Active light-sensitive or radiation-sensitive resin composition, active light-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic device

Abstract

The present invention provides: an active light-sensitive or radiation-sensitive resin composition that contains (A) a resin which has a group that is decomposed by the action of an acid, thereby generating a carboxy group or a hydroxyl group, and which has a repeating unit (a) that is represented by a specific general formula (a); an active light-sensitive or radiation-sensitive film which uses the active light-sensitive or radiation-sensitive resin composition; a pattern forming method; and a method for manufacturing an electronic device.

Description

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

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

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

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] Various resins are known for use in actinic ray-sensitive or radiation-sensitive resin compositions. For example, Patent Document 1 specifically describes an actinic ray-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit derived from t-butylcinnamic acid.

[0005] U.S. Patent No. 6,312,870

[0006] In recent years, progress has been made in miniaturizing patterns, and further improvements in the performance of actinic ray-sensitive or radiation-sensitive resin compositions for forming such patterns are required. However, the actinic ray-sensitive or radiation-sensitive resin composition described in Patent Document 1 leaves room for further improvement in resolution, line width roughness (LWR) performance, and pattern shape of the obtained pattern. LWR performance refers to the ability to reduce the LWR of the pattern.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can obtain a good pattern shape in the formation of an ultrafine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a hole pattern with a hole diameter of 50 nm or less, etc.) Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing the following resin (A): (A) a resin having a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group, the resin containing a repeating unit (a) represented by the following general formula (a):

[0010]

[0011] In general formula (a), R １０１ and R １０２each independently represents a hydrogen atom or a substituent; A represents an aromatic ring group; R ａ represents a hydrogen atom or a substituent.

[0012] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin (A) further contains a repeating unit having an acid group in addition to the repeating unit (a). [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit having an acid group is a repeating unit having a phenolic hydroxyl group. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (B):

[0013]

[0014] In general formula (B), R ３ represents a hydrogen atom or a monovalent organic group. ４ and R ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group. ２ represents a single bond or an ester group. ３ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. ６ represents a hydroxyl group or a fluorinated alcohol group. ７ represents a halogen atom, m represents an integer of 1 or more, and n represents 0 or an integer of 1 or more.

[0015] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [2] to [4], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (c):

[0016]

[0017] In general formula (c), R ６１ ~R ６３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ６２ may be bonded to Ar to form a ring, in which case R ６２represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R ６２ When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

[0018] [6] R in the repeating unit (a) ａ [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein R in the repeating unit (a) is a group that is decomposed and eliminated by the action of a hydrogen atom or an acid. ａ is a group that is decomposed and eliminated by the action of an acid and is a group represented by the following general formula (b):

[0019]

[0020] In general formula (b), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group; R ｂ１ ~R ｂ３ Two of R may be linked to each other to form a ring. ｂ１ ~R ｂ３ At least two of the groups are independently an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. * indicates the bonding position.

[0021] [8] R in the above general formula (b) ｂ１ ~R ｂ３ [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the total number of carbon atoms contained in each group of R in the general formula (b) is 5 to 10. ｂ１ is an aryl group or a heteroaryl group, and R ｂ２ is an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0022]

[10] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].

[11] A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9]; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

[12] A method for producing an electronic device, comprising the pattern forming method according to

[11] .

[0023] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can obtain a good pattern shape in the formation of an ultrafine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a hole pattern with a hole diameter of 50 nm or less, etc.). The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0024] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0025] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0026] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0027] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0028] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0029] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0030] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0031] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

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

[0033] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will 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" will be adopted.

[0034] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0035] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A): (A) a resin having a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group, the resin containing a repeating unit (a) represented by the following general formula (a):

[0036]

[0037] In general formula (a), R １０１ and R １０２ each independently represents a hydrogen atom or a substituent; A represents an aromatic ring group; R ａ represents a hydrogen atom or a substituent.

[0038] The reason why the composition of the present invention is capable of providing excellent resolution and LWR performance and a good pattern shape in the formation of ultrafine patterns is not entirely clear, but the present inventors speculate as follows: The resin (A) contained in the composition of the present invention is a resin having a group that decomposes under the action of an acid to generate a carboxy group or a hydroxyl group, and also contains the repeating unit (a). The repeating unit (a) has an aromatic ring group and a -C(=O)OR group on the same carbon atom in the main chain. ａ In a resin in which the same carbon atom in the main chain has the above-mentioned multiple substituents in its side chains, molecular motion of the main chain is suppressed, thereby improving the glass transition temperature (Tg) of the resin. It is presumed that an improvement in the Tg of the resin suppresses the diffusion of generated acid in the actinic ray-sensitive or radiation-sensitive film obtained from the composition of the present invention, improving resolution, LWR performance, and pattern shape.

[0039] The composition of the present invention is typically a resist composition and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be either a resist composition for alkali development or a resist composition for organic solvent development. Of these, a positive resist composition for alkali development is preferred. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0040] <Resin (A)> (A) A resin having a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group, and containing a repeating unit (a) represented by general formula (a) (also referred to as "resin (A)") will be described. Resin (A) preferably has a repeating unit having a group that decomposes under the action of an acid to increase polarity (hereinafter also referred to as "acid-decomposable group"), and is preferably a resin having a repeating unit having an acid-decomposable group (hereinafter also referred to as "acid-decomposable resin"). More specifically, resin (A) is preferably a resin having a repeating unit that decomposes under the action of an acid to generate a carboxy group or a hydroxy group, and has a group that increases polarity.

[0041] Resin (A) is preferably a resin whose solubility in a developer changes under the action of an acid. The resin whose solubility in a developer changes under the action of an acid may be a resin whose solubility in a developer increases under the action of an acid, or a resin whose solubility in a developer decreases under the action of an acid.

[0042] Since the resin (A) has a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group, typically, in the pattern formation method of the present invention, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is suitably formed.

[0043] The resin (A) may have a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group in the following repeating unit (a), in a repeating unit other than the repeating unit (a), or in both, but it is preferable that the group be present in the repeating unit (a).

[0044] (Repeating Unit (a)) The resin (A) contains a repeating unit (a) represented by the following general formula (a).

[0045]

[0046] In general formula (a), R １０１ and R １０２ each independently represents a hydrogen atom or a substituent; A represents an aromatic ring group; R ａ represents a hydrogen atom or a substituent.

[0047] In general formula (a), R １０１ and R １０２ R each independently represents a hydrogen atom or a substituent. １０１ and R １０２ The substituent represented by ══ may be an organic group or a halogen atom.

[0048] R １０１ and R １０２Examples of the organic group represented by include an alkyl group, an alkenyl group, a cycloalkyl group, or an aromatic ring group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 10, and more preferably 2 to 3. The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in this cycloalkyl group is preferably 3 to 8.

[0049] The aromatic ring group may be an aryl group or a heteroaryl group. Examples of the aryl group include an aryl group having 6 to 15 carbon atoms, and specific preferred examples include a phenyl group, a naphthyl group, and an anthryl group. Examples of the heteroaryl group include a heteroaryl group having 2 to 15 carbon atoms, and specific preferred examples include a 5- to 10-membered ring, and specific preferred examples include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group. R １０１ and R １０２ The organic group represented by may further have a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a thiol group, a group that decomposes and leaves when acted upon by the action of an acid (leaving group) as described below, etc. The number of further substituents may be one or more. When two or more substituents are present, they may be bonded to each other to form a ring.

[0050] R １０１ and R １０２ Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0051] In general formula (a), R １０１ and R １０２ are preferably each independently a hydrogen atom or an alkyl group, and R １０１ and R １０２is more preferably a hydrogen atom.

[0052] In formula (a), A represents an aromatic ring group.

[0053] Examples of the aromatic ring group represented by A include an aryl group or a heteroaryl group. Examples of the aryl group include an aryl group having 6 to 15 carbon atoms, and specific preferred examples include a phenyl group, a naphthyl group, and an anthryl group. Examples of the heteroaryl group include a heteroaryl group having 2 to 15 carbon atoms, and examples of the heteroaryl group include 5- to 10-membered rings. Among these, monocyclic or polycyclic aromatic heterocyclic groups having a 5-membered ring skeleton containing S, O, N, Se, or Te are preferred, and 5-membered aromatic heterocyclic groups containing S, O, N, Se, or Te are more preferred. Specific preferred examples include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a group in which S in a thienyl group is replaced with Se or Te, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

[0054] The aromatic ring group represented by A may further have a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a thiol group, a group that decomposes and leaves when acted upon by the action of an acid described below (leaving group), a group containing a group that decomposes when acted upon by the action of an acid described below to generate a carboxy group or a hydroxy group, etc. The further substituent may be one or two or more. When two or more substituents are present, they may be bonded to each other to form a ring.

