Actinic-ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for producing electronic device, and compound

Abstract

The present invention provides an actinic-ray-sensitive or radiation-sensitive resin composition with which a pattern having a rectangular cross-sectional shape can be formed. An actinic-ray-sensitive or radiation-sensitive resin composition according to the present invention contains a compound (N) represented by formula (1), and a resin.

Description

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

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a method for producing an electronic device, and a compound.

[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 actinic ray- or radiation-sensitive resin compositions (hereinafter simply referred to as "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] For example, Patent Document 1 discloses a resist composition containing a salt represented by the following formula (I) as "a resist composition capable of obtaining a pattern with excellent line edge roughness." In formula (I), R １ and R ２ represents a fluorine atom or a perfluoroalkyl group. ３ represents a hydrogen atom. １ represents a divalent saturated hydrocarbon group, a hydrogen atom contained in the group may be substituted with a fluorine atom, and —CH ２- may be replaced by -O- or -CO-. ２ represents a single bond or an alkylene group, and —CH ２ - may be replaced by -O-, -NH- or -CO-. ４ represents a cyclic hydrocarbon group, and a hydrogen atom contained in the group may be substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom, or an amino group. １＋ represents an organic cation.

[0005] JP 2011-201859 A

[0006] The present inventors have investigated the resist composition described in Patent Document 1 and have found that there is a problem with the cross-sectional shape of the resulting resist pattern, and that there is room for improvement in order to form a pattern that is closer to a rectangular shape.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a rectangular cross-sectional shape. Another object of the present invention is to provide a resist film, a pattern forming method, a device manufacturing method, and a compound.

[0008] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, they have found that the above problems can be solved by the following configuration.

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) represented by the formula (1) described below and a resin. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (N) is a compound represented by the formula (2) described below. [3] R １ [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein m is a hydrogen atom. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein m is 1 or more. ２ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R３ , or -SO ３ -R ３ and R ３ represents a monovalent organic group. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to [4], ２ ) ｒ [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein Z is —SO ３ － [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein X is a single bond. [9] M ＋

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein M is a sulfonium cation or an iodonium cation. ＋is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms.

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

[10] , wherein n is an integer of 3 or more.

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

[11] , further comprising an acid diffusion controller.

[13] The actinic ray-sensitive or radiation-sensitive resin composition according to

[12] , wherein the acid diffusion controller is a compound selected from the group consisting of a basic compound (CA), a low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. However, when the compound (CC) is an onium salt compound (CD) that is relatively weakly acidic compared to the compound (N), the onium salt compound (CD) is a compound containing an anion moiety represented by any one of formulas (BB-1) to (BB-7) described below.

[14] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to

[13] .

[15] A pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to

[13] ; exposing the resist film; and developing the exposed resist film using a developer.

[16] A method for manufacturing an electronic device, comprising the pattern forming method described in

[15] .

[17] A compound represented by formula (21) described below.

[0010] According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a rectangular cross-sectional shape. The present invention also provides a resist film, a pattern forming method, a device manufacturing method, and a compound.

[0011] 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.

[0012] 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. In this specification, "exposure" refers to not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0013] 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. In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Furthermore, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0014] 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).

[0015] 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:

[0016] (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, an acryloyl group, a methoxy group, a methyl ... Examples of the substituent T include acyl groups such as an acrylyl group and a methoxalyl group; a sulfanyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxy groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (e.g., a monoalkylamino group, a dialkylamino group, an arylamino group, a trifluoromethyl group, etc.).

[0017] 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".

[0018] 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).

[0019] 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.

[0020] 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.

[0021] In this specification, "solids" refers to components contained in an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition") that form a resist film, and does not include solvents. Furthermore, any component contained in a resist composition that forms a resist film is considered to be a solid, even if it is in a liquid state.

[0022] [Actinic Ray- or Radiation-Sensitive Resin Composition] The actinic ray- or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as "resist composition") will be described in detail below. The resist composition of the present invention contains a compound (N) represented by formula (1) described below, and a resin. The resist composition may be either a positive resist composition or a negative resist composition, but is preferably a negative resist composition. Furthermore, the resist composition is preferably a resist composition for organic solvent development. The resist composition may be either a chemically amplified resist composition or a non-chemically amplified resist composition, but is preferably a chemically amplified resist composition.

