Photosensitive or radiation-sensitive resin compositions, resist films, pattern forming methods, methods for manufacturing electronic devices, and compounds

Abstract

The present invention provides a photosensitive or radiation-sensitive resin composition with excellent LWR performance, a resist film formed using the photosensitive or radiation-sensitive resin composition, a pattern formation method and a method for manufacturing an electronic device using the photosensitive or radiation-sensitive resin composition, and compounds useful for the photosensitive or radiation-sensitive resin composition. [Solution] A photosensitive or radiation-sensitive resin composition containing a compound (A) represented by formula (1) or formula (2) described in the specification and a resin (B) whose polarity increases by the action of an acid; a resist film formed using the photosensitive or radiation-sensitive resin composition; a pattern forming method and a method for manufacturing an electronic device using the photosensitive or radiation-sensitive resin composition; and a compound represented by formula (1) or formula (2) described in the specification.

Description

[Technical Field]

[0001] The present invention relates to photosensitive or radiation-sensitive resin compositions, resist films, pattern formation methods, methods for manufacturing electronic devices, and compounds. More specifically, the present invention relates to photosensitive or radiation-sensitive resin compositions, resist films, pattern formation methods, and methods for manufacturing electronic devices that can be suitably used in ultramicrolithography processes applicable to manufacturing processes for ultra-large-scale integration (ULSI) and high-capacity microchips, processes for creating molds for nanoimprints, and processes for manufacturing high-density information recording media, as well as other photofabrication processes, and compounds useful for the above-mentioned photosensitive or radiation-sensitive resin compositions. [Background technology]

[0002] Traditionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations), microfabrication has been performed using lithography with resist compositions. In recent years, with the increasing integration of integrated circuits, there has been a growing demand for the formation of ultrafine patterns in the submicron or quarter-micron region. Accordingly, there has been a trend toward shorter exposure wavelengths, from the g-line to the i-line, and further to KrF excimer laser light. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as the light source have been developed. Furthermore, as a technique to further improve resolution, development of the so-called immersion method has been progressing, which involves filling the space between the projection lens and the sample with a liquid with a high refractive index (hereinafter also referred to as "immersion liquid").

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is currently under development. Accordingly, resist compositions that are effectively sensitive to various types of active light or radiation are being developed.

[0004] Patent Document 1 describes a resist composition containing a base component whose solubility in a developer changes due to the action of an acid, and a compound having a specific sulfonic acid anion structure that includes an imide bond. Furthermore, Patent Document 2 describes a resist composition comprising a sulfonium salt having a specific sulfonic acid anion structure, an acrylic resin, and an acid generator. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 7507993 specification [Patent Document 2] Japanese Patent Publication No. 2011-191745 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In recent years, the performance requirements for resist compositions have become increasingly stringent. In particular, there is a growing demand for improved line width roughness (LWR) performance when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern.

[0007] The object of this invention is to provide a photosensitive or radiation-sensitive resin composition with excellent LWR performance. Furthermore, the present invention aims to provide a resist film formed using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern formation method using the above-mentioned photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Furthermore, the present invention aims to provide compounds useful for the above-mentioned photosensitive or radiation-sensitive resin compositions. [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 compound (A) represented by the following formula (1) or the following formula (2) and a resin (B) whose polarity increases by the action of an acid.

[0010] [Chemical formula]

[0011] In formula (1), R , , , <f 2 , , m+ , , , , , , 1 , , 2 , ,

[0014] , 2 , , b , ,

[0013] , , , 1 and R 2 each independently represents an organic group. R 1 and R 2 may combine with each other to form a ring. L 1 represents a single bond or a divalent linking group. M a n+ represents an n-valent cation. n represents an integer of 1 or more.

[0012] [Chemical formula] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ In the above equation (1), L 1 , or L in formula (2) above 2 The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the active component is -CO- or -SO2-.

[0015] [4] R in equation (1) above 1 and R 2 The photosensitive or radiation-sensitive resin composition according to [2], wherein at least one of the members is an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom. [5] R in equation (1) above 1 and R 2 The photosensitive or radiation-sensitive resin composition according to [4], wherein at least one of the members has an alicyclic hydrocarbon group which may have a heteroatom.

[0016] [6] In the above formula (1), M a n+ , or M in formula (2) above b m+ The photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the cation is a sulfonium cation or an iodonium cation. [7] A resist film formed using a photosensitive or radiation-sensitive resin composition described in any one of items [1] to [6].

[0017] [8] A pattern forming method comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of items [1] to [6]; exposing the resist film; and developing the exposed resist film using a developer. [9] A method for manufacturing an electronic device, including the pattern formation method described in [8].

[0018]

[10] A compound represented by the following formula (1) or formula (2).

[0019] [ka]

[0020] In formula (1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring. L 1 This represents a single bond or a divalent linking group. M a n+ This represents an n-valent cation. n represents an integer greater than or equal to 1.

[0021] [ka]

[0022] In formula (2), L 2 This represents a single bond or a divalent linking group. W represents a cyclic group. M b m+ This represents a cation with m-valence. m represents an integer greater than or equal to 1.

[0023]

[11] R in equation (1) above 1 and R 2 However, each may independently have a hydrocarbon group (R) which may have a heteroatom. 1 and R 2 The compound described in

[10] , wherein the atoms may bond to each other to form a ring.

[12] In the above equation (1), L 1 , or L in formula (2) above 2 The compound according to

[10] or

[11] , wherein the compound is -CO- or -SO2-.

[13] R in equation (1) above 1 and R 2 The compound according to

[11] , wherein at least one of the members is an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom.

[14] R in equation (1) above 1 and R 2 The compound according to

[13] , wherein at least one of the members has an alicyclic hydrocarbon group which may have a heteroatom.

[15] In the above formula (1), M a n+ , or M in formula (2) above b m+ The compound is one of the items in any one of

[10] to

[14] , wherein the compound is a sulfonium cation or an iodonium cation. [Effects of the Invention]

[0024] The present invention provides a photosensitive or radiation-sensitive resin composition with excellent LWR performance. Furthermore, the present invention can provide a resist film formed using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern formation method and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition, and compounds useful for the above-mentioned photosensitive or radiation-sensitive resin composition. [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.

[0026] 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, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it include the lower and upper limits, respectively.

[0027] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Also, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0028] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw / Mn) of a resin 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).

[0029] 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. Examples of substituents include monovalent nonmetallic groups excluding hydrogen atoms, and can be selected from, for example, the following substituents T.

[0030] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl. Examples include nyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups (heteroaryl groups); hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; cyano groups; nitro groups; cycloalkyloxycarbonyl groups; heteroaryloxycarbonyl groups; alkylcarbonyl groups; arylcarbonyl groups; heteroarylcarbonyl groups; cycloalkyloxy groups; heteroaryloxy groups; alkylsulfonyl groups; arylsulfonyl groups; cycloalkylsulfinyl groups; heteroarylsulfonyl groups; alkylsulfinyl groups; arylsulfinyl groups; cycloalkylsulfinyl groups; heteroarylsulfinyl groups; etc. Furthermore, if these substituents can have one or more substituents, groups having one or more substituents selected from the substituents listed above as further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, etc.) are also included as examples of substituent T.

[0031] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. The above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0032] 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. All pKa values ​​described herein are calculated using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0033] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0034] 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.

[0035] In this specification, "solids" means components that form a film (preferably a resist film) using a photosensitive or radiation-sensitive resin composition, and does not include solvents. Furthermore, any component that forms a film (preferably a resist film) using a photosensitive or radiation-sensitive resin composition is considered a solid, even if its properties are liquid.

[0036] <Actinic ray-sensitive or radiation-sensitive resin composition> The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is a photosensitive or radiation-sensitive resin composition containing a compound (A) represented by the following formula (1) or formula (2) and a resin (B) whose polarity increases by the action of an acid.