[0055] In general formula (a), R ａ represents a hydrogen atom or a substituent. ａ The substituent represented by R is not particularly limited as long as it is a monovalent substituent, and examples thereof include an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these. ａ When contains a carbon atom, R ａ The number of carbon atoms in is not particularly limited, but is, for example, 1 to 30, and preferably 1 to 20.

[0056] R ａ can constitute a group that is decomposed and eliminated by the action of an acid (leaving group), or a group that contains a group that is decomposed by the action of an acid to produce a carboxyl group or a hydroxyl group.

[0057] As described above, it is preferable that the resin (A) has, in the repeating unit (a), a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group. ａ It is preferable that the group has the above group, and R ａ is a group that is decomposed and eliminated by the action of an acid, and —C(═O)O—R ａ It is more preferable that the group is one that decomposes under the action of an acid to generate a carboxy group.

[0058] R ａ Examples of the group (leaving group) that decomposes and leaves when acted upon by an acid, represented by the formula (Y1), include groups represented by the formulas (Y1) to (Y4). １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0059] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Each of Rx independently represents 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). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３Preferably, each independently represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining the two 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. １ ~Rx ３In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and bond to form the above-mentioned cycloalkyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a composition for EUV exposure, Rx １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and Rx １ ~Rx ３ The ring formed by combining these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0060] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. In addition, R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８The group formed by bonding together R and another substituent carried on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ The ring formed by bonding these groups together preferably further has a fluorine atom or an iodine atom as a substituent.

[0061] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0062]

[0063] Here, L １ and L ２ Each 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 represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. In addition, L １ and L ２ It is preferred that one of Q, M, and L is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. １ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). ２is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0064] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a composition for EUV exposure, the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn preferably have a fluorine atom and an iodine atom as a substituent.

[0065] R ａ The group that is decomposed and eliminated by the action of an acid (eliminating group) represented by the formula (I) is also preferably a group represented by the following general formula (b).

[0066]

[0067] In general formula (b), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group; R ｂ１ ~R ｂ３ Two of R may be linked to each other to form a ring. ｂ１ ~R ｂ３ At least two of the groups are independently an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. * indicates the bonding position.

[0068] R ｂ１ ~R ｂ３The alkyl group represented by the formula (I) may be a linear or branched alkyl group having 1 to 8 carbon atoms, and is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

[0069] R ｂ１ ~R ｂ３ The cycloalkyl group represented by the formula (I) may be a monocyclic or polycyclic cycloalkyl group having 3 to 10 carbon atoms, preferably a monocyclic cycloalkyl group having 4 to 6 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.

[0070] R ｂ１ ~R ｂ３ The aryl group represented by the formula (I) includes aryl groups having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group.

[0071] R ｂ１ ~R ｂ３ Examples of the heteroaryl group represented by the formula (I) include heteroaryl groups having 2 to 15 carbon atoms, such as a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a group in which S in a thienyl group is replaced with Se or Te, a pyridyl group, a benzofuranyl group, a benzothienyl group, a thienothienyl group, a quinolinyl group, and a carbazolyl group. Among these, a monocyclic or polycyclic aromatic heterocyclic group having a five-membered ring skeleton containing S, O, N, Se, or Te is preferred.

[0072] R ｂ１ ~R ｂ３ The alkenyl group represented by the formula (I) includes alkenyl groups having 2 to 6 carbon atoms, and is preferably an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a 1-methylvinyl group, a 1-propenyl group, an allyl group, or a 2-methyl-1-propenyl group.

[0073] R ｂ１ ~R ｂ３ The alkynyl group represented by the formula (I) includes an alkynyl group having 2 to 6 carbon atoms.

[0074] R ｂ１ ~R ｂ３ two of R may be linked to each other to form a ring; ｂ１ ~R ｂ３When two of these are linked to each other to form a ring, they preferably form a cycloalkyl group or a cycloalkenyl group.

[0075] R ｂ１ ~R ｂ３ Examples of the cycloalkyl group formed by linking two of the above groups together include monocyclic or polycyclic cycloalkyl groups having 3 to 10 carbon atoms, such as monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Of these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.

[0076] R ｂ１ ~R ｂ３ The cycloalkenyl group formed by combining two of the above may be a monocyclic or polycyclic cycloalkenyl group having 3 to 10 carbon atoms, and among these, a monocyclic cycloalkenyl group having 5 to 6 carbon atoms is preferred.

[0077] R ｂ１ ~R ｂ３ The substituent represented by may be further substituted with an organic group. ｂ１ ~R ｂ３ When each group of the above-mentioned substituents represented by R is substituted with an organic group, examples of the organic group include an alkyl group (having 1 to 4 carbon atoms) and an alkoxy group (having 1 to 4 carbon atoms). ｂ１ ~R ｂ３ One of the methylene groups in the above substituent represented by may be replaced by a group having a hetero atom such as a carbonyl group.

[0078] R ｂ１ ~R ｂ３ In the cycloalkyl group and cycloalkenyl group formed by bonding two of the above, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom or a sulfur atom, or a group having a heteroatom such as a carbonyl group or an ester group.

[0079] R ｂ１ ~R ｂ３The total number of carbon atoms contained in each group is preferably 5 to 10. By making the total number of carbon atoms 5 or more, the deprotection reactivity of the protecting group can be increased, which is preferable. Furthermore, the total number of carbon atoms is preferably 10 or less. By making the total number of carbon atoms 10 or less, the cleaved product released from the resin (A) by the acid generated by the compound (B) described below is less likely to remain in the actinic ray-sensitive or radiation-sensitive film, thereby further improving the resolution.

[0080] R ｂ１ is an aryl group or a heteroaryl group, and R ｂ２ is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0081] Examples of groups containing a group that decomposes under the action of an acid to generate a carboxyl group or a hydroxyl group include groups having a structure in which the carboxyl group or hydroxyl group is protected by a group that decomposes and leaves under the action of an acid (leaving group). For example, groups represented by the above formulas (Y1) to (Y4) or groups represented by the above general formula (b) are preferred. Examples of groups represented by the above formulas (Y1) to (Y4) or groups represented by the above general formula (b) having a structure in which the carboxyl group or hydroxyl group is protected include alkyl groups or aryl groups having a structure in which the carboxyl group or hydroxyl group is protected by a group represented by the above formulas (Y1) to (Y4) or groups represented by the above general formula (b). Furthermore, groups represented by the above formulas (Y1) to (Y4) or groups represented by the above general formula (b) may also have a structure in which the carboxyl group or hydroxyl group is protected.

[0082] The substituent represented by Ra may further have a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a thiol group, a group that decomposes and leaves when acted upon by the action of the above-mentioned acid (leaving group), a group containing a group that decomposes when acted upon by the action of the above-mentioned acid to generate a carboxyl group or a hydroxyl group, etc. The further substituent may be one or may be two or more. When two or more substituents are present, they may be bonded to each other to form a ring.

[0083] Rａ is preferably a group that is decomposed and eliminated by the action of a hydrogen atom or an acid, more preferably a group that is decomposed and eliminated by the action of an acid, and even more preferably a group represented by the above general formula (b).

[0084] The repeating unit represented by formula (a) is preferably a repeating unit represented by the following formula (a-1).

[0085]

[0086] In general formula (a-1), R １０１ and R １０２ each independently represents a hydrogen atom or a substituent; A represents an aromatic ring group; R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group; R ｂ１ ~R ｂ３ Two of R may be linked to each other to form a ring. ｂ１ ~R ｂ３ At least two of are independently an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.

[0087] In general formula (a-1), R １０１ , R １０２ , and A is R in the above general formula (a). １０１ , R １０２ In general formula (a-1), R has the same meaning as A, and preferred examples are also the same. ｂ１ ~R ｂ３ represents R in the general formula (b). ｂ１ ~R ｂ３ The same applies to preferred examples.

[0088] Specific examples of the monomer corresponding to the repeating unit (a) are shown below, but the present invention is not limited thereto: Me represents a methyl group.

[0089]

[0090] The resin (A) may contain one type of repeating unit (a) alone or two or more types in combination.

[0091] The content of repeating unit (a) contained in resin (A) (the total content if there are multiple repeating units (a)) is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units of resin (A). By making it 15 mol% or more, the effects of the present invention are more likely to be achieved. Furthermore, the content of repeating unit (a) contained in resin (A) (the total content if there are multiple repeating units (a)) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total repeating units of resin (A).