[0023] Although the reason why the resist composition having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effects are obtained. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still included in the scope of the present invention.

[0024] The resist composition of the present invention contains compound (N). Compound (N) is characterized by having an iodine atom and an amide bond. When the resist composition of the present invention is used, for example, as an EUV resist, the absorption efficiency of EUV light is generally poor, and in particular, EUV light absorption at the bottom of the resist pattern is insufficient, leading to deterioration of the pattern shape, making it difficult to obtain a pattern with high rectangularity. Herein, as described above, compound (N) contains an iodine atom, which increases the absorption efficiency of EUV light. Furthermore, compound (N) contains an amide bond, which improves the dispersibility of compound (N) in the resist composition, making it easy to increase the absorption of EUV light at the bottom of the resist pattern. Therefore, it is presumed that compound (N) having the above-described structure enables the formation of a pattern with a cross-sectional shape that is more rectangular. Hereinafter, the ability to form a pattern with a cross-sectional shape that is more rectangular using the resist composition of the present invention is also referred to as "the effects of the present invention being superior."

[0025] [Compound (N)] The resist composition of the present invention contains compound (N) represented by formula (1). Compound (N) can generate an acid upon irradiation with actinic rays or radiation (hereinafter also referred to simply as "exposure", with EUV light being preferred). In a resist pattern formed using the resist composition, the generation of the acid can create a difference in solubility in a developer between areas irradiated with actinic rays or radiation and areas not irradiated with actinic rays or radiation, allowing the formation of a resist pattern.

[0026] It is preferable that compound (N) generates an acid having a pKa of less than 0 upon exposure. The pKa of the acid generated from compound (N) upon exposure is preferably −0.1 or less, more preferably −0.5 or less. The pKa of the acid generated from compound (N) upon exposure is preferably −4.5 or more, more preferably −3.5 or more. The molecular weight of compound (N) is not particularly limited, but is preferably 500 to 3,000, more preferably 600 to 2,500, and even more preferably 700 to 2,000. Formula (1) will be described in detail below.

[0027]

[0028] In formula (1), Z is —SO３ － , or -SO ２ -N － -SO ２ Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Z represents —SO ３ － is preferred. Rf is preferably an alkyl group having a fluorine atom. In the alkyl group having a fluorine atom, the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. In addition, the number of fluorine atoms in the alkyl group is not particularly limited, but the alkyl group is preferably a perfluoroalkyl group.

[0029] In formula (1), Y is -(CR ２ ) ｒ or an arylene group having the above-mentioned substituent F. Each R independently represents a hydrogen atom or a monovalent substituent, and at least one of R represents the above-mentioned substituent F. Y represents -(CR ２ ) ｒ R is preferably a hydrogen atom or the above-mentioned substituent F, and more preferably a hydrogen atom or a fluorine atom. Among these, -(CR ２ ) ｒ In -, it is preferable that all R are fluorine atoms. Examples of the monovalent substituent represented by R include groups selected from the above-mentioned substituents T. r represents an integer of 1 or more. r is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, and even more preferably 1 or 2.

[0030] The arylene group having the substituent F is preferably an arylene group having a fluorine atom. When the arylene group has a fluorine atom, the number of fluorine atoms in the arylene group is preferably 1 to 6, and more preferably 1 to 4. In the arylene group having a fluorine atom, the number of carbon atoms in the arylene group is preferably 6 to 20, and more preferably 6 to 10. Specific examples of the arylene group include a phenylene group and a naphthylene group, with a phenylene group being preferred.

[0031] In formula (1), X represents a single bond or a divalent linking group. X is preferably a single bond. The divalent linking group represented by X is not particularly limited, but examples thereof include -(CR ｆ ２ ) ｒ - (R ｆ each independently represents a hydrogen atom or a monovalent substituent, R ｆ At least one of the groups represents the substituent F. r represents an integer of 1 or more. ), —CO—, —O—, —S—, —NH—, —SO—, —SO ２ Examples thereof include -, -COO-, -CONH-, an alkylene group (preferably having 1 to 6 carbon atoms, and more preferably having 1 or 2 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these.

[0032] In the above formula (1), R １ represents a hydrogen atom or a monovalent organic group. １ is preferably a hydrogen atom. １ Examples of the monovalent organic group represented by the formula (R) include substituents containing one or more carbon atoms selected from the above-mentioned substituents T. １ Among these, the monovalent organic group represented by the formula (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear.