[0037] [ka]

[0038] In formula (1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring. L 1 This represents a single bond or a divalent linking group. M a n+ This represents an n-valent cation. n represents an integer greater than or equal to 1.

[0039] [ka]

[0040] In formula (2), L2 This represents a single bond or a divalent linking group. W represents a cyclic group. M b m+ This represents a cation with m-valence. m represents an integer greater than or equal to 1.

[0041] The mechanism by which the composition of the present invention exhibits superior LWR performance is not clear, but the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism described below. Compound (A) is SO3 - It has a structure in which -SO2- is bonded to the nitrogen atom to which it is bonded. In the field of resists, from the viewpoint of strong oxidation, SO3 - While compounds with fluorine atoms in the vicinity tend to be used, -SO2- is more hydrophilic than fluorine atoms, so it is thought that the compatibility between compound (A) and resin (B), whose polarity increases due to the action of the acid, will be improved and the variation in acid will be suppressed. In addition, it is thought that the presence of -SO2- will increase the interaction with resin (B) and suppress the diffusion of acid. Furthermore, since -SO2- has strong electron-withdrawing properties, it is thought that the contrast will be improved. These effects are thought to improve LWR performance.

[0042] The compositions of the present invention are typically resist compositions, and may be either positive-type or negative-type resist compositions. The compositions of the present invention may be resist compositions for alkaline development or resist compositions for organic solvent development. The composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition. Preferably, the composition of the present invention is a chemically amplified resist composition. A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. In the following, we will first describe in detail the various components of the composition of the present invention.

[0043] [Compound (A)] Compound (A) included in the composition of the present invention will be described below. Compound (A) is represented by the following formula (1) or formula (2).

[0044] (The compound represented by formula (1))

[0045] [ka]

[0046] In formula (1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring. L 1 This represents a single bond or a divalent linking group. M a n+ This represents an n-valent cation. n represents an integer greater than or equal to 1.

[0047] M in equation (1) a n+ The symbol represents an n-valent cation. n represents an integer of 1 or more. It is preferable that n represents 1 or 2, and more preferably 1. M a n+ It is preferable that represents a sulfonium cation or an iodonium cation. M a n+ Preferably, represents a cation represented by the following formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the following formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0048] [ka]

[0049] In the above equation (ZaI), R201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The number of carbon atoms of the organic group as R 201 ~R 203 is preferably 1 to 30, more preferably 1 to 20. Two of R 201 ~R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R 201 ~R 203 include, for example, an alkylene group (e.g., a butylene group and a pentylene group), and -CH2-CH2-O-CH2-CH2-.

[0050] Preferred embodiments of the organic cation in formula (ZaI) include the cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) described below.

[0051] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 ~R 203 in the above formula (ZaI) is an aryl group. The arylsulfonium cation may have all of R 201 ~R 203 as aryl groups, or some of R 201 ~R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups. R 201 ~R 203 One of R 201 ~R 203 is an aryl group, and the remaining two of R 201 ~R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203Examples 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.

[0052] 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.

[0053] R 201 ~R 203The substituents that the aryl group, alkyl group, and cycloalkyl group may have are preferably 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 (preferably chlorine, bromine, or iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible. The above substituents may also preferably form an acid-degradable group in any combination.

[0054] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 However, each of these independently represents a cation that is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0055] R 201 ~R 203 Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, norbornyl group). R201 ~R 203 may be further substituted by a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. R 201 ~R 203 The substituents of ~R preferably form an acid-decomposable group by any combination of substituents, respectively independently.

[0056] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0057] [Chemical formula]

[0058] In formula (ZaI-3b), R 1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group (e.g., t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R 1c ~R 7c and the substituents of R x and R y preferably form an acid-decomposable group by any combination of substituents, respectively independently.

[0059] R1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These elements may bond to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0060] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of groups formed by the bonding of these atoms include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0061] R 1c ~R 5c , R 6c , R 7c , R x , R y , and also, R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and Ry The rings formed by the bonding of these elements to each other may have substituents.

[0062] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0063] [ka]

[0064] In equation (ZaI-4b), l represents an integer between 0 and 2, and r represents an integer between 0 and 8. R 13 This represents a group containing a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. R 14 R represents a hydroxyl group, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. 14 If multiple instances exist, each independently represents one of the above-mentioned groups, such as a hydroxyl group. R 15 Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R 15It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R 15 The ring formed by the bonding of these elements may have substituents.

[0065] In equation (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. R 13 ~R 15 , and also, R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0066] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0067] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 The substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include, for example, an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Also, the substituents of R

[0068] Specific examples of M a n+ are shown below, but are not limited thereto.

[0069] [Chemical formula]

[0070] [Chemical formula]

[0071] [Chemical formula]

[0072] When n represents an integer of 2 or more, M in formula (1) a n+ may be n M a + . M a + preferably represents a sulfonium cation or an iodonium cation. M a +Preferably, represents a cation represented by the above formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the above formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0073] In formula (1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring.

[0074] R 1 and R 2 The organic group represented is not particularly limited, but it is preferable to represent a hydrocarbon group which may have a heteroatom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0075] Examples of aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, as well as alicyclic hydrocarbon groups such as cycloalkyl groups, cycloalkenyl groups, and cycloalkynyl groups.

[0076] R 1 and R 2 The alkyl group represented by may be linear or branched, preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms. 1 and R 2 Examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. 1 and R 2 The alkyl group represented by may have substituents.

[0077] R 1 and R 2 The alkenyl group represented by may be linear or branched, and an alkenyl group having 2 to 12 carbon atoms is preferred. 1 and R 2Examples of alkenyl groups represented by include vinyl groups. 1 and R 2 The alkenyl group may have substituents.

[0078] R 1 and R 2 The alkynyl group represented by may be linear or branched, and an alkynyl group having 2 to 12 carbon atoms is preferred. 1 and R 2 Examples of alkynyl groups represented by include the ethynyl group. 1 and R 2 The alkynyl group may have substituents.

[0079] R 1 and R 2 The cycloalkyl group represented by may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably having 4 to 15 carbon atoms, and even more preferably having 5 to 10 carbon atoms. 1 and R 2 Examples of cycloalkyl groups represented by include cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, adamantyl group, 1-ethyladamantyl group, norbornyl group, tetracyclodecanyl group, and tetracyclododecanyl group. 1 and R 2 The cycloalkyl group represented by may have substituents.

[0080] R 1 and R 2 The cycloalkenyl group represented by may be monocyclic or polycyclic, and a cycloalkenyl group having 3 to 20 carbon atoms is preferred. 1 and R 2 The cycloalkenyl group represented by may have substituents.

[0081] R 1 and R 2 The cycloalkynyl group represented by may be monocyclic or polycyclic, and a cycloalkynyl group having 3 to 20 carbon atoms is preferred. 1 and R2 The cycloalkynyl group represented by may have substituents.

[0082] Examples of aromatic hydrocarbon groups include the aryl group. R 1 and R 2 The aryl group represented is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. 1 and R 2 The aryl group represented by may have substituents.

[0083] R 1 and R 2 The hydrocarbon group represented by may have a heteroatom. The heteroatom is not particularly limited, but examples include an oxygen atom, a nitrogen atom, and a sulfur atom. The hydrocarbon group may also have a group containing a heteroatom such as a carbonyl group, -NR-, -COO-, -SO2-, or -SO3-. R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. For explanations, specific examples, and preferred ranges of the alkyl, cycloalkyl, and aryl groups represented by R, see L below. 1 The R in -NR- is the same as the R in alkyl, cycloalkyl, and aryl groups.

[0084] Examples of hydrocarbon groups having heteroatoms include, specifically, R 1 and R 2 A structure in which one or more methylene groups constituting the alkyl group represented by are replaced by the aforementioned heteroatoms or groups containing heteroatoms; R 1 and R 2 Examples include structures in which one or more methylene groups constituting the cycloalkane ring of a cycloalkyl group represented by are replaced by the aforementioned heteroatoms or groups containing heteroatoms; other heterocyclic groups such as 1-piperidinyl groups and heteroaryl groups; and so on.