[0092] (Repeating unit having an acid-decomposable group) As a repeating unit other than the repeating unit (a) that has a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group and thereby increases polarity, known repeating units can be used as appropriate. For example, repeating units that have a group that decomposes under the action of an acid to generate a carboxy group or a hydroxy group and thereby increases polarity, which are contained in known resins disclosed in paragraphs

[0055] to

[0191] of U.S. Patent Application Publication No. 2016 / 0274458 A1, paragraphs

[0035] to

[0085] of U.S. Patent Application Publication No. 2015 / 0004544 A1, and paragraphs

[0045] to

[0090] of U.S. Patent Application Publication No. 2016 / 0147150 A1, can be suitably used.

[0093] The content of the repeating units having an acid-decomposable group contained in the resin (A) (including the repeating unit (a), if there are a plurality of repeating units having an acid-decomposable group, the total content thereof) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %, based on the total repeating units of the resin (A).

[0094] (Repeating unit having an acid group) In addition to the repeating unit (a), the resin (A) preferably further comprises a repeating unit having an acid group. The acid group is preferably an acid group having an acid dissociation constant (pKa) of 13 or less. The acid dissociation constant of the acid group indicates a value calculated using the above software package 1 for the monomer that is the raw material for the repeating unit having an acid group. As the repeating unit having an acid group, a repeating unit having a phenolic hydroxyl group is particularly preferred. In addition to the repeating unit (a), the resin (A) preferably further comprises a repeating unit having a phenolic hydroxyl group.

[0095] The repeating unit having an acid group is preferably a repeating unit represented by formula (B).

[0096]

[0097] R ３ represents a hydrogen atom or a monovalent organic group. ４ -R ８ A group represented by the following formula is preferred. ４ represents a single bond or an ester group. ８ The group may be an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.

[0098] R ４ and R ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0099] L ２ represents a single bond or an ester group. ３ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of aromatic hydrocarbon ring groups include a benzene ring group and a naphthalene ring group. Examples of alicyclic hydrocarbon ring groups include monocyclic or polycyclic ring groups, such as cycloalkyl ring groups. R ６represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). ６ When is a hydroxyl group, L ３ is preferably an (n+m+1)-valent aromatic hydrocarbon ring group. ７ represents a halogen atom. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. m represents an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. n represents 0 or an integer of 1 or more. n is preferably an integer of 1 to 4. It is preferable that (n+m+1) is an integer of 1 to 5.

[0100] The repeating unit having an acid group is also preferably a repeating unit represented by the following general formula (c) (repeating unit (c)): It is preferable that the resin (A) further contains a repeating unit (c) represented by the following general formula (c).

[0101]

[0102] In general formula (c), R ６１ ~R ６３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ６２ may be bonded to Ar to form a ring, in which case R ６２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R ６２ When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

[0103] In general formula (c), R ６１ ~R ６３ represents a hydrogen atom, an organic group, or a halogen atom. ６１ ~R ６３ The organic group represented by is, for example, an alkyl group, a cycloalkyl group, a cyano group, or an alkoxycarbonyl group.

[0104] R ６１ ~R ６３The alkyl group represented by is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0105] R ６１ ~R ６３ The cycloalkyl group represented by may be a monocyclic or polycyclic group. Among them, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is preferred. ６１ ~R ６３ The alkyl group contained in the alkoxycarbonyl group represented by R ６１ ~R ６３ The same alkyl groups as those in the above are preferred.

[0106] R ６２ When R is bonded to Ar to form a ring, ６２ The alkylene group of the above R ６１ ~R ６３ A group in which one arbitrary hydrogen atom has been removed from the alkyl group in the formula (I) is preferred.

[0107] R ６１ ~R ６３ Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0108] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

[0109] In general formula (c), Ar represents a (k+1)-valent aromatic ring group. When k is 1, the divalent aromatic ring group may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or an aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring.

[0110] Specific examples of the (k+1)-valent aromatic ring group when k is an integer of 2 or greater include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (k+1)-valent aromatic ring group may further have a substituent.

[0111] Examples of the substituent that the (k+1)-valent aromatic ring group may have include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.

[0112] Ar is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. The repeating unit represented by general formula (c) preferably has a hydroxystyrene structure. That is, Ar is preferably a benzene ring group, more preferably a phenylene group (divalent benzene ring group).

[0113] In the general formula (c), L represents a single bond or a divalent linking group. The divalent linking group represented by L is, for example, *-X ４ -L ４ In the above formula, X ４ represents a single bond, —COO—, or —CONR ６４ represents -, and R ６４ represents a hydrogen atom or an alkyl group. ４represents a single bond or an alkylene group. * represents the bonding position to a carbon atom of the main chain in general formula (c), and ** represents the bonding position to Ar.

[0114] X ４ -CONR ６４ - (R ６４ represents a hydrogen atom or an alkyl group) ６４ Examples of the alkyl group of X include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or less carbon atoms are preferred. ４ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

[0115] L ４ The alkylene group in is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.

[0116] L is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond.

[0117] In formula (c), k represents an integer of 1 to 5. k is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0118] The repeating unit having an acid group is preferably a repeating unit represented by the following general formula (1).

[0119]

[0120] In general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are multiple Rs, they may be the same or different. When there are multiple Rs, they may combine with each other to form a ring. R is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (3-a).

[0121] Specific examples of repeating units having an acid group are shown below, but the present invention is not limited to these. In the formula, a represents an integer of 1 to 3.

[0122]

[0123]

[0124]

[0125] Among the above repeating units, the repeating units specifically described below are preferred: In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0126]

[0127] The content of the repeating unit having an acid group is preferably from 10 to 80 mol %, more preferably from 15 to 75 mol %, and even more preferably from 20 to 70 mol %, based on all repeating units in the resin (A).

[0128] (Repeating Unit Having a Lactone Group or a Sultone Group) The resin (A) may further have a repeating unit having a lactone group or a sultone group. Any group having a lactone structure or a sultone structure can be used as the lactone group or sultone group. Preferably, the lactone group or sultone group is a group having a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure, and more preferably, a group in which another ring structure is fused to the 5- to 7-membered cyclic lactone structure in the form of a bicyclo structure or a spiro structure, or a group in which another ring structure is fused to the 5- to 7-membered cyclic sultone structure in the form of a bicyclo structure or a spiro structure. It is more preferred to have a repeating unit having a group having a lactone structure represented by any of the following general formulae (LC1-1) to (LC1-21) or a group having a sultone structure represented by any of the following general formulae (SL1-1) to (SL1-3). Furthermore, the group having a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures include groups represented by general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-6), general formula (LC1-13), and general formula (LC1-14).

[0129]

[0130] The lactone structure portion or the sultone structure portion may be a substituent (Rb ２ ) may have a preferable substituent (Rb ２ ) includes an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ２ may be different, and multiple Rb ２ They may be bonded to each other to form a ring.

[0131] Examples of the repeating unit having a group having a lactone structure or a sultone structure include a repeating unit represented by the following general formula (AI).

[0132]

[0133] In general formula (AI), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ Preferred substituents that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０ Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these. Among these, a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group having a lactone structure or a sultone structure. As the group having a lactone structure or a sultone structure represented by V, a group represented by any of general formulas (LC1-1) to (LC1-21) and general formulas (SL1-1) to (SL1-3) is preferred.

[0134] A repeating unit having a group having a lactone structure or a sultone structure usually has optical isomers, and any of these optical isomers may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0135] Specific examples of repeating units having a group having a lactone structure or a sultone structure are listed below, but the present invention is not limited to these. ３ , C.H. ２ OH, or CF ３ Represents.

[0136]

[0137]

[0138] The content of the repeating unit having a lactone group or a sultone group is preferably from 1 to 60 mol %, more preferably from 5 to 50 mol %, and even more preferably from 10 to 40 mol %, based on all repeating units in the resin (A).

[0139] (Repeating unit having a fluorine atom or an iodine atom) The resin (A) may have a repeating unit having a fluorine atom or an iodine atom. Examples of the repeating unit having a fluorine atom or an iodine atom include the repeating units described in paragraphs 0080 to 0081 of JP 2019-045864 A.

[0140] (Repeating unit having a photoacid generating group) The resin (A) may have a repeating unit having a group that generates an acid upon irradiation with radiation as a repeating unit other than the above. Examples of the repeating unit having a photoacid generating group include the repeating units described in paragraphs 0092 to 0096 of JP 2019-045864 A.