[0033] L represents a single bond or an alkylene group. When the alkylene group has two or more carbon atoms, the methylene group in the alkylene group may be substituted with —O—, a carbonyl group, —S—, or —NRＮ -, and a divalent linking group selected from a sulfonyl group. Ｎ represents a hydrogen atom or an alkyl group. L is preferably a single bond. The alkylene group represented by L may be linear, branched, or cyclic. The linear alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. The branched alkylene group preferably has 3 to 10 carbon atoms, more preferably 3 to 6. The cyclic alkylene group preferably has 3 to 15 carbon atoms, and more preferably 3 to 10. The methylene group in the alkylene group is preferably substituted with at least one of -O- and a carbonyl group.

[0034] W represents an (n+1)-valent aromatic group which may have a substituent other than an iodine atom. n represents an integer of 1 or greater. n is preferably an integer of 2 or greater, more preferably an integer of 3 or greater. The upper limit of n may be, for example, 10 or less. The aromatic ring constituting the (n+1)-valent aromatic group represented by W may be either a monocyclic or polycyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. The number of ring atoms in the aromatic ring is preferably 5 to 20, more preferably 5 to 15, and even more preferably 6 to 10. When the aromatic ring is an aromatic heterocyclic ring, it preferably has a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. Among these, the aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0035] Examples of the substituent other than an iodine atom that W may have include the substituents other than an iodine atom selected from the above-mentioned substituents T. ｎ Among these, the group represented by formula (W) below is preferred as the group represented by formula (W):

[0036]

[0037] In formula (W), L represents a single bond or an alkylene group. When the alkylene group has two or more carbon atoms, the methylene group in the alkylene group may be —O—, a carbonyl group, —S—, or —NR Ｎ -, and a divalent linking group selected from a sulfonyl group. Ｎ represents a hydrogen atom or an alkyl group. L is preferably a single bond. Specific examples and preferred embodiments of the alkylene group represented by L are as described above.

[0038] In formula (W), Ar represents an (n+m+1)-valent aromatic group. m represents an integer of 0 or greater. m is preferably 1 to 3, and more preferably 1 or 2. The aromatic ring constituting the (n+m+1)-valent aromatic group may be either a monocyclic or polycyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. The number of ring atoms in the aromatic ring is preferably 5 to 20, more preferably 5 to 15, and even more preferably 6 to 10. When the aromatic ring is an aromatic heterocyclic ring, it preferably has a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. Among these, the aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0039] In the above formula (W), R ２ represents a halogen atom other than an iodine atom, or a monovalent organic group. ２ The halogen atom represented by R is preferably a bromine atom. ２ Examples of the monovalent organic group represented by the formula (R) include substituents containing one or more carbon atoms selected from the above-mentioned substituents T. ２ Among them, m R ２ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is preferable that R ３ represents a monovalent organic group.

[0040] Examples of electron-withdrawing groups include those having a positive value as the Hammett's rule substituent constant (σp value). The Hammett's rule substituent constant is a numerical representation of the effect of a substituent on the acid dissociation equilibrium constant of a substituted benzoic acid, and is a parameter indicating the strength of the electron-withdrawing and electron-donating properties of the substituent. In this specification, the Hammett's rule substituent constant refers to the substituent constant σ when the substituent is located at the para position of the benzoic acid. The Hammett's rule substituent constant (σp value) can be cited from "Hansch et al., Chemical Reviews, 1991, Vol. 91, No. 2, 165-195". For groups for which the σp value is not shown in the above literature, the σp value can be calculated using the software "ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08)" based on the difference between the pKa of benzoic acid and the pKa of a benzoic acid derivative having a substituent at the para position.

[0041] Examples of the electron-withdrawing group include -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), and -CO ２ R ＥＷＧ (σp:R ＥＷＧ is an ethyl group, +0.45), -CONH ２ (σp: +0.36), -COR ＥＷＧ (σp:R ＥＷＧ is a methyl group, +0.50), -CF ３ (σp: +0.54), -SO ２ R ＥＷＧ (σp:R ＥＷＧ is a methyl group, +0.72), and -NO ２ (σp: +0.78). ＥＷＧ R each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. ＥＷＧ The aliphatic hydrocarbon group represented by the formula (I) may have an oxygen atom between the carbon-carbon bond, and one or more carbon atoms may be substituted with a carbonyl carbon (C═O). Examples of the substituent include groups selected from the above-mentioned substituent T.