[0085] R 1 and R2 Preferably, each of these independently represents an alkyl group which may have a heteroatom, a cycloalkyl group which may have a heteroatom, or an aryl group which may have a heteroatom.

[0086] R 1 and R 2 Each of the above-mentioned groups represented by may have further substituents. Examples of substituents include the substituent T mentioned above. Furthermore, the substituent is R 1 and R 2 It is also preferable that the hydrocarbon group may have the aforementioned heteroatom represented by . Furthermore, the substituent may have an ionic group, for example, -CO2 - Mc + , -SO3 - Mc + (Mc + It may have (where represents a cation), etc. Mc + The cation represented by is preferably the cation represented by the above formula (ZaI) or the cation represented by the formula (ZaII).

[0087] When each of the above-mentioned groups has an ionic group as a substituent, the sum of the valencies of the anionic group and the sum of the valencies of the cationic group are the same in the compound represented by formula (1) above.

[0088] R 1 and R 2 Preferably, at least one of these groups has an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom. As a group having an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom, a group represented by the following formula (y-1) or formula (y-2) is preferred.

[0089] [ka]

[0090] In equations (y-1) and (y-2), R Y This represents an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom. In equation (y-2), s represents either 1 or 2. * indicates the connection position.

[0091] In alicyclic hydrocarbon groups that may have heteroatoms, the above-mentioned R is an example of an alicyclic hydrocarbon group. 1 and R 2 Examples include alicyclic hydrocarbon groups. The aromatic hydrocarbon group in the aromatic hydrocarbon group which may have a heteroatom is the above-mentioned R 1 and R 2 Aromatic hydrocarbon groups are one example. As for heteroatoms, the above-mentioned R 1 and R 2 Examples of heteroatoms that a hydrocarbon group may have include alicyclic hydrocarbon groups and aromatic hydrocarbon groups, which may have groups containing the aforementioned heteroatoms. The alicyclic hydrocarbon group which may have a heteroatom and the aromatic hydrocarbon group which may have a heteroatom may further have substituents.

[0092] R 1 and R 2 It is more preferable that at least one of them has an alicyclic hydrocarbon group which may have a heteroatom.

[0093] In formula (1), L 1 This represents a single bond or a divalent linking group. L 1 The divalent linking group represented by is not particularly limited, but examples include -O-, -CO-, -COO-, -OCOO-, -NR-, -CONR-, -S-, -SO-, -SO2-, alkylene group, cycloalkylene group, alkenylene group, arylene group, heterocyclic group, or a group formed by a combination of two or more of these groups. R represents a hydrogen atom, alkyl group, cycloalkyl group, or aryl group. L 1The alkylene group represented by is not particularly limited, but alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene groups, are preferred. L 1 The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group and an ester bond, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a vinylene group. L 1 The alkenylene group represented by is not particularly limited, but for example, an alkenylene group having 2 to 8 carbon atoms is preferred. L 1 The arylene group represented by is not particularly limited, but examples include arylene groups having 6 to 20 carbon atoms, and arylene groups having 6 to 15 carbon atoms are preferred. The arylene group is preferably a phenylene group or a naphthylene group, and is particularly preferably a phenylene group. L 1 The heterocyclic group represented by is not particularly limited, but examples include a divalent aromatic ring group or a divalent non-aromatic ring group whose ring members include at least one selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms. 1 The number of ring member atoms of the heterocyclic group represented by is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15. 1 The number of carbon atoms in the heterocyclic group represented by is not particularly limited, but 1 to 19 is preferred, and 2 to 14 is more preferred.

[0094] L 1 In -NR- and -CONR-, R represents a hydrogen atom, alkyl group, cycloalkyl group, or aryl group.

[0095] The alkyl group represented by R may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of alkyl groups represented by R include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups. The alkyl group represented by R may have substituents.

[0096] The cycloalkyl group represented by R may be monocyclic or polycyclic, with a preference for cycloalkyl groups having 3 to 20 carbon atoms, more preferably cycloalkyl groups having 4 to 15 carbon atoms, and even more preferably cycloalkyl groups having 5 to 10 carbon atoms. Examples of cycloalkyl groups represented by R include cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, adamantyl group, 1-ethyladamantyl group, norbornyl group, tetracyclodecanyl group, and tetracyclododecanyl group. The cycloalkyl group represented by R may have substituents. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group represented by R may be replaced with heteroatoms such as oxygen atoms, groups having heteroatoms such as carbonyl groups and ester bonds, or vinylidene groups. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group represented by R may be replaced with vinylene groups.

[0097] The aryl group represented by R is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. The aryl group represented by R may have substituents.

[0098] L 1The alkylene group, cycloalkylene group, alkenylene group, and arylene group represented by , and the alkyl group, cycloalkyl group, and aryl group represented by R may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above.

[0099] L 1 It is preferable that it represents a divalent linking group, more preferably -CO-, -SO2-, or an alkylene group, and even more preferably -CO- or -SO2-.

[0100] The compound represented by formula (1) above is preferably represented by the following formula (1-1).

[0101] [ka]

[0102] In formula (1-1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring. L 11 This represents -CO- or -SO2-. M a + This represents a monovalent cation.

[0103] R in equation (1-1) 1 and R 2 This is R in equation (1) above. 1 and R 2 This is synonymous with the preferred example, and the same applies to the preferred example. M in equation (1-1) a + M in equation (1) above a n+ This is equivalent to (n=1), and the preferred example is similar.

[0104] (The compound represented by formula (2))

[0105] [ka]

[0106] In formula (2), L 2 This represents a single bond or a divalent linking group. W represents a cyclic group. M b m+ This represents a cation with m-valence. m represents an integer greater than or equal to 1.

[0107] M in equation (2) b m+ The symbol represents a cation with an m-valence. m represents an integer of 1 or more. m is preferably 1 or 2, and more preferably 1. M b m+ It is preferable that represents a sulfonium cation or an iodonium cation. M b m+ It is preferable that represents a cation represented by the above formula (ZaI) or a cation represented by the formula (ZaII).

[0108] In formula (2), L 2 This represents a single bond or a divalent linking group. L 2 The divalent linking group represented by is L in formula (1) above. 1 One example is a divalent linking group.

[0109] L 2 It is preferable that it represents a divalent linking group, more preferably -CO-, -SO2-, or an alkylene group, and even more preferably -CO- or -SO2-.

[0110] In equation (2), W represents a cyclic group. Examples of cyclic groups represented by W include alicyclic hydrocarbon groups which may have heteroatoms, and aromatic hydrocarbon groups which may have heteroatoms.

[0111] Examples of alicyclic hydrocarbon groups that may have a heteroatom represented by W include cycloalkane rings, cycloalkene rings, and cycloalkyne rings.

[0112] The cycloalkane ring may be monocyclic or polycyclic, with cycloalkanes having 3 to 20 carbon atoms being preferred, cycloalkanes having 4 to 15 carbon atoms being more preferred, and cycloalkanes having 5 to 10 carbon atoms being even more preferred. Examples of cycloalkanes include cyclopentane, 1-methylcyclopentane, cyclohexane, adamantane, 1-ethyladamantane, norbornane, tetracyclodecane, and tetracyclododecane. The cycloalkane may have substituents.

[0113] The cycloalkene ring may be monocyclic or polycyclic, and a cycloalkene having 3 to 20 carbon atoms is preferred. The cycloalkene may have substituents.

[0114] The cycloalkyne ring may be monocyclic or polycyclic, and cycloalkynes having 3 to 20 carbon atoms are preferred. The cycloalkyne may have substituents.

