect suppression and LWR performance in the same manner as described in Examples 1-1 to 1-96 and Comparative Examples 1-1 to 1-8.

[0333] The evaluation results are shown in Tables 11-12 below.

[0334] [Table 11]

[0335] [Table 12]

[0336] As shown in Tables 11-12 above, the resist composition of the present invention was confirmed to exhibit excellent defect performance (defect suppression) and LWR performance even when forming extremely fine patterns by alkaline aqueous solution development. On the other hand, the resist composition of the comparative example exhibited insufficient performance in these areas.

[0337] Furthermore, even when an electron beam is used as the exposure light source, the resist composition of the present invention exhibits excellent defect performance (defect suppression) and LWR performance when forming extremely fine patterns, similar to Examples 1-1 to 1-96 and Examples 2-1 to 2-96. [Industrial applicability]

[0338] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that can suppress the occurrence of defects in the formation of extremely fine patterns (for example, line-and-space patterns with a line width of 35 nm or less, or hole patterns with a pore diameter of 35 nm or less, etc.) and has excellent roughness performance, a photosensitive or radiation-sensitive resin film formed from the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0339] 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. 2022-105172 filed on June 29, 2022, and Japanese Patent Application No. 2023-037998 filed on March 10, 2023, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiation-sensitive resin composition containing a resin (A) comprising a repeating unit (i) represented by the following general formula (N-0), a repeating unit (ii) having a cyano group and a lactone structure, and a repeating unit (iii) having a phenolic hydroxyl group, A photosensitive or radiation-sensitive resin composition wherein the content of repeating units having acid-degradable groups in the resin (A) is 35 mol% or more relative to the total repeating units in the resin (A). 【Chemistry 1】 In the general formula (N-0), X Ｎ１ represents a hydrogen atom, a halogen atom, a hydroxy group or an organic group. k represents 0 or 1. R Ｎ１ ~R Ｎ３ each independently represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. Two of R Ｎ１ ~R Ｎ３ may combine to form a ring. R Ｎ４ represents a halogen atom, a hydroxy group or an organic group. When there are a plurality of R Ｎ１ ~R Ｎ４ , the plurality of R Ｎ１ ~R Ｎ４ may be the same or different from each other. R Ｎ５ represents a hydrogen atom or an organic group. R Ｎ４ and R Ｎ５ may combine to form a ring. t1 represents an integer of 1 or more and (5 + 2k) or less. t2 represents an integer of 0 or more and (5 + 2k - t1) or less.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-1). 【Chemistry 2】 In general formula (N-1), X Ｎ１ , R Ｎ１ ~R Ｎ５ k, t1, and t2 are X in the general formula (N-0), respectively. Ｎ１ , R Ｎ１ ~R Ｎ５ , represents the same meaning as k, t1 and t2.

3. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-2). 【Transformation 3】 In general formula (N-2), X Ｎ１ , R Ｎ１ ~R Ｎ４ These are the X in the general formula (N-0), respectively. Ｎ１ , R Ｎ１ ~R Ｎ４ It has the same meaning. t3 represents an integer between 1 and 5 (inclusive). t4 represents an integer between 0 and 4 (inclusive).

4. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (ii) is a repeating unit represented by the following general formula (Q-1). 【Chemistry 4】 In general formula (Q-1), X Ｑ１ L represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. Ｑ１ R represents a single bond or a divalent organic group. Ｑ１ and R Ｑ２ Each independently represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C1-C5 alkylthio group, or R Ｑ１ and R Ｑ２ The two atoms combine to form a C1-C6 alkylene group, an ether bond, or a thioether bond, which may contain at least one oxygen atom and a sulfur atom. Ｑ３ m1 represents a halogen atom, hydroxyl group, or organic group. m1 represents an integer from 1 to 6. m2 represents an integer from 0 to 5.

5. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (i) is a repeating unit represented by the following general formula (N-3). 【Transformation 5】 In general formula (N-3), X Ｎ２ R represents a hydrogen atom, halogen atom, or methyl group. Ｎ６ represents a methyl group or an ethyl group. t5 represents 1 or 2.

6. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) includes a repeating unit represented by the following general formula (E-1). 【Transformation 6】 In general formula (E-1), X Ｅ１ R represents a hydrogen atom, halogen atom, hydroxyl group, or organic group. Ｅ１ ~R Ｅ３ Each of these independently represents a hydrocarbon group having 1 to 12 carbon atoms. Ｅ１ ~R Ｅ３ Two of them may combine to form a ring. Ｅ１ ~R Ｅ３ If the hydrocarbon group represented by includes an alkylene group, some of the alkylene groups may be replaced by an ether group, a thioether group, or a carbonyl group.

7. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the content of repeating units having acid-degradable groups in the resin (A) is 40 mol% or more relative to the total repeating units in the resin (A).

8. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the content of repeating units having acid-degradable groups in the resin (A) is 45 mol% or more relative to the total repeating units in the resin (A).

9. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) includes a repeating unit represented by the following general formula (E-2). 【Transformation 7】 In general formula (E-2), X Ｅ２ R represents a hydrogen atom, halogen atom, or methyl group. Ｅ４ represents a hydrocarbon group with 6 or fewer carbon atoms. u1 represents 1 or 2.

10. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the molecular weight dispersion of the resin (A) is 1.70 or less.

11. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, comprising an onium salt compound as a compound other than the resin (A).

12. A photosensitive or radiation-sensitive resin composition according to claim 1 or 2, comprising a photoacid generator.

13. The aforementioned R Ｎ１ ~R Ｎ３ The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the total number of carbon atoms is 3 to 25.

14. A photosensitive or radiation-sensitive film formed from the photosensitive or radiation-sensitive resin composition described in claim 1 or 2.

15. A step of forming a photosensitive or radiation-sensitive film on a substrate using the photosensitive or radiation-sensitive resin composition according to claim 1 or 2, 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.

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

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