[0042] As mentioned above, m R ２ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is preferable that R ３ represents a monovalent organic group. ２ All of these are -CO-O-R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is preferable that R ３ Examples of the monovalent organic group represented by the formula (R) include substituents containing one or more carbon atoms selected from the above-mentioned substituents T. ３ Among these, an alkyl group having 1 to 10 carbon atoms or -alkylene group-aliphatic heterocyclic group is preferred.

[0043] The alkyl group may be linear, branched, or cyclic, but is preferably linear. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The alkylene group may be linear, branched, or cyclic, but is preferably linear. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. In the aliphatic heterocyclic group, the number of ring atoms in the aliphatic heterocycle is preferably 5 to 20, more preferably 5 to 10. The aliphatic heterocyclic group preferably has at least one of an oxygen atom and a carbonyl carbon as a ring atom. Among these, the aliphatic heterocyclic group is preferably a tetrahydrofuran ring group or an ethylene carbonate ring group.

[0044] In the above formula (1), M ＋ represents a cation. ＋ The cation represented by M is a monovalent cation. There are no particular limitations on the cation, but it is preferable that M represents an organic cation. ＋The cation represented by the formula (I) preferably has a fluorine atom. The number of fluorine atoms contained in the cation is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and even more preferably 5 or more. The upper limit is, for example, 20 or less, and preferably 15 or less. ＋ Among these, sulfonium cations or iodonium cations are preferred, with sulfonium cations having three or more fluorine atoms or iodonium cations having three or more fluorine atoms being more preferred, and sulfonium cations having 3 to 15 fluorine atoms or iodonium cations having 3 to 15 fluorine atoms being even more preferred. As the sulfonium cation, a cation represented by formula (ZaI) described later is preferred, with cation (ZaI-1) described later or cation (ZaI-4b) described later being more preferred. Furthermore, as the iodonium cation, a cation represented by formula (ZaII) described later is preferred.

[0045] In terms of achieving better effects of the present invention, the compound (N) is preferably a compound represented by formula (2), and more preferably a compound represented by formula (21) described below.

[0046]

[0047] In formula (2), Z, Y, X, R １ , n and M ＋ The definitions and preferred embodiments of Y, X, R in the above formula (1) are as follows: １ , n and M ＋ In formula (2), Ar represents an aromatic group having a valence of (n+m+1). m represents an integer of 0 or more. The preferred embodiments of Ar and m are the same as the preferred embodiments of Ar and m in formula (W). Among them, m is preferably an integer of 1 or more, more preferably 1 to 3, and even more preferably 1 or 2. In formula (2), R ２ represents a halogen atom other than an iodine atom, or a monovalent organic group. ２ Specific examples and preferred embodiments of the formula (W) are ２ The specific examples and preferred embodiments are the same as those of the above. ２ At least one of the groups is —CO—O—R３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is preferable that R ３ The definition and preferred embodiments of R in formula (W) ３ The definition and preferred embodiments are the same as those of the above.

[0048] The above formula (21) will be described in detail below. The present invention also includes the invention of a compound, and the above compound is a compound represented by formula (21).

[0049]

[0050] In formula (21), Z is —SO ３ － , or -SO ２ -N － -SO ２ Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Y represents -(CR ２ ) ｒ - or an arylene group having the above-mentioned substituent F. Each R independently represents a hydrogen atom or a monovalent substituent, and at least one R represents the above-mentioned substituent F. r represents an integer of 1 or more. X represents a single bond or a divalent linking group. n represents an integer of 1 or more. M ＋ In formula (21), Z, Y, X, n, and M each represent a cation. ＋ Specific examples and preferred embodiments of the formula (1) include Y, X, n, and M ＋ The specific examples and preferred embodiments are the same as those of the above.