[0115] In the aromatic hydrocarbon ring group which may have a heteroatom represented by W, the aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms, even more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, particularly preferably a benzene ring or a naphthalene ring, and most preferably a benzene ring. The aromatic hydrocarbon ring may have substituents.

[0116] Alicyclic hydrocarbon groups and aromatic hydrocarbon ring groups may have heteroatoms. The heteroatoms are not particularly limited, but examples include oxygen, nitrogen, and sulfur atoms. Furthermore, alicyclic hydrocarbon groups and aromatic hydrocarbon ring groups may have groups containing heteroatoms such as carbonyl groups, -NR-, -COO-, -SO2-, and -SO3- groups. R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Descriptions, specific examples, and preferred ranges of the alkyl, cycloalkyl, and aryl groups represented by R are given in the preceding L section, respectively. 1 The R in -NR- is the same as the R in alkyl, cycloalkyl, and aryl groups.

[0117] Examples of the cyclic groups having heteroatoms include structures in which one or more methylene groups constituting a cycloalkane ring are replaced by the aforementioned heteroatoms or groups containing heteroatoms; aromatic heterocycles, etc.

[0118] The cyclic group represented by W may have further substituents. Examples of substituents include the substituent T mentioned above. Furthermore, the substituent may have an ionic group, for example, -CO2 - Mc + , -SO3 - Mc + (Mc + It may have (where represents a cation), etc. Mc + The cation represented by is preferably the cation represented by the above formula (ZaI) or the cation represented by the formula (ZaII).

[0119] When the cyclic group represented by W has an ionic group as a substituent, the sum of the valencies of the anionic group and the sum of the valencies of the cationic group are the same in the compound represented by formula (2) above.

[0120] The two carbon atoms that are ring member atoms in W as explicitly shown in formula (2) may be adjacent or not, but it is preferable that they be adjacent.

[0121] The compound represented by formula (2) above is preferably represented by the following formula (2-1).

[0122] [ka]

[0123] In formula (2-1), L 21 This represents -CO- or -SO2-. W 1 This represents a cyclic group. M b + This represents a monovalent cation.

[0124] W in equation (2-1) 1 The cyclic group represented by is the same as the cyclic group represented by W in formula (2) above. However, W is explicitly stated in equation (2-1). 1 The two carbon atoms that are ring members in this compound are assumed to be adjacent to each other. That is, the two carbon atoms are connected by a single or double bond. M in equation (2-1) b + M in equation (2) above is b m+ This is equivalent to (m=1), and the preferred example is similar.

[0125] Specific examples of compounds represented by formula (1) among compound (A) include A-2 to A-18, as described in the examples below. Specific examples of compounds represented by formula (2) include A-1, A-19 to A-20, as described in the examples below. However, the present invention is not limited thereto.

[0126] Compound (A) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Furthermore, compound (A) may be a combination of both a low molecular weight compound and a polymer. If compound (A) is in the form of a low molecular weight compound, the molecular weight of compound (A) is preferably 5000 or less, more preferably 3000 or less, and particularly preferably 2000 or less. Furthermore, the molecular weight of compound (A) is preferably 100 or more, and more preferably 200 or more. If compound (A) is incorporated into a polymer, it may be incorporated into a resin (B), or into a resin different from resin (B). Compound (A) is preferably in the form of a low molecular weight compound.

[0127] Compound (A) functions as a photoacid generator. A photoacid generator is a compound that generates acid upon exposure to light. Furthermore, if compound (A) has a structure containing (for example, R in general formula (I)) 1 , and R 2 If compound (A) further contains weak acid anions such as sulfonate anions (weaker acid anions than the sulfonate anions bonded to the nitrogen atom of general formula (1)) or carboxylic acid anions, compound (A) can also function as an acid diffusion control agent. The acid diffusion control agent can act as a quencher that traps the acid generated from the photoacid generator during exposure and suppresses the reaction of resin (B) in the unexposed areas due to excess generated acid.

[0128] The synthesis method for compound (A) is not particularly limited, but for example, it can be obtained by introducing a sulfonic acid group by reacting a sulfonic acid halide or sulfur trioxide with a compound having a sulfonamide bond (-SO2-NH-), and then substituting the sulfonic acid group with a sulfonate salt.

[0129] The content of compound (A) in the composition of the present invention is not particularly limited, but is preferably 1.0 to 50.0% by mass, more preferably 3.0 to 45.0% by mass, and even more preferably 5.0 to 40.0% by mass, based on the total solid content of the composition of the present invention. Compound (A) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0130] [Resins whose polarity increases due to the action of acid] The composition of the present invention contains a resin (B) (also simply referred to as "resin (B)") whose polarity increases upon the action of an acid. The resin (B) preferably contains a group that decomposes and increases in polarity due to the action of an acid (also called an "acid-degradable group"), and more preferably contains repeating units having an acid-degradable group. When the resin (B) has an acid-degradable group, in the pattern forming method using the composition of the present invention, 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.

[0131] (Repeating unit with acid-degradable group) The acid-degradable group is preferably a group that decomposes upon the action of an acid to produce a polar group. The acid-degradable group is preferably a structure in which the polar group is protected by a group that is left behind upon the action of an acid (leaving group). The resin (B) preferably has repeating units having a group that decomposes upon the action of an acid to produce a polar group, thereby increasing its polarity upon the action of an acid, increasing its solubility in alkaline developer, and decreasing its solubility in organic solvents. Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0132] 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)

[0133] 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). 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. Rx1 to Rx3 each preferably independently represent a linear or branched alkyl group, and more preferably 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 cycloalkyl groups Rx1 to Rx3 may also be cycloalkyl groups having 3 to 20 carbon atoms. 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.

[0134] 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.

[0135] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0136] [ka]

[0137] Here, L Y1 and L Y2 Each of these independently represents 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 Y1 This represents a single bond or a divalent linking group. Q Y1This represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Note L Y1 and L Y2 Preferably, one of the groups is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. Q Y1 M Y1 , and L Y1 At least two of these may be joined together to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L Y2 It is preferable that the group is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, which ensures film strength and suppresses fogging.

[0138] If the composition of the present invention is, for example, a resist composition for EUV lithography, then L Y1 and L Y2The alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by the above formula may further preferably have a fluorine atom or an iodine atom as a substituent. In addition to fluorine and iodine atoms, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups may also preferably contain heteroatoms such as oxygen atoms. Specifically, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, 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, a resist composition for EUV lithography, then Q Y1 In alkyl groups, cycloalkyl groups, aryl groups, amino groups, ammonium groups, mercapto groups, cyano groups, aldehyde groups, and combinations thereof, which may contain heteroatoms, it is also preferable that the heteroatom is selected from the group consisting of fluorine, iodine, and oxygen atoms. In equation (Y3-1), * represents the bonding position.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (HA) is also preferred.

[0143] [ka]

[0144] L 1H R represents a divalent linking group which may have a fluorine atom or an iodine atom. 1H R represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. 2H This represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. However, L 1H , R 1H , and R 2H At least one of them has a fluorine atom or an iodine atom. L 1H Examples of divalent linking groups that may have a fluorine atom or an iodine atom, represented by , include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. Among these, L 1H Preferably, the group is -CO-, an arylene group, or an alkylene group having an arylene group with a fluorine or iodine atom, and more preferably, -CO-, or an arylene group having an alkylene group with a fluorine or iodine atom. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0145] R 1H The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. R 1H The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, as represented by , is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. R 1H The alkyl group represented by may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0146] R 2H Examples of leaving groups that may have a fluorine atom or an iodine atom, as represented by the formulas (Y1) to (Y4) above, include the leaving groups that may have a fluorine atom or an iodine atom.

[0147] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0148] [ka]

[0149] 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).

[0150] 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.

[0151] 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.

[0152] 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 cycloalkyl groups Rx1 to Rx3 may also be cycloalkyl groups having 3 to 20 carbon atoms. 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.

[0153] 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.

[0154] 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).

[0155] Resin (B) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (HB) is preferred.