[0141] (Repeating Unit Having an Alkali-Soluble Group) The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulfonylimide group, and an aliphatic alcohol (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. The resin (A) having a repeating unit having an alkali-soluble group improves resolution in contact hole applications. Examples of the repeating unit having an alkali-soluble group include repeating units in which the alkali-soluble group is directly bonded to the main chain of the resin, such as repeating units based on acrylic acid and methacrylic acid, or repeating units in which the alkali-soluble group is bonded to the main chain of the resin via a linking group. The linking group may have a monocyclic or polycyclic hydrocarbon structure. The repeating unit having an alkali-soluble group is preferably a repeating unit based on acrylic acid or methacrylic acid.

[0142] (Repeating unit having neither an acid-decomposable group nor a polar group) The resin (A) may further have a repeating unit having neither an acid-decomposable group nor a polar group. The repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure.

[0143] Examples of repeating units having neither an acid-decomposable group nor a polar group include the repeating units described in paragraphs 0236 to 0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0144] In addition to the repeating structural units described above, the resin (A) may have various repeating units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0145] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as measured by GPC in terms of polystyrene, 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 dispersity (molecular weight distribution, Pd, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0146] The resin (A) contained in the composition of the present invention may be one type or two or more types.

[0147] In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9 mass %, more preferably 60.0 to 90.0 mass %, based on the total solid content of the composition of the present invention. The resin (A) may be used alone or in combination.

[0148] <(B) Compound that generates an acid upon irradiation with actinic rays or radiation> The composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (also referred to as "compound (B)", "photoacid generator", or "photoacid generator (B)"). The photoacid generator may be in the form of a low molecular weight compound, or may be in the form incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular restriction on the lower limit, but 100 or more is preferable. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of -10 or more and 5 or less upon irradiation with actinic rays or radiation.

[0149] The compound (B) is preferably a compound represented by the following general formula (1).

[0150]

[0151] In general formula (1), R １ and R ５ R each independently represents an aryl group or a heteroaryl group. ２ ~R ４ each independently represents a hydrogen atom or a substituent. ｎ＋ represents a cation, and n represents an integer of 1 or more.

[0152] The compound represented by general formula (1) has an aromatic ring group such as an aryl group or a heteroaryl group, or a sulfo group. Therefore, due to the action of π-π interaction with the aromatic ring group of the repeating unit (a) in the resin (A) and hydrogen bonding with the ester bond of the repeating unit (a), the compatibility between the resin (A) and the compound (B) is increased, resulting in a more uniform material distribution, and thereby enabling further improvement in LWR performance and pattern shape.

[0153] R １ and R ５The aryl group as R is, for example, an aryl group having 6 to 15 carbon atoms, and specific preferred examples include a phenyl group, a naphthyl group, and an anthryl group. １ and R ５ Examples of the heteroaryl group as R include heteroaryl groups having 2 to 15 carbon atoms, and 5- to 10-membered rings, and specific examples include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. ２ ~R ４ The substituent as the radical is not particularly limited as long as it is a monovalent substituent, and examples thereof include an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these.

[0154] R ２ ~R ４ Examples of the alkyl group include alkyl groups having 1 to 30 carbon atoms. Preferred alkyl groups are those having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, and more preferably those having 1 to 8 carbon atoms.

[0155] R ２ ~R ４ The alkenyl group as R may be, for example, an alkenyl group having 2 to 30 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms is preferred. ２ ~R ４ The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 8.

[0156] R ２ ~R ４ The aryl group as R is, for example, an aryl group having 6 to 15 carbon atoms, and specific preferred examples include a phenyl group, a naphthyl group, and an anthryl group.２ ~R ４ Examples of the halogen atom as include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0157] Examples of groups containing a hetero atom include a hydroxyl group, a carboxyl group, an alkoxy group, a thiol group, a thioether group, a nitro group, a nitroso group, a cyano group, an amino group, an acyloxy group, an acylamide group, a heteroaryl group, an ether bond, a carbonyl bond, and combinations of two or more of these.

[0158] The number of carbon atoms in the alkoxy group, acyloxy group, and acylamide group is preferably 20 or less, and more preferably 8 or less. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butyloxy group, a t-butoxy group, and an octyloxy group. Among these, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a t-butoxy group are particularly preferred. The thioether group is also similar to the alkoxy group, except that a sulfur atom is used instead of an oxygen atom. An example of the acyloxy group is an acetyloxy group. An example of the acylamide group is an acetylamide group. Examples of the heteroaryl group include R １ and R ５ Examples of the heteroaryl group include the same as those mentioned above.

[0159] R １ and R ５ The aryl group and heteroaryl group as may further have a substituent. Examples of the further substituent include an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these. The alkyl group; the alkenyl group; the cycloalkyl group; the aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these are each represented by R ２ ~R ４The specific examples of the substituent as R are the same as the alkyl group, alkenyl group, cycloalkyl group, aryl group, halogen atom, group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom, and combinations of two or more of these. １ and R ５ When the aryl group or heteroaryl group has a plurality of substituents, at least two of the substituents may be bonded to each other to form a ring.

[0160] R ２ ~R ４ The alkyl group, alkenyl group, cycloalkyl group, aryl group, and group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or silicon atom as a substituent of the above may further have a substituent. Examples of the further substituent include an alkyl group, alkenyl group, cycloalkyl group, aryl group, amino group, amido group, ureido group, urethane group, hydroxy group, carboxy group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, and combinations of two or more of these.

[0161] The above R １ and R ５ can constitute a group containing a polar group as described below, a group containing a group that decomposes under the action of an acid to increase its polarity, or a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer. ２ ~R ４ can constitute a group containing a polar group described below, a group containing a group that is decomposed by the action of an acid to increase its polarity, or a group containing a group that is decomposed by the action of an alkaline developer to increase its solubility in the alkaline developer.

[0162] In the above general formula (1), R ３ Preferably, R represents an aryl group. ３ The aryl group as R １ and R ５ Examples of the aryl group include the same as the aryl group as R ３ The aryl group as R may further have a substituent. １and R ５ Specific examples of the substituent that may be further possessed by R include the groups described above. ３ When the aryl group as has a plurality of substituents, at least two of the substituents may be bonded to each other to form a ring.

[0163] In the above general formula (1), R １ ~R ５ At least one of the groups is preferably a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase its polarity, or a group containing a group that is decomposed by the action of an alkaline developer to increase its solubility in the alkaline developer.

[0164] R １ ~R ５ Examples of the polar group in the group containing a polar group, which is at least one of the above, include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.

[0165] The alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, excluding aliphatic alcohols (e.g., hexafluoroisopropanol group) in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).

[0166] The group containing a polar group may also include a group having a carbonyl bond. Examples of the group having a carbonyl bond include an alkylcarbonyl group and an arylcarbonyl group. Examples of the alkyl group in the alkylcarbonyl group include R ２ ~R ４ Examples of the aryl group in the arylcarbonyl group include those similar to the alkyl group represented by R １ and R ５ The group having a carbonyl bond is a group in which the carbonyl bond and the ether bond are not adjacent to each other.

[0167] The alkylcarbonyl group and arylcarbonyl group as groups having a carbonyl bond may further have a substituent. Examples of the further substituent include an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these. The alkyl group; the alkenyl group; the cycloalkyl group; the aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these are each represented by R ２ ~R ４ aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these in the specific examples of the substituent as

[0168] The group containing a polar group is not particularly limited, but can include an organic group containing a polar group. Examples of the organic group containing a polar group include an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a group that is a combination of two or more of these and has a polar group. The alkyl group; the alkenyl group; the cycloalkyl group; the aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and a combination of two or more of these are each represented by R ２ ~R ４ aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these in the specific examples of the substituent as

[0169] Examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group. Examples of the alkyl group in the alkyl group containing a polar group include R ２ ~R ４ Examples of the aryl group in the aryl group containing a polar group include the aryl group represented by R １ and R ５ Examples of the aryl group include the same as the aryl group as mentioned above. Furthermore, the group containing a polar group may be the polar group itself.

[0170] R １ ~R ５ The group that decomposes under the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group") in the group containing the group that decomposes under the action of an acid to increase its polarity, as at least one of the above, preferably has a structure in which the polar group is protected with a group that decomposes under the action of an acid and leaves (leaving group). １ ~R ５ At least one of the above may be the same as the polar group in the group containing a polar group.

[0171] Examples of the group that decomposes and leaves under the action of an acid (leaving group) include those described in paragraphs

[0030] to

[0035] and

[0037] to

[0039] of WO 2022 / 024928.