[0051] In formula (21), Ar represents an aromatic group having a valence of (n+q+1). q represents an integer of 1 or more. q is preferably an integer of 1 or more, more preferably 1 to 3, and even more preferably 1 or 2. In formula (21), R ２１ represents a halogen atom other than an iodine atom or a monovalent organic group, and q R ２１ At least one of the groups is —CO—O—R ３ , —O—CO—R ３, -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is. ３ represents a monovalent organic group. ３ Specific examples and preferred embodiments of the formula (W) are ３ The specific examples and preferred embodiments are the same as those of q R ２１ All of these are -CO-O-R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is preferable that:

[0052] The content of compound (N) in the resist composition is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the resist composition. Furthermore, the content of compound (N) is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, and even more preferably 30.0 mass% or less, based on the total solid content of the resist composition. Only one type of compound (N) may be used, or two or more types may be used. When two or more types of compound (N) are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0053] [Photoacid Generator] The resist composition may contain a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also simply referred to as "exposure"), and is a compound other than the above-mentioned compound (N). The photoacid generator preferably generates an acid having a pKa of less than 0 upon exposure. The pKa of the acid generated from the photoacid generator upon exposure is preferably -0.1 or less, more preferably -0.5 or less. Furthermore, the pKa of the acid generated from the photoacid generator upon exposure is preferably -5.0 or more, more preferably -4.5 or more.

[0054] 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 resin. Furthermore, both the form of a low molecular weight compound and the form incorporated into a part of a resin may be used in combination. The photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is not particularly limited, but is preferably 500 to 3000, more preferably 600 to 2500, and even more preferably 700 to 2000. When the photoacid generator is in the form incorporated into a part of a resin, it may be incorporated into a part of an acid-decomposable resin, or may be incorporated into a resin different from the acid-decomposable resin.

[0055] Examples of the photoacid generator include "M ＋ 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.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0056] "M ＋ X － In the compound represented by the formula ", M ＋ represents a cation, preferably an organic cation. The cation may have a valence of monovalent or divalent or higher. The cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0057]

[0058] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ When the resist composition of the present invention is used as an EUV resist, R ２０１ ~R ２０５ It is preferable that the cation represented by formula (ZaI) contains a fluorine atom or an iodine atom as a substituent. Suitable embodiments of the cation represented by formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0059] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, diarylcycloalkylsulfonium cations, aryldialkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0060] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. The alkyl group or cycloalkyl group that the arylsulfonium cation may have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0061] The aryl group may have a substituent, and examples of the substituent 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 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine and iodine), a hydroxy group, a carboxy group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and an alkyloxycarbonylalkyleneoxy group. The substituent may further have a substituent if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferable that the substituents form an acid-decomposable group in any combination. The acid-decomposable group is a group that decomposes under the action of acid to increase its polarity, and preferably has a structure in which a polar group is protected by a group that is eliminated under the action of acid.

[0062] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0063] R ２０１ ~R ２０３Examples of the alkyl group and cycloalkyl group represented by R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxy group, a cyano group, or a nitro group.

[0064] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0065]

[0066] In formula (ZaI-3b), 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 hydroxy group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0067] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙmay be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0068] 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 of R include alkylene groups such as butylene and pentylene. A methylene group in the alkylene group may be substituted with a heteroatom such as an oxygen atom. 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.

[0069] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0070] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0071]

[0072] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxy group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxy group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When there are multiple R, they may be independent or different. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0073] In formula (ZaI-4b), R １３ , R １４ and R １５ The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0074] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R２０５ 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. Alternatively, it may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle 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, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0075] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the 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 hydroxy group, and a phenylthio group.

[0076] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0077]

[0078]

[0079] "M ＋ X － In the compound represented by the formula "X －represents an anion, preferably an organic anion. The valence of the anion may be monovalent or divalent or higher. The anion is preferably an anion with a significantly low ability to cause a nucleophilic reaction, more preferably a non-nucleophilic anion. The organic anion may be used alone or in combination of two or more kinds.

[0080] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0081] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0082] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0083] The alkyl groups, cycloalkyl groups, and aryl groups listed above may have a substituent. Examples of the substituent include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxy group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms). When the resist composition of the present invention is used as an EUV resist, it is preferable that the substituent contain a fluorine atom or an iodine atom, and more preferably contain an iodine atom. There is no limit to the number of fluorine atoms or iodine atoms, but from the viewpoint of the absorption efficiency of EUV light, the more the number, the better.

[0084] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0085] An example of the sulfonylimide anion is a saccharin anion.

[0086] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents on these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure.

[0087] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0088] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, pentafluorobenzenesulfonate anion, and 3,5-bis(trifluoromethyl)benzenesulfonate anion are even more preferred.

[0089] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0090]

[0091] In formula (AN1), R １ and R２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxy groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups, and -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred. R′ is a monovalent hydrocarbon group. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0092] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl.