[0156] [ka]

[0157] In formula (HB), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0158] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0159] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0160] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl groups Ry1 to Ry3 may also be cycloalkyl groups having 3 to 20 carbon atoms. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. An ethynyl group is preferred as the alkynyl group for Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (HB), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Ry3 are bonded together to form the aforementioned cycloalkyl group or cycloalkenyl group.

[0161] 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.

[0162] The repeating units represented by formula (HB) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0163] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (B). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (B). Specific examples of repeating units having an acid-degradable group containing an unsaturated bond include, for example, the repeating units described in paragraphs

[0067] to

[0071] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0164] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (B). Furthermore, the upper limit is preferably 90 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 (B).

[0165] The resin (B) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of the following repeating units (20) to (25). (20) Repeating units having an acid group (21) Repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom. (22) Repeating units having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups (23) Repeating units having photoacid generators (24) Repeating units represented by formula (V-1) or formula (V-2) (25) Repeating units for reducing the mobility of the main chain Furthermore, the repeating units represented by formulas (A) to (E), which will be described later, correspond to (25) repeating units for reducing the mobility of the main chain. Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group

[0166] The resin (B) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When the resin (B) has acidic groups, the interaction between the resin (B) and the acid generated from the photoacid generator is improved. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0167] Resin (B) may have at least one repeating unit selected from the group consisting of A above. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (B) has at least one repeating unit selected from the group consisting of A above. Resin (B) may contain at least one of fluorine atoms and iodine atoms. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (B) contains at least one of fluorine atoms and iodine atoms. If resin (B) contains both fluorine atoms and iodine atoms, resin (B) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (B) may contain two types of repeating units: repeating units containing fluorine atoms and repeating units containing iodine atoms. The resin (B) may have repeating units having aromatic groups. When the composition of the present invention is used as a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the resin (B) has repeating units having aromatic groups. The resin (B) may have at least one repeating unit selected from the group consisting of the above-mentioned group B. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (B) has at least one repeating unit selected from the group consisting of the above-mentioned group B. Furthermore, when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (B) does not contain either fluorine atoms or silicon atoms. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (B) does not have aromatic groups.

[0168] (Repeating units containing acidic groups) The resin (B) may have repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (B) has acid groups with a pKa of 13 or less, the content of acid groups in resin (B) 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 well, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. 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 acid described above, and the repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group, as described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom. Specific examples of repeating units having an acid group include, for example, the repeating units described in paragraphs

[0088] to

[0089] and

[0103] to

[0110] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0169] As a repeating unit having an acid group, the repeating unit represented by the following formula (b1-1) is preferred.

[0170] [ka]

[0171] In formula (b1-1), A a1 R represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. 21 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, and if there are multiple Rs, they may be the same or different. 21 If they have R, they may form a ring together. 21 A hydrogen atom is preferred. 'a' represents an integer from 1 to 3. 'b' represents an integer from 0 to (5-a).

[0172] When resin (B) contains repeating units having acidic groups, the content of repeating units having acidic groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (B). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (B).

[0173] (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 (B) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. It is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group> and the <repeating units having a photoacid-generating group> described later.

[0174] As the unit X, a repeating unit represented by formula (HC) is preferred.

[0175] [ka]

[0176] 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. Specific examples of repeating units having fluorine or iodine atoms include, for example, the repeating units described in paragraphs

[0116] to

[0117] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0177] The content of unit X is 0 mol% or more relative to the total repeating units in resin (B), may be 5 mol% or more, or 10 mol% or more. Furthermore, the upper limit may be 50 mol% or less, 45 mol% or less, or 40 mol% or less relative to the total repeating units in resin (B).

[0178] The total content of repeating units in resin (B) that contain at least one of a fluorine atom, a bromine atom, and an iodine atom may be 10 mol% or more, 20 mol% or more, 30 mol% or more, or 40 mol% or more relative to the total repeating units of resin (B). There is no particular upper limit, and it is 100 mol% or less relative to the total repeating units of resin (B). 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.

[0179] (A repeating unit having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups) The resin (B) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0180] The lactone group only needs to have a lactone structure. A 5- to 7-membered ring lactone structure is preferred. Among these, a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo or spiro structure is more preferred. The slutone group only needs to have a slutone structure. A 5- to 7-membered ring slutone structure is preferred. Among these, a 5- to 7-membered ring slutone structure in which another ring structure is fused to form a bicyclo or spiro structure is more preferred. Examples of lactone groups include those obtained by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22). Examples of sultone groups include those obtained by removing one or more hydrogen atoms from the ring member atoms of a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3). Examples of carbonate groups include carbonate groups obtained by removing one or more hydrogen atoms from the ring member atoms of a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2). The lactone group, sultone group, and carbonate group may be directly bonded to the main chain of resin (B). For example, the ring member atoms of the lactone group, sultone group, and carbonate group may constitute the main chain of resin (B). The lactone group, sultone group, and carbonate group may have substituents.

[0181] R in the following structural formula L R represents a substituent. LIf multiple R L They can be the same or they can be different. L Examples include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. If there are multiple e1s, they may be the same or different. If e1 is 2 or more, there may be multiple R L They may be the same or different, and there may be multiple Rs. L They may join together to form a ring.

[0182] [ka]

[0183] As an example of the unit Y, a repeating unit represented by the following formula (AI-2) can be cited.

[0184] [ka]

[0185] In formula (AI-2), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by Rb0 may have substituents. Examples of substituents that the alkyl group represented by Rb0 may have include hydroxyl groups and halogen atoms. Examples of halogen atoms represented by 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 (LC1-22), 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), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate ester structure represented by any of the formulas (CC1-1) to (CC1-2).

[0186] 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.

[0187] A cyclic carbonate ester group is preferred as the carbonate group. For repeating units having cyclic carbonate ester groups, see, for example, paragraphs

[0127] to

[0133] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0188] If resin (B) contains unit Y, the content of unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to the total repeating units in resin (B). Furthermore, the content of unit Y is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (B).

[0189] (Repeating unit having a photoacid-generating group) Resin (B) 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).

[0190] [ka]

[0191] R 41 L represents a hydrogen atom or a methyl group. 41 L represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain. Specific examples of repeating units having photoacid generating groups include, for example, the repeating units described in paragraphs

[0094] to

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

[0094] of International Publication No. 2018 / 193954, and the repeating units described in paragraph

[0138] of International Publication No. 2022 / 024928. The above descriptions are incorporated herein by reference.

[0192] 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.

[0193] If resin (B) 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 (B). Furthermore, the content of repeating units having photoacid generating groups 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 (B).

[0194] (The repeating unit is represented by formula (V-1) or formula (V-2) below) The resin (B) 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.

[0195] [ka]

[0196] 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.

[0197] (A repeating unit that reduces the mobility of the main chain) Resin (B) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have excellent dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of polymers such as resin (B) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). The calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0198] To increase the Tg of resin (B) (preferably to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (B). For repeating units to reduce the mobility of the main chain, refer to the contents of

[0144] to

[0160] of International Publication No. 2022 / 024928.

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

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

[0081] to

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

[0201] The resin (B) 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 (B) 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.

[0202] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (B) 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.

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

[0204] [ka]

[0205] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

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

[0206] (Other repeating units) Furthermore, resin (B) may have other repeating units besides those described above. For example, resin (B) 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.

[0207] In addition to the repeating structural units described above, resin (B) 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.