[0172] The group containing an acid-decomposable group is not particularly limited as long as it contains an acid-decomposable group, and examples thereof include organic groups containing an acid-decomposable group. Examples of organic groups containing an acid-decomposable group include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these groups that contain an acid-decomposable group. The alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these groups are each represented by R ２ ~R ４ aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these in the specific examples of the substituent as

[0173] Examples of the group containing an acid-decomposable group include an alkyl group containing an acid-decomposable group and an aryl group containing an acid-decomposable group. Examples of the alkyl group in the alkyl group containing an acid-decomposable group include R ２ ~R ４ Examples of the aryl group in the aryl group containing an acid-decomposable group include those similar to the alkyl group represented by R １ and R ５ Examples of the aryl group include the same as the aryl group in the above formula (1). Furthermore, the group containing an acid-decomposable group may be the acid-decomposable group itself.

[0174] R １ ~R ５Among the groups containing a group that is decomposed by the action of an alkaline developer and increases the solubility in an alkaline developer, the group that is decomposed by the action of an alkaline developer and increases the solubility in an alkaline developer is also called a "polarity conversion group", and specific examples thereof include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate ester group (-OC(O)O-), a sulfate ester group (-OSO ２ O-), sulfonate ester group (-SO ２ O-) and the like.

[0175] Examples of groups containing a polarity conversion group include an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and an imide group.

[0176] The number of carbon atoms in the acyl group in the acyloxy group is preferably 1 to 30, more preferably 1 to 8. The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group is preferably 1 to 30, more preferably 1 to 8.

[0177] The number of carbon atoms in the aryl group in the aryloxycarbonyloxy group is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the aryl group in the aryloxycarbonyl group is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1 to 30, more preferably 1 to 8. The imido group is a group in which one hydrogen atom has been removed from imide.

[0178] The acyloxy group, the alkoxycarbonyloxy group, the aryloxycarbonyloxy group, the aryloxycarbonyl group, the alkoxycarbonyl group, the carbamoyl group, and the imido group may further have a substituent. １ and R ５ Specific examples of the substituent that may be further substituted include the groups described above.

[0179] In one preferred embodiment of the present invention, the polarity conversion group is a group represented by X in the partial structure represented by general formula (KA-1) or (KB-1).

[0180]

[0181] X in the general formula (KA-1) or (KB-1) represents a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, a carboxylic acid thioester group: -COS-, a carbonate ester group: -OC(O)O-, or a sulfate ester group: -OSO ２ O-, sulfonic acid ester group: -SO ２ represents O-. １ and Y ２ may be the same or different and represent an electron-withdrawing group. In one preferred embodiment of the present invention, the compound represented by the general formula (1) has a group having a partial structure represented by the general formula (KA-1) or (KB-1) as a group containing a polarity conversion group, and the partial structure represented by the general formula (KA-1), Y １ and Y ２ When the partial structure does not have a bond, such as in the case of the partial structure represented by (KB-1) where is monovalent, the group having the partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure.

[0182] The partial structure represented by general formula (KA-1) is a structure that forms a ring structure together with the group represented by X. X in general formula (KA-1) is preferably a carboxylic acid ester group (i.e., when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate ester group. A carboxylic acid ester group is more preferred. The ring structure represented by general formula (KA-1) may have a substituent, and may, for example, have a substituent Z ｋａ１ It may have nka of Z. ｋａ１ When there are a plurality of Z, each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group. ｋａ１ They may be linked together to form a ring.ｋａ１ Examples of the ring formed by linking together include a cycloalkyl ring and a heterocycle (such as a cyclic ether ring or a lactone ring). nka represents an integer of 0 to 10. It is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, even more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

[0183] Z ｋａ１ The electron-withdrawing group as Y is typified by a halogen atom. １ and Y ２ The electron-withdrawing group may be substituted with another electron-withdrawing group.

[0184] Z ｋａ１ is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group. The ether group is preferably one substituted with an alkyl group or a cycloalkyl group, i.e., an alkyl ether group, etc. Preferred examples of the electron-withdrawing group include the ether groups Y １ and Y ２ The electron-withdrawing group Z is the same as that of the electron-withdrawing group Z. ｋａ１ Examples of the halogen atom as Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. ｋａ１The alkyl group may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decanyl group. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and examples thereof include an i-propyl group, an i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, an i-hexyl group, a t-hexyl group, an i-heptyl group, a t-heptyl group, an i-octyl group, a t-octyl group, an i-nonyl group, and a t-decanoyl group. Preferred are those having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl groups. ｋａ１ The cycloalkyl group as defined above may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. Preferred monocyclic groups are cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl. Preferred polycyclic groups include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms, and preferred cycloalkyl groups are those having 6 to 20 carbon atoms, such as adamantyl, norbornyl, isobornyl, camphanyl, dicyclopentyl, α-pinel, tricyclodecanyl, tetracyclododecyl, and androstanyl. The following structure is also preferred as a cycloalkyl group. Some of the carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0185]

[0186] Preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group. Substituents for these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. Preferred alkyl groups include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and more preferred are a methyl group, an ethyl group, a propyl group, and an isopropyl group. Preferred alkoxy groups include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

[0187] Z ka１ Examples of the lactone ring group include groups in which a hydrogen atom has been removed from any of the structures represented by (KA-1-1) to (KA-1-17) described below.

[0188] Z ka１ Examples of the aryl group include a phenyl group and a naphthyl group.

[0189] Z ka１Examples of substituents that the alkyl group, cycloalkyl group, and aryl group may further have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl groups, alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group, alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group, a benzyl group, a fluoro ... Examples include aralkyl groups such as eneethyl and cumyl groups, aralkyloxy groups, acyl groups such as formyl, acetyl, butyryl, benzoyl, cyanamyl and valeryl groups, acyloxy groups such as butyryloxy groups, the above-mentioned alkenyl groups, alkenyloxy groups such as vinyloxy, propenyloxy, allyloxy and butenyloxy groups, the above-mentioned aryl groups, aryloxy groups such as phenoxy groups, and aryloxycarbonyl groups such as benzoyloxy groups.

[0190] It is preferred that X in general formula (KA-1) is a carboxylic acid ester group, and that the partial structure represented by general formula (KA-1) is a lactone ring, preferably a 5- to 7-membered lactone ring. As shown in the following (KA-1-1) to (KA-1-17), it is preferred that another ring structure is fused to the 5- to 7-membered lactone ring as the partial structure represented by general formula (KA-1) in the form of a bicyclo structure or a spiro structure. Examples of peripheral ring structures to which the ring structure represented by general formula (KA-1) may be bonded include those shown in the following (KA-1-1) to (KA-1-17) and those similar thereto.

[0191] As the structure containing a lactone ring structure represented by general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferred. The lactone structure may be directly bonded to the main chain. Preferred structures are (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), and (KA-1-17).

[0192]

[0193] The structure containing the lactone ring structure may or may not have a substituent. Preferred substituents include the same as the substituents that may be possessed by the ring structure represented by general formula (KA-1) above.

[0194] Some lactone structures exist in optically active forms, and any of these optically active forms may be used. Furthermore, one type of optically active form may be used alone, or multiple optically active forms may be used in combination. When one type of optically active form is primarily used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

[0195] A preferred example of X in formula (KB-1) is a carboxylic acid ester group (—COO—).

[0196] Y in formula (KB-1) １ and Y ２ each independently represents an electron-withdrawing group.

[0197] The electron-withdrawing group is preferably a partial structure represented by the following formula (EW): In formula (EW), * represents a bond directly bonded to (KA-1) or a bond directly bonded to X in (KB-1).

[0198]

[0199] In formula (EW), n ｅｗ Ha-C(R ｅｗ１ ) (R ｅｗ２ n is the number of repetitions of the linking group represented by -, and represents an integer of 0 or 1. ｅｗ When is 0, it represents a single bond, and Y ｅｗ１ indicates that Y is bonded. ｅｗ１ represents a halogen atom, a cyano group, a nitrile group, a nitro group, or —C(R ｆ１ ) (R ｆ２ )-R ｆ３Examples of the electron-withdrawing group include halo(cyclo)alkyl groups, haloaryl groups, oxy groups, carbonyl groups, sulfonyl groups, sulfinyl groups, and combinations thereof, and the electron-withdrawing group may have the following structure, for example. Note that the term "halo(cyclo)alkyl group" refers to an alkyl group or cycloalkyl group that is at least partially halogenated. R ｅｗ３ , R ｅｗ４ R each independently represents an arbitrary structure. ｅｗ３ , R ｅｗ４ In any structure, the partial structure represented by formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

[0200]

[0201] Y ｅｗ１ When Y is a divalent or higher valent group, the remaining bond forms a bond with any atom or substituent. ｅｗ１ is preferably a halogen atom or —C(R ｆ１ ) (R ｆ２ )-R ｆ３ R is a halo(cyclo)alkyl group or a haloaryl group represented by the formula: ｅｗ１ , R ｅｗ２ R each independently represents an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. ｅｗ１ , R ｅｗ２ and Y ｅｗ１ At least two of these may be linked to each other to form a ring.