[0208] As for resin (B), in particular when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0209] Resin (B) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight (Mw) of resin (B), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Mw / Mn) of resin (B) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0210] The content of resin (B) in the composition of the present invention is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 99.9% by mass, and even more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. Resin (B) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0211] [Compounds that generate acid upon irradiation with active light or radiation (C)] The composition of the present invention may further contain a compound (C) different from compound (A), which is a compound that generates acid upon irradiation with active light or radiation (photoacid generator). Compound (C) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Furthermore, compound (C) may be a combination of a low molecular weight compound and a polymer incorporated as part of a polymer. If compound (C) is in the form of a low molecular weight compound, the molecular weight of compound (C) is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3000 or less. There is no particular lower limit to the molecular weight of compound (C), but it is preferably 100 or more. If compound (C) is incorporated into a polymer, it may be incorporated into a resin (B) or into a resin different from resin (B). Compound (C) is preferably in the form of a low molecular weight compound.

[0212] For example, compound (C) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0213] "M + X - In the compound represented by ", M + M represents a cation. +The valency of the cation represented by is 1 or greater. + Preferably, represents an organic cation. M + When M represents an organic cation + The explanation, specific examples, and preferred range of M in formula (1) above are given by a n+ It is similar to the one in [location / place].

[0214] "M + X - In the compound represented by ", X - represents an anion, preferably 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.

[0215] 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.

[0216] 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).

[0217] 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.

[0218] 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).

[0219] 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.

[0220] An example of a sulfonylimid anion is the saccharin anion.

[0221] 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.

[0222] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4) - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0223] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0224] [ka]

[0225] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. The non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0226] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0227] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0228] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0229] In formula (AN1-1), * a R in equation (AN1) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) 1 )(R 2 )- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. However, X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1)2a and R 2b If all of them are hydrogen atoms, then Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. * A R in equation (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0230] In formula (AN1), R 3 This represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0231] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-22) and (SL1-1) to (SL1-3) described above.

[0232] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0233] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0234] [ka]

[0235] In equation (AN2), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0236] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0237] R 4 and R 5 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. 4 and R 5 A hydrogen atom is preferred as the element.

[0238] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0239] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0240] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0241] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0242] The anion represented by formula (AN2) is SO3. - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q’-W is preferred. Here, L, q, and W are the same as in equation (AN2). q' represents an integer from 0 to 10.

[0243] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0244] [ka]

[0245] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0246] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations of these.

[0247] B represents a hydrocarbon group. For B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group) is more preferred.

[0248] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, R q R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. q They may be joined to each other to form a ring. Two Rq The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0249] Compound (C) is also preferably at least one selected from the group consisting of compounds (I) to (II).

[0250] (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, a structural site which 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.

[0251] 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 above 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.

[0252] 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.

[0253] If compound (I) is a compound that generates an acid having, for example, two first acidic sites 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 two HA1 and one HA2". When the acid dissociation constant of compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the acid dissociation constant when a compound having one A1 - A compound having one HA1 and one HA2 is "two A1 - The acid dissociation constant when forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation site M1 corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the acid dissociation constant when a compound has the above-mentioned cation site M1 in the above-mentioned structural site X corresponds to the acid dissociation constant a2. + to H + When a compound PI has multiple acid dissociation constants derived from the acidic site represented by HA1, the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1.- Let aa be the acid dissociation constant when it becomes "a compound having one HA1 and one HA2", and "one A1" - When the "compound having one HA1 and one HA2" becomes the "compound having two A1s" - Let ab be the acid dissociation constant when it becomes "a compound having two A1s and one HA2". The relationship between aa and ab satisfies aa < ab.

[0254] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1s - and two or more of the above M1s + may be the same or different from each other. In the compound (I), the above A1 - and the above A2 - and the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0255] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit value of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less.

[0256] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. As the lower limit value of the acid dissociation constant a2, -4.0 or more is preferably satisfied.

[0257] 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.

[0258] 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.

[0259] [ka]

[0260] [ka]

[0261] 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.

[0262] (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.

[0263] 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.

[0264] 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 site 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.

[0265] 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.

[0266] 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.

[0267] [ka]

[0268] 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.

[0269] Examples of non-cationic sites that compound (I) and compound (II) may possess are given below.

[0270] [ka]

[0271] [ka]

[0272] Specific examples of compound (C) include, for example, the compounds described in sections

[0320] to

[0321] of International Publication No. 2022 / 172715. The above description is incorporated herein by reference.

[0273] If the composition of the present invention contains compound (C), the content of compound (C) is not particularly limited, but 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. Furthermore, the content of compound (C) is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% by mass or less, relative to the total solid content of the composition of the present invention. Compound (C) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0274] [Acid diffusion control agent] The composition of the present invention may further contain an acid diffusion control agent (also referred to as "compound (D)" or "acid diffusion control agent (D)"). Compound (D) is a different compound from compound (A). Furthermore, compound (D) may be the same compound as compound (C), or it may be a different compound. The acid diffusion control agent can act as a quencher, trapping the acid generated from the photoacid generator during exposure and suppressing the reaction of the resin, where the polarity increases due to the action of the acid in the unexposed areas caused by the excess generated acid. Compound (D) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Furthermore, compound (D) may be in both the form of a low molecular weight compound and the form incorporated as part of a polymer. If compound (D) is in the form of a low molecular weight compound, the molecular weight of compound (D) is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3000 or less. The lower limit of the molecular weight of compound (D) is not particularly limited, but it may be, for example, 100 or more. If compound (D) is incorporated into a polymer, it may be incorporated into a resin (B) or into a resin different from resin (B). Compound (D) is preferably in the form of a low molecular weight compound.

[0275] The type of compound (D) is not particularly limited and includes, for example, basic compounds (DA), low molecular weight compounds (DB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (DC) include onium salt compounds (DD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (DE) whose basicity decreases or disappears upon irradiation with active light or radiation. Specific examples of basic compounds (DA) include, for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (DE) 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 (DB) 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 (DDs) 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.

[0276] 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.

[0277] If the composition of the present invention contains compound (D), the content of compound (D) is not particularly limited, but is preferably 0.01 to 30.0% by mass, more preferably 0.05 to 20.0% by mass, and even more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention. Compound (D) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0278] [Hydrophobic resin] The composition of the present invention may further contain a hydrophobic resin different from resin (B) (also referred to as "hydrophobic resin (E)"). The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resin (E) include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0279] The hydrophobic resin (E) 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, from the viewpoint of uneven distribution on the film surface. 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 chain. Examples of hydrophobic resins (E) include the compounds described in paragraphs

[0275] to

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

[0280] When the composition of the present invention contains a hydrophobic resin (E), the content of the hydrophobic resin (E) is not particularly limited, but 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. The hydrophobic resin (E) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0281] [Surfactants] The composition of the present invention may contain a surfactant. The inclusion of a surfactant results in superior adhesion and the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0282] Surfactants may be used individually or in combination of two or more types.

[0283] If the composition of the present invention contains a surfactant, the amount of surfactant is not particularly limited, but 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. Surfactants may be used individually or in combination of two or more types. When two or more types are used, it is preferable that their total content is within the range of the preferred content described above.

[0284] [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).

[0285] Combining the solvent and resin described above is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The solvent described above has a good balance of solubility, boiling point, and viscosity with the resin described above, which can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0286] 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.

[0287] The solvent content in the composition of the present invention is not particularly limited, but it is preferable to set it so that the solid content concentration in the composition of the present invention 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.

[0288] [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).

[0289] 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.

[0290] The composition of the present invention is also suitably used as a photosensitive composition for EUV exposure.

[0291] <Method for forming patterns on photosensitive or radiation-sensitive films> The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive or radiation-sensitive film of the present invention is preferably a resist film. 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 a resist film on a substrate using the composition of the present invention. Step 2: Exposure of the resist film Step 3: Developing the exposed resist film using a developer solution. The following details the steps for each of the above processes.

[0292] (Step 1: Resist film formation process) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0293] One method for forming a resist film on a substrate using the composition of the present invention is to coat the substrate with the composition of the present invention. 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.

[0294] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide) 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 resist film. If necessary, various undercoats (inorganic film, organic film, anti-reflective film) may be formed beneath the resist film.

[0295] 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.

[0296] The thickness of the resist 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, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0297] Alternatively, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist 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 the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be included in the composition of the present invention. 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.

[0298] (Step 2: Exposure process) Step 2 is the process of exposing the resist film. One method of exposure is to irradiate the formed resist 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 being particularly preferred. Specifically, these include KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0299] 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.

[0300] (Process 3: Development process) Step 3 is the process of developing the exposed resist film using a developer solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0301] 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 exposed or 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] (Other processes) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0306] 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.

[0307] 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.

[0308] 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).

[0309] 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.

[0310] The compositions and pattern-forming methods of the present invention, as well as the various materials used (e.g., solvents, developers, rinses, anti-reflective film-forming compositions, topcoat-forming compositions, etc.), preferably do not contain 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 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.

[0311] 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.

[0312] 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®.

[0313] 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 (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred.

[0314] 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.

[0315] <Method of manufacturing electronic devices> The present invention also relates to a method for manufacturing an electronic device, including the pattern formation method described above, and to an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present invention is one in which it is mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment).

[0316] <Compound> The present invention also relates to compounds represented by the following formula (1) or formula (2).

[0317] [ka]

[0318] In formula (1), R 1 and R 2 Each of these independently represents an organic group. 1 and R 2 These may be joined together to form a ring. L 1 This represents a single bond or a divalent linking group. M a n+ This represents an n-valent cation. n represents an integer greater than or equal to 1.

[0319] [ka]

[0320] In formula (2), L 2 This represents a single bond or a divalent linking group. W represents a cyclic group. M b m+ This represents a cation with an m-valence. m represents an integer greater than or equal to 1.

[0321] R in equation (1) 1 , R 2 , L 1 M a n+ and n are R in formula (1) in the description of compound (A) above. 1 , R 2 , L 1 M a n+ This is synonymous with n, and the preferred example is similar. L in equation (2) 2 W, M b m+ and m are L in formula (2) in the description of compound (A) above. 2 W, M b m+ It is synonymous with m, and the preferred example is similar.

[0322] That is, R in equation (1) above 1 and R 2 However, each may independently have a hydrocarbon group (R) which may have a heteroatom. 1 and R 2 It is preferable that the elements are bonded to each other to form a ring. In the above equation (1), L 1 , or L in formula (2) above 2 However, it is preferable that it be -CO- or -SO2-. R in equation (1) above 1 and R 2 Preferably, at least one of these groups has an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom. R in equation (1) above 1 and R2 Preferably, at least one of them has an alicyclic hydrocarbon group which may have a heteroatom. In the above formula (1), M a n+ , or M in formula (2) above b m+ However, it is preferable that the cation be a sulfonium cation or an iodonium cation. [Examples]

[0323] 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.

[0324] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0325] <Compound (A)> Compounds A-1 to A-20 are used as compound (A). Z-1 and Z-2 are comparative compounds. A-1 to A-20 and Z-1 to Z-2 are used as photoacid generators.

[0326] [ka]

[0327] [ka]

[0328] [ka]

[0329] [ka]

[0330] An example of the synthesis of compound (A) is shown below.

[0331] (Synthesis Example 1: Synthesis of A-1)

[0332] [ka]

[0333] In a three-necked flask, 2.5 g of saccharin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 8.0 g of chlorosulfonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed under a nitrogen atmosphere and stirred at 50°C for 3 hours. After cooling to 0°C, 50 mL of methylene chloride, 20 mL of hexane, and 50 mL of distilled water were added, and the aqueous layer was removed using a separatory funnel. The solvent was removed from the organic layer under reduced pressure, and the resulting solid was washed with ethylene chloride to obtain 1.3 g of a white solid of A-1-(I).

[0334] [ka]

[0335] In a three-necked flask, under a nitrogen atmosphere, 1.0 g of A-1-(I), 1.9 g of A-1-(II), 0.5 g of sodium bicarbonate, 13 mL of distilled water, and 13 mL of methylene chloride were mixed and stirred at 20°C for 1 hour. After removing the aqueous layer with a separatory funnel, the organic layer was washed twice with 10 mL of 0.1 M hydrochloric acid and 20 mL of deionized water. The solvent was removed from the washed organic layer under reduced pressure to obtain an oil, to which 7.5 g of methylene chloride was added, and further crystallization was performed with 20 mL of tert-butyl methyl ether to obtain 1.1 g of A-1 as a white solid. Identification of the obtained A-1 is as follows: 1 The analysis was performed using 1H-NMR (nuclear magnetic resonance). 1 H-NMR(400 MHz, acetone-d6)d =7.48-7.52(m, 2H), 7.65-7.78(m, 11H), 7.80-7.84(m, 6H) ppm

[0336] A-2 to A-20 can be synthesized using the same method as A-1.

[0337] <Resin (B)> Resins (B) (resins whose polarity increases due to the action of acid) are used, specifically B-1 to B-26. The structural formulas and content (mol%) of each repeating unit contained in B-1 to B-26, the weight-average molecular weight (Mw) of B-1 to B-26, and the degree of dispersion (Mw / Mn) are shown below. The content of each repeating unit is the molar ratio of each repeating unit to the total number of repeating units contained in each resin. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). Furthermore, the repeating unit content is as follows: 13 Measurement is performed using 1C-NMR (nuclear magnetic resonance).

[0338] [ka]

[0339] [ka]

[0340] [ka]

[0341] [ka]

[0342] <Compound (C)> A photoacid generator is used, and compound (C) is different from compound (A), using C-1 to C-18. Me represents a methyl group.

[0343] [ka]

[0344] [ka]

[0345] <Acid diffusion control agent (D)> D-1 to D-16 are used as acid diffusion control agents.

[0346] [ka]

[0347] [ka]

[0348] <Hydrophobic resin (E)> E-1 to E-12 are used as hydrophobic resins. The structural formulas and content (mol%) of each repeating unit contained in E-1 to E-12, as well as the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of E-1 to E-12, are shown below. The content of each repeating unit is the molar ratio of each repeating unit to the total number of repeating units contained in each resin. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). Furthermore, the repeating unit content is as follows: 13 Measurement is performed by 13C-NMR.

[0349] [ka]

[0350] [ka]

[0351] <Surfactant (F)> F-1 is used as the surfactant (F). F-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0352] <Solvent (G)> The solvent (G) to be used is shown below. G-1: Propylene glycol monomethyl ether acetate (PGMEA) G-2: Propylene glycol monomethyl ether (PGME) G-3: γ-Butyrolactone G-4: Ethyl lactate G-5: Cyclohexanone G-6:2-heptanone

[0353] (ArF exposure) <Preparation of the resist composition> The components shown in Tables 1-4 are dissolved in the solvents shown in the tables to prepare a solution with a solid content concentration of 3.0% by mass. This solution is then filtered through a polyethylene filter with a pore size of 0.03 μm to prepare the resist composition. Solid content refers to all components other than the solvent. In the table, the "mass%" column indicates the content (mass%) of each component relative to the total solids in the resist composition. When using two or more types of resin (B), each type and its content should be indicated separated by a " / ". The order in which the types and their contents are listed, separated by " / ", should correspond. When using two or more of the following: compound (A), compound (C), acid diffusion control agent (D), and hydrophobic resin (E), each type and its content should be listed in separate columns. The order in which the separated types and their contents are listed should correspond. Tables 1-4 also list the types and mass ratios of solvents used. The order in which the solvent types and mass ratios are listed corresponds to the order in which they are listed.

[0354] [Table 1]

[0355] [Table 2]

[0356] [Table 3]

[0357] [Table 4]

[0358] <Pattern formation method (1): ArF exposure, alkaline development (positive)> An organic anti-reflective film ARC29SR (manufactured by Brewer) is applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 95 nm. A resist composition shown in Table 5 is applied on top of the anti-reflective film and baked at 100°C for 60 seconds to form a resist film with a thickness of 85 nm. An ArF excimer laser immersion scanner (ASML; XT1700i, NA1.20) was used to expose the resist film through a 6% halftone mask of a 1:1 line-and-space pattern with a line width of 60 nm. Ultrapure water was used as the immersion solution. After exposure, the resist film was baked at 95°C for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. Subsequently, it was spin-dried to obtain a positive-type pattern.