[0202] Here, R ｆ１ represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, and even more preferably a fluorine atom or a trifluoromethyl group. ｆ２ , R ｆ３ each independently represents a hydrogen atom, a halogen atom, or an organic group; R ｆ２ and R ｆ３and may be linked to form a ring. The organic group represents, for example, an alkyl group, a cycloalkyl group, an alkoxy group, etc., which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably, R ｆ２ , R ｆ３ is a (halo)alkyl group. ｆ２ is R ｆ１ or R ｆ３ It is more preferable that R is linked to R to form a ring. ｆ１ and R ｆ３ may be linked to form a ring, and examples of the ring formed include a (halo)cycloalkyl ring and a (halo)aryl ring. ｆ１ ~R ｆ３ As the (halo)alkyl group in the formula (I), for example, the above-mentioned Z ｋａ１ and halogenated alkyl groups thereof. ｆ１ ~R ｆ３ In or R ｆ２ and R ｆ３ Examples of the (per)halocycloalkyl group and (per)haloaryl group in the ring formed by linking and include the above-mentioned Z ｋａ１ a structure in which the cycloalkyl group is halogenated, more preferably -C （ｎ） F （２ｎ－２） fluorocycloalkyl groups represented by H, and -C （ｎ） F （ｎ－１） Here, the number of carbon atoms n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0203] R ｅｗ１ , R ｅｗ２ and Y ｅｗ１ The ring that may be formed by bonding at least two of the above is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

[0204] The compound represented by the general formula (1) may have a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or both the partial structure of the general formula (KA-1) and the general formula (KB-1). １ or Y ２ For example, when X in general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group may also serve as an electron-withdrawing group as Y in general formula (KB-1). １ or Y ２ It is also possible for the hydroxyl group to function as an electron-withdrawing group.

[0205] The group containing a polarity conversion group is not particularly limited, but can include an organic group containing a polarity conversion group. Examples of the organic group containing a polarity conversion group include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these groups that have a polarity conversion group. The alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these groups are each represented by R ２ ~R ４ aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these in the specific examples of the substituent as

[0206] Examples of the group containing a polarity conversion group include an alkyl group containing a polarity conversion group and an aryl group containing a polarity conversion group. Examples of the alkyl group in the alkyl group containing a polarity conversion group include R ２ ~R ４ Examples of the aryl group in the aryl group containing a polarity conversion group include those similar to the alkyl group represented by R １ and R ５Examples of the aryl group include the same as the aryl group as mentioned above.

[0207] In the above general formula (1), R １ , R ３ , and R ５ are preferably groups represented by the following general formula (Ar).

[0208]

[0209] In the general formula (Ar), R ６ ~R １０ R each independently represents a hydrogen atom or a substituent. ６ ~R １０ At least one of the groups is a group containing a polar group, a group containing a group that decomposes under the action of an acid to increase its polarity, or a group containing a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer. * represents a bond to the benzene ring in general formula (1).

[0210] R ６ ~R １０ Specific examples of the substituent as R ２ ~R ４ The specific examples of the substituents are the same as those of R. ６ ~R １０ At least one of R is a group containing a polar group, a group containing a group that decomposes under the action of an acid to increase its polarity, or a group containing a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer. １ ~R ５ The group containing a group that is decomposed by the action of an acid to increase its polarity is the same as the group containing a polar group, which is at least one of R １ ~R ５ The group containing a group that is decomposed by the action of an acid and has increased polarity, which is at least one of R １ ~R ５ The present invention is similar to the group containing at least one of the groups that is decomposed by the action of an alkaline developer and has an increased solubility in the alkaline developer.

[0211] In addition, in the general formula (1), R１ , R ３ , and R ５ are preferably groups represented by the following general formula (Ar1).

[0212]

[0213] In general formula (Ar1), R １１ ~R １５ each independently represents a hydrogen atom or a substituent, R １１ ~R １５ At least one of the * represents a bond to the benzene ring in general formula (1). Substituent Y: a hydroxy group, a carboxyl group, a group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, or an imido group.

[0214] R １１ ~R １５ Specific examples of the substituent as R ２ ~R ４ The specific examples of the substituents are the same as those of R. １１ ~R １５ At least one of these represents the substituent Y.

[0215] Specific examples of the group having a carbonyl bond as the substituent Y are the same as the specific examples of the group having a carbonyl bond as the group having a polar group described above. The number of carbon atoms in the acyl group in the acyloxy group as the substituent Y is preferably 1 to 30, more preferably 1 to 8. The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group as the substituent Y is preferably 1 to 30, more preferably 1 to 8. The number of carbon atoms in the aryl group in the aryloxycarbonyl group as the substituent Y is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the aryl group in the aryloxycarbonyl group as the substituent Y is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group as the substituent Y is preferably 1 to 30, more preferably 1 to 8. The imido group as the substituent Y is a group obtained by removing one hydrogen atom from imide.

[0216] The group having a carbonyl bond, the acyloxy group, the alkoxycarbonyloxy group, the aryloxycarbonyloxy group, the aryloxycarbonyl group, the alkoxycarbonyl group, and the imide group as the substituent Y may further have a substituent. １ and R ５ Specific examples of the substituent that may be further substituted include the groups described above.

[0217] In the anion moiety of general formula (1), n ​​represents the number of anions. n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is, for example, 4. n is preferably 1.

[0218] M in the above general formula (1) ｎ＋ represents a cation. In the cation moiety of general formula (1), n ​​represents the valence of the cation. n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is, for example, 4. It is preferable that n is 1. M ｎ＋The cation as is not particularly limited as long as it is a cation with a valence of one or more, but is preferably an onium cation, and more preferably a cation represented by the following general formula (ZIA) or general formula (ZIIA).

[0219]

[0220] In the above general formula (ZIA), R ２０１ , R ２０２ and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ and R ２０３ The number of carbon atoms in the organic group represented by R is generally 1 to 30, and preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0221] Suitable embodiments of the cation represented by general formula (ZIA) include cations (ZI-11) and (ZI-12) described below. When n is 2 or more, the divalent or higher cation may be a cation having a plurality of structures represented by general formula (ZIA). Examples of such cations include R ２０１ ~R ２０３ and at least one of R of another cation represented by general formula (ZIA) ２０１ ~R ２０３ and a divalent cation having a structure in which at least one of the above is bonded via a single bond or a linking group.

[0222] First, the cation (ZI-11) will be described. The cation (ZI-11) is a cation represented by the formula (ZIA) R ２０１ ~R ２０３is an aryl group, i.e., an arylsulfonium cation. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0223] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

[0224] R ２０１ ~R ２０３The aryl group, alkyl group, and cycloalkyl group may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, or a phenylthio group as a substituent. Examples of the lactone ring group include groups obtained by removing a hydrogen atom from any of the structures represented by (KA-1-1) to (KA-1-17) described above.

[0225] Next, the cation (ZI-12) will be described. The cation (ZI-12) is a cation represented by the formula (ZIA) R ２０１ ~R ２０３ are compounds in which each independently represents an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The organic group having no aromatic ring as R generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group.

[0226] R ２０１ ~R ２０３ The alkyl group and cycloalkyl group in R preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0227] Next, the cation (ZI-13) will be described.

[0228]

[0229] In general formula (ZI-13), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond. １ｃ and R ２ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. １ｃ and R ２ｃ may be bonded to form a ring. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, or an alkenyl group. ｘ and R ｙ may be bonded to form a ring. １ｃ and R ２ｃ At least two selected from the above may be bonded to form a ring structure, and the ring structure may contain a carbon-carbon double bond.