[0359] <Performance Evaluation> [LWR (line width roughness)] A pattern formed with the optimal exposure amount for resolving a 1:1 line-and-space pattern with a line width of 60 nm is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi CG-4100)). The line width is measured at 50 arbitrary points, and its standard deviation (σ) is calculated. The measurement variability of the line width is evaluated using 3σ, and the value of 3σ is defined as LWR (nm). This value is then evaluated according to the following evaluation criteria. A smaller LWR value indicates better LWR performance. An LWR of 4.4 nm or less is preferable.

[0360] [Evaluation Criteria] S:LWR≦3.3 A: 3.3 <LWR≦3.5 B:3.5 <LWR≦3.8 C:3.8 <LWR≦4.1 D:4.1 <LWR≦4.4 E:4.4 <LWR

[0361] The results are shown in Table 5.

[0362] [Table 5]

[0363] <Pattern formation method (2): ArF exposure, organic solvent development (negative)> An organic anti-reflective film ARC29SR (manufactured by Brewer) is applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 95 nm. A resist composition shown in Table 6 is applied on top of the anti-reflective film and baked at 100°C for 60 seconds to form a resist film with a thickness of 85 nm. An ArF excimer laser immersion scanner (ASML; XT1700i, NA1.20) was used to expose the resist film through a 6% halftone mask of a 1:1 line-and-space pattern with a line width of 60 nm. Ultrapure water was used as the immersion solution. After exposure, the resist film was heated at 95°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative-type pattern.

[0364] The LWR is evaluated using the same method as the performance evaluation of the pattern formation method (1) described above. The results are shown in Table 6.

[0365] [Table 6]

[0366] (EUV exposure) <Preparation of the resist composition> The components shown in Tables 1-4 above are mixed to a solid content concentration of 2.0% by mass. The resulting mixture is then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, to prepare the resist composition. Solid content refers to all components except the solvent. In the table, the "mass%" column indicates the content (mass%) of each component relative to the total solids in the resist composition. If two or more types of resin (B) are used, each type and its content should be indicated separated by a " / ". The order in which the types and their contents are listed, separated by " / ", corresponds to the order in which they are listed. If two or more of the following are used: compound (A), compound (C), acid diffusion control agent (D), and hydrophobic resin (E), each type and its content should be listed in separate columns. The order in which the separated types and their contents are listed should correspond. Tables 1-4 also list the types and mass ratios of solvents used. The order in which the solvent types and mass ratios are listed corresponds to the order in which they are listed.

[0367] <Pattern formation method (3): EUV exposure, alkaline development (positive)> A base layer formation composition AL412 (manufactured by Brewer Science) is applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer with a thickness of 20 nm. A resist composition shown in Table 7 is applied on top of the base layer and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. A silicon wafer with the obtained resist film is patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 25 nm and a line-to-space ratio of 1:1 is used as the reticle. After exposure, the resist film is 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. This is then spin-dried to obtain a positive-type pattern.

[0368] <Performance Evaluation> [LWR] When a 1:1 line-and-space pattern with a line width of 25 nm is resolved using the optimal exposure amount, the line width is observed from the top of the pattern using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)) and its standard deviation (σ) is calculated. The measurement variability of the line width is evaluated using 3σ, and the value of 3σ is defined as LWR (nm), which is then evaluated according to the following evaluation criteria. A smaller LWR value indicates better LWR performance. An LWR of 4.4 nm or less is preferable.

[0369] [Evaluation Criteria] S:LWR≦3.3 A: 3.3 <LWR≦3.5 B:3.5 <LWR≦3.8 C:3.8 <LWR≦4.1 D:4.1 <LWR≦4.4 E:4.4 <LWR

[0370] The results are shown in Table 7.

[0371] [Table 7]

[0372] <Pattern formation method (4): EUV exposure, organic solvent development (negative)> A base layer formation composition AL412 (manufactured by Brewer Science) is applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer with a thickness of 20 nm. A resist composition shown in Table 8 is applied on top of the base layer and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. A silicon wafer with the obtained resist film is patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 25 nm and a line-to-space ratio of 1:1 is used as the reticle. After exposure, the resist film is baked at 90°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and finally spin-dried to obtain a negative-type pattern.

[0373] The LWR is evaluated using the same method as the performance evaluation for the pattern formation method (3) described above. The results are shown in Table 8.

[0374] [Table 8]

[0375] From these results, it can be seen that the resist composition used in the examples can form patterns with excellent LWR performance.

Claims

1. A photosensitive or radiation-sensitive resin composition comprising a compound (A) represented by the following formula (1) or formula (2), and a resin (B) whose polarity increases upon the action of an acid. 【Chemistry 1】 In formula (1), R １ and R ２ Each of these independently represents an organic group. １ and R ２ These may be joined together to form a ring. L １ This represents a single bond or a divalent linking group. M ａ ｎ＋ This represents an n-valent cation. n represents an integer greater than or equal to 1. 【Chemistry 2】 In formula (2), L ２ This represents a single bond or a divalent linking group. W represents a cyclic group. M ｂ ｍ＋ represents a cation with a valence of m. m represents an integer greater than or equal to 1.

2. R in formula (1) １ and R ２ However, each may independently have a hydrocarbon group (R) which may have a heteroatom. １ and R ２ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the elements may bond to each other to form a ring.

3. L in formula (1) １ , or L in formula (2) above ２ However, -CO- or -SO ２ - The photosensitive or radiation-sensitive resin composition according to claim 1.

4. R in formula (1) １ and R ２ The photosensitive or radiation-sensitive resin composition according to claim 2, wherein at least one of the members has an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom.

5. R in formula (1) １ and R ２ The photosensitive or radiation-sensitive resin composition according to claim 4, wherein at least one of the members has an alicyclic hydrocarbon group which may have a heteroatom.

6. In formula (1) above, M ａ ｎ＋ , or M in formula (2) above ｂ ｍ＋ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the cation is a sulfonium cation or an iodonium cation.

7. A resist film formed using the photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 6.

8. A pattern forming method comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 6; exposing the resist film; and developing the exposed resist film using a developer.

9. A method for manufacturing an electronic device, comprising the pattern formation method described in claim 8.

10. A compound represented by the following formula (1) or formula (2). 【Transformation 3】 In formula (1), R １ and R ２ Each of these independently represents an organic group. １ and R ２ These may be joined together to form a ring. L １ This represents a single bond or a divalent linking group. M ａ ｎ＋ This represents an n-valent cation. n represents an integer greater than or equal to 1. 【Chemistry 4】 In formula (2), L ２ This represents a single bond or a divalent linking group. W represents a cyclic group. M ｂ ｍ＋ This represents a cation with an m-valence. m represents an integer greater than or equal to 1.

11. R in formula (1) １ and R ２ However, each may independently have a hydrocarbon group (R) which may have a heteroatom. １ and R ２ The compound according to claim 10, wherein the elements may bond to each other to form a ring.

12. L in equation (1) １ , or L in formula (2) above ２ However, -CO- or -SO ２ - The compound according to claim 10.

13. R in formula (1) １ and R ２ The compound according to claim 11, wherein at least one of the members is an alicyclic hydrocarbon group which may have a heteroatom, or an aromatic hydrocarbon group which may have a heteroatom.

14. R in formula (1) １ and R ２ The compound according to claim 13, wherein at least one of the members has an alicyclic hydrocarbon group which may have a heteroatom.

15. In formula (1) above, M ａ ｎ＋ , or M in formula (2) above ｂ ｍ＋ The compound according to claim 10, wherein the compound is a sulfonium cation or an iodonium cation.

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