[0230] In general formula (ZI-13), the alkyl group and cycloalkyl group represented by M are preferably a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a branched alkyl group having 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specific examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a norbornyl group. The aryl group represented by M is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

[0231] The above M may further have a substituent. In this embodiment, for example, M may be a benzyl group. When M has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

[0232] R １ｃ and R ２ｃ Examples of the alkyl group, cycloalkyl group, and aryl group represented by R include the same as those described above for M, and the preferred embodiments thereof are also the same. １ｃ and R ２ｃ may be bonded to form a ring. １ｃ and R ２ｃ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0233] R ｘ and R ｙ Examples of the alkyl group and cycloalkyl group represented by R include the same as those described above for M, and preferred embodiments thereof are also the same. ｘ and R ｙ The alkenyl group represented by the above formula (R) is preferably an allyl group or a vinyl group. ｘ and R ｙ may further have a substituent. In this embodiment, for example, R ｘ and R ｙ Examples of R include a 2-oxoalkyl group and an alkoxycarbonylalkyl group. ｘ and R ｙ Examples of the 2-oxoalkyl group represented by the formula (I) include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specific examples thereof include a 2-oxopropyl group and a 2-oxobutyl group. ｘ and R ｙ Examples of the alkoxycarbonylalkyl group represented by the formula (I) include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). ｘ and R ｙ may be bonded to form a ring. ｘ and R ｙThe ring structure formed by linking these may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

[0234] In general formula (ZI-13), M and R １ｃ may be bonded to form a ring structure, and the ring structure formed may contain a carbon-carbon double bond.

[0235] The cation (ZI-13) is preferably the cation (ZI-13A), which is a phenacylsulfonium cation represented by the following general formula (ZI-13A):

[0236]

[0237] In general formula (ZI-13A), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ As the group, R in the above-mentioned general formula (ZI-13) １ｃ and R ２ｃ The preferred embodiments thereof are also the same. ｘ and R ｙ As the group, R in the above-mentioned general formula (ZI-13) ｘ and R ｙ The preferred embodiments thereof are also the same.

[0238] R １ｃ ~R ５ｃ Two or more of the following, R ｘ and R ｙ may be bonded to each other to form a ring structure, and each ring structure may independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond. ５ｃ and R ６ｃ , R ５ｃ and R ｘmay be bonded to each other to form a ring structure, and each ring structure may independently contain a carbon-carbon double bond. ６ｃ and R ７ｃ may be bonded to each other to form a ring structure. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0239] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding R include a butylene group and a pentylene group. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0240] Next, the cation (ZI-14) will be described. The cation (ZI-14) is represented by the following general formula (ZI-14).

[0241]

[0242] In formula (ZI-14), l represents an integer of 0 to 2. r represents an integer of 0 to 8. １３ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent. R １４ When a plurality of R are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent. １５Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and are bonded to each other to form a ring structure.

[0243] In general formula (ZI-14), R １３ , R １４ and R １５ The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0244] Next, general formula (ZIIA) will be described. In general formula (ZIIA), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0245] R ２０４ and R ２０５The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ ~R ２０５ Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, and a phenylthio group. Examples of the lactone ring group include groups in which a hydrogen atom has been removed from the structure represented by any one of the above (KA-1-1) to (KA-1-17).

[0246] M in general formula (1) ｎ＋ Preferred examples of (cation) are shown below, but the present invention is not limited to these: Me represents a methyl group, and Bu represents an n-butyl group.

[0247]

[0248]

[0249]

[0250] Preferred examples of the anion moiety in general formula (1) are shown below, but the present invention is not limited to these: Me represents a methyl group.

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257] The pKa of the acid generated by the compound (B) is preferably −10 or more and 5 or less.

[0258] Preferred examples of the compound represented by general formula (1) include compounds in which the above anions and the above cations are combined, but the present invention is not limited to these.

[0259] The compound represented by the general formula (1) can be synthesized, for example, by a method using a coupling reaction.

[0260] The coupling reaction can be performed by, for example, Suzuki coupling. The counter cation can be converted to the desired cation M by a known anion exchange method or a conversion method using an ion exchange resin, as described in, for example, JP-A-6-184170. ＋ Examples of coupling reactions include the following:

[0261]

[0262] X represents a halogen atom, A represents an alkyl group, R represents a substituent, and Y represents a group that forms a compound XY by a coupling reaction.

[0263] As the compound (B), in addition to the compound represented by the general formula (1), for example, ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0264] "M ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation. The organic cation is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. Among these, the organic cation is preferably a cation represented by the general formula (ZIA) or the general formula (ZIIA).

[0265] "M ＋ X － In the compound represented by the formula "X － represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0266] Examples of the non-nucleophilic anion include those described in paragraphs

[0284] to

[0289] of WO 2022 / 024928. In addition to the compound represented by general formula (1), examples of compound (B) include other photoacid generators described in paragraphs

[0290] to

[0291] of WO 2022 / 024928.

[0267] The content of the photoacid generator (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention, in order to make the cross-sectional shape of the formed pattern more rectangular. The content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention. The photoacid generator (B) may be used alone or in combination of two or more.

[0268] <Acid Diffusion Controller> The composition of the present invention may contain an acid diffusion controller. The acid diffusion controller traps acid generated from a photoacid generator or the like upon exposure and acts as a quencher to suppress reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are weakly acidic relative to the photoacid generator, and basic compounds (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

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

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

[0156] to

[0163] of WO 2020 / 066824. Specific examples of the onium salt compound (CD) that is a weak acid relative to the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0269] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller.

[0270] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (the total content if multiple types are present) is preferably 0.1 to 15.0 mass%, and more preferably 0.5 to 15.0 mass%, based on the total solid content of the composition of the present invention. In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more types.

[0271] <Hydrophobic Resin> The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (D)") different from resin (A). The hydrophobic resin (D) is preferably designed so as to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. Effects of adding hydrophobic resin (D) include control of the static and dynamic contact angle of water on the surface of the actinic ray-sensitive or radiation-sensitive film, and suppression of outgassing.

[0272] The hydrophobic resin (D) contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of the hydrophobic resin (D) include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0273] When the composition of the present invention contains the hydrophobic resin (D), the content of the hydrophobic resin (D) is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 15.0 mass%, based on the total solid content of the composition of the present invention.

[0274] <Surfactant> The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0275] The surfactant may be used alone or in combination of two or more.

[0276] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably from 0.0001 to 2.0 mass%, more preferably from 0.0005 to 1.0 mass%, and still more preferably from 0.1 to 1.0 mass%, relative to the total solid content of the composition of the present invention.

[0277] <Solvent> The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0278] Combining the above-mentioned solvent with the above-mentioned resin 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 above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and can therefore suppress unevenness in the film thickness of the actinic ray-sensitive or radiation-sensitive film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

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

[0279] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0280] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0281] The term "solid content" refers to all components other than the solvent, and as described above, refers to components that form an actinic ray-sensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the mass of components other than the solvent relative to the total mass of the composition of the present invention. The term "total solid content" refers to the total mass of components excluding the solvent from the entire composition of the present invention. As described above, the term "solid content" refers to components excluding the solvent, and may be, for example, solid or liquid at 25°C.

[0282] <Other Additives> The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0283] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0284] The composition of the present invention is suitable for use as a photosensitive composition for EB or EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, and therefore the number of incident photons is smaller when exposed at the same sensitivity. As a result, the effect of "photon shot noise," in which the number of photons varies stochastically, is significant, leading to deterioration of line edge roughness (LER) and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at a trade-off with the demand for higher sensitivity.

[0285] [Actinic ray- or radiation-sensitive film, pattern forming method] The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The pattern obtained using the composition of the present invention may be either positive or negative, but is preferably positive. The procedure for forming a pattern using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention; Step 2: exposing the actinic ray- or radiation-sensitive film; Step 3: developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure for each of the above steps will be described in detail below.

[0286] (Step 1: Actinic Ray- or Radiation-Sensitive Film Forming Step) Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention.

[0287] An example of a method for forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention is to coat the composition of the present invention on the substrate. It is preferable to filter the composition of the present invention before coating, 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.

[0288] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

[0289] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0290] The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0291] A top coat may be formed on top of the actinic ray-sensitive or radiation-sensitive film using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the actinic ray-sensitive or radiation-sensitive film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the actinic ray-sensitive or radiation-sensitive film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0292] (Step 2: Exposure Step) Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film. Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and include far ultraviolet light with a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam are particularly preferred.

[0293] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0294] (Step 3: Development Step) Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer). The developer is preferably an alkaline developer.

[0295] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0296] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0297] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0298] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0299] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0300] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0301] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0302] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0303] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0304] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0305] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0306] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0307] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferred.

[0308] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0309] [Method for Manufacturing an Electronic Device] The present specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0310] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0311] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0312] <Resin (A)> Resins A-1 to A-16 were used as resins (A). AT-1 to AT-2 were used as resins other than resin (A). For convenience, AT-1 to AT-2 are also listed in the resin (A) column in Table 3 below. Resin (A) was synthesized in accordance with the synthesis method for resin A-1 (Synthesis Example 1) described below.

[0313] Table 1 shows the composition ratio (mol % ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown below. The weight average molecular weight (Mw) and dispersity (Pd=Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of the repeating unit is １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0314]

[0315] The structures of the repeating units a-1 to a-16, b-1 to b-6, b-9 to b-12, c-1, c-3 to c-7, c-10, c-11, and d-1 to d-6 shown in Table 1 are shown below. For a-1 to a-16, the structures of the corresponding monomers are shown.

[0316]

[0317]

[0318]

[0319]

[0320] <Synthesis Example: Synthesis of Resin A-1> A synthesis example of A-1 is shown below. Other resins (A) were synthesized in the same manner.

[0321] (Synthesis of Monomer (a-1))

[0322]

[0323] Atropic acid (4.99 g, 33.7 mmol), 1-ethylcyclopentanol (4.62 g, 40.5 mmol), 50 ml of methylene chloride, and 4-dimethylaminopyridine (4.53 g, 37.1 mmol) were charged and cooled to -10°C. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (7.11 g, 37.1 mmol) was added at -10°C, and the mixture was warmed to room temperature and stirred for 14 hours. The organic phase was washed with purified water, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 3 / 97, volume ratio) to obtain 5.82 g of monomer (a-1). The compound was identified by ESI (electrospray ionization)-MS (mass spectrometry). MS-ESI (positive) m / z=229.3 [M] ＋

[0324] (Synthesis of Resin A-1)

[0325]

[0326] Using (a-1), (b-2), and (c-1) as monomers, each monomer was mixed to a molar ratio of (b-2): (a-1): (c-1) = 69 / 28 / 3, cyclohexanone was added so that the monomer concentration became a 30% by mass solution, and 7 mol% of initiator dimethyl 2,2'-azobis(2-methylpropionate) was added to prepare a monomer solution. Under a nitrogen atmosphere, 0.1 times the mass of cyclohexanone was heated to 85 ° C., and the monomer solution was added dropwise over 2 hours, and then the reaction was continued for another 2 hours at 85 ° C. The resulting resin solution was added dropwise to a 1:9 (volume ratio) mixed solvent of ethyl acetate and n-heptane, and the resin was precipitated, filtered, collected, and then vacuum-dried to obtain resin (A-1) in a yield of 73%.

[0327] The following resins (AX-1) to (AX-7) were used in the comparative examples: The numbers to the bottom right of each repeating unit indicate the content ratio (molar ratio) of each repeating unit.

[0328]

[0329]

[0330] <Photoacid Generator (B)> Of the compounds (B-1) to (B-80) shown in Table 2 below, compounds (B-1) to (B-4), (B-9) to (B-13), (B-20), (B-27), (B-35), (B-38), (B-44), (B-46), (B-48), (B-56), (B-59), (B-63), and (B-77) were used as the photoacid generator (B). Compounds (B-1) to (B-80) are formed by combining a cation shown in Table 2 with an anion shown in Table 2.

[0331] Using the above software package 1, it was confirmed that the pKa of the acids generated by the compounds (B-1) to (B-80) was −10 or more and 5 or less.

[0332]

[0333] The structures of the cations listed in Table 2 are shown below, where Me represents a methyl group and Bu represents an n-butyl group.

[0334]

[0335]

[0336] The structures of the anions listed in Table 2 are shown below, where Me represents a methyl group and Bu represents an n-butyl group.

[0337]

[0338]

[0339]

[0340] The following compounds (BX-1) and (BX-2) were also used as the photoacid generator (B).

[0341]

[0342] <Acid Diffusion Controller> As the acid diffusion controller, the following C-1 to C-14 were used.

[0343]

[0344] <Surfactant> The following surfactants W-1 to W-4 were used: W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicone-based) W-2: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based) W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

[0345] <Solvents> The solvents used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Diacetone alcohol (DAA) S-3: Propylene glycol monomethyl ether (PGME) S-4: Ethyl lactate (EL) S-5: Ethyl 3-ethoxypropionate (EEP) S-6: 2-heptanone (MAK) S-7: Methyl 3-methoxypropionate (MMP) S-8: 3-methoxybutyl acetate S-9: γ-butyrolactone

[0346] <Preparation of Resist Compositions> The components shown in Table 3 were dissolved in the solvents shown in the same table to prepare solutions with the solid content concentrations shown in the same table. These were then filtered through a polyethylene filter with a pore size of 0.02 μm to obtain resist compositions R-1 to R-22 and RX-1 to RX-7. Note that the solid content refers to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples.

[0347]

[0348] <Coating of Resist Composition> The prepared resist composition was applied to a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. Here, 1 inch is 0.0254 m. Note that similar results were obtained even if the Si wafer was replaced with a chromium substrate.

[0349] <Pattern Forming Method (1): EB Exposure, Alkali Development (Positive)> The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, lithography was performed so as to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0350] [Evaluation] The irradiation energy required to resolve a 1:1 line and space pattern with a line width of 50 nm was taken as sensitivity (Eop).

[0351] <L / S Resolution> The limiting resolving power (the minimum line width at which a line and a space (line:space=1:1) are separately resolved) at the exposure dose exhibiting the above sensitivity (Eop) was taken as the resolving power (nm).

[0352] <Line Width Roughness (LWR) Performance> Line width roughness was measured at the above Eop by measuring the line width at 50 arbitrary points within 0.5 μm in the longitudinal direction of a line and space pattern (line:space=1:1) with a line width of 50 nm, determining the standard deviation (σ) and calculating 3σ (nm). A smaller value indicates better performance.

[0353] <Pattern Shape> The cross-sectional shape of a 1:1 line and space pattern with a line width of 50 nm at an irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.) The cross-sectional shape of the line pattern was evaluated as follows: when the ratio of [line width at the top portion (surface portion) of the line pattern / line width at the middle portion of the line pattern (height position half the height of the line pattern)] was 1.1 or more, it was defined as "reverse tapered," when this ratio was 1.03 or more but less than 1.1, it was defined as "slightly reverse tapered," and when this ratio was less than 1.03, it was defined as "rectangle."

[0354] The resist compositions used and the results are shown in Table 4 below.

[0355]

[0356] <Pattern Forming Method (2): EUV Exposure, Alkali Development (Positive)> The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0357] [Evaluation] The resolution, LWR performance, and pattern shape were evaluated in the same manner as described above.

[0358] The resist compositions used and the results are shown in Table 5 below.

[0359]

[0360] The results in Tables 4 and 5 show that the resist compositions used in the examples are excellent in resolution and LWR performance, and can provide excellent pattern shapes.

[0361] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can obtain a good pattern shape in the formation of an ultrafine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a hole pattern with a hole diameter of 50 nm or less, etc.). The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0362] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-148831) filed on September 13, 2023, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray- or radiation-sensitive resin composition containing the following resin (A): (A) A resin having a group that decomposes under the action of an acid to generate a carboxy group or a hydroxyl group, the resin containing a repeating unit (a) represented by the following general formula (a): In general formula (a), R １０１ and R １０２ Each of R independently represents a hydrogen atom or a substituent. A represents an aromatic ring group. ａ represents a hydrogen atom or a substituent.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) further contains a repeating unit having an acid group in addition to the repeating unit (a).

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit having a phenolic hydroxyl group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (B): In general formula (B), R ３ represents a hydrogen atom or a monovalent organic group. ４ and R ５ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group. ２ represents a single bond or an ester group. ３ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. ６ represents a hydroxyl group or a fluorinated alcohol group. ７ represents a halogen atom. m represents an integer of 1 or more. n represents 0 or an integer of 1 or more.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (c): In general formula (c), R ６１ ~R ６３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ６２ may be bonded to Ar to form a ring, in which case R ６２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R ６２ When it bonds with the aromatic ring to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

6. R in the repeating unit (a) ａ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein is a group which is decomposed and eliminated by the action of a hydrogen atom or an acid.

7. R in the repeating unit (a) ａ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein is a group which is decomposed and eliminated by the action of an acid and is a group represented by the following general formula (b): In general formula (b), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group; R ｂ１ ~R ｂ３ Two of R may be linked together to form a ring. ｂ１ ~R ｂ３ At least two of the groups are independently an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. * indicates the bonding position.

8. R in the above general formula (b) ｂ１ ~R ｂ３ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein the total number of carbon atoms contained in each of the groups is 5 to 10.

9. R in the above general formula (b) ｂ１ is an aryl group or a heteroaryl group, R ｂ２ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7 , wherein is an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

10. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2.

11. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

12. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 11.

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