[0093] L represents a divalent linking group. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0094] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR ２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0095] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different. However, when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ However, X+Y in formula (AN1-1) is 1 or more, and R in formula (AN1-1) ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0096] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may have a substituent, or may have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). Among these, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may have, for example, a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). The heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure.

[0097] The organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and more preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be a monocyclic group (e.g., a cyclohexyl group) or a polycyclic group (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms.

[0098] R ３ Preferably, R contains a halogen atom. ３ The halogen atom contained in is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred. When the resist composition of the present invention is used as an EUV resist, the greater the number of halogen atoms, the better from the viewpoint of EUV light absorption efficiency.

[0099] Examples of the anion represented by formula (AN1) include

[0040] to

[0044] of JP 2018-155908 A,

[0184] to

[0185] ,

[0197] to

[0198] of JP 2021-128331 A,

[0124] to

[0125] ,

[0137] to

[0138] of WO 2022 / 064863, and anions described in

[0056] to

[0061] of JP 2023-177048 A, the above descriptions are incorporated herein.

[0100] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0101]

[0102] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10. L represents a divalent linking group. The definition of L is the same as that of L in formula (AN1).

[0103] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with one or more fluorine atoms, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with one or more fluorine atoms is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that all of Xf are fluorine atoms.

[0104] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms. ４ and R ５ If there are multiple ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0105] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0106] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0107] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group.

[0108] W preferably contains a halogen atom. The halogen atom contained in W is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred. When the resist composition of the present invention is used as an EUV resist, the greater the number of halogen atoms, the better from the viewpoint of the absorption efficiency of EUV light.

[0109] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. q' represents an integer of 0 to 10. L, q and W are the same as in formula (AN2).

[0110] Examples of the anion represented by formula (AN2) include

[0076] in WO 2023 / 157455,

[0071] to

[0089] in JP 2021-081708 A,

[0033] to

[0045] in JP 2018-005224 A,

[0031] to

[0039] in JP 2021 Examples include the anions described in

[0176] to

[0183] ,

[0186] to

[0196] of WO 2022 / 064863,

[0116] to

[0123] ,

[0126] to

[0136] of WO 2023 / 157455, and

[0076] of WO 2023 / 157455, the descriptions of which are incorporated herein by reference.

[0111] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0112]

[0113] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxy group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0114] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0115] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0116] B preferably contains a halogen atom. The halogen atom contained in B is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred. When the resist composition is used as an EUV resist, the greater the number of halogen atoms, the better, from the viewpoint of the absorption efficiency of EUV light.

[0117] Examples of the anion represented by formula (AN3) include the anions described in

[0029] to

[0034] of JP-A-2018-159744,

[0045] of JP-A-2018-155908, and

[0037] to

[0055] and

[0062] to

[0064] of JP-A-2023-177048, and the above descriptions are incorporated herein.

[0118] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ It is an anion represented by R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0119] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0120]

[0121] In formula (d1-1), R ５１represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxy group). Examples of the anion represented by formula (d1-1) include those described in

[0041] to

[0047] of JP 2017-219836 A,

[0026] to

[0028] of JP 2018-155902 A,

[0040] to

[0041] and

[0128] of JP 2020-154212 A,

[0049] to "0061" and

[0278] to

[0279] of JP 2021-091666 A, and those described in WO 2022 / 014444. JP-A-2022-077505

[0013] to

[0015] , JP-A-2022-141598

[0026] to

[0031] ,

[0050] to

[0051] , JP-A-2023-108593

[0147] , and WO 2023 / 157455

[0088] anions described therein are included, and the above descriptions are incorporated herein.

[0122] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃ The hydrocarbon group in the formula (I) may be linear or branched, or may have a cyclic structure. Furthermore, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom in the norbornyl group may be a carbonyl carbon.

[0123] The anion represented by formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above. For example, Z ２ｃ is preferably other than an aryl group. ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ －The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0124] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group. Examples of the anion represented by formula (d1-3) include the anions described in

[0040] to

[0046] of JP 2019-211751 A,

[0039] to

[0047] of JP 2021-128331 A,

[0043] to

[0060] of JP 2021-165824 A, and

[0062] and

[0075] of WO 2023 / 119910, and the above descriptions are incorporated herein.

[0125] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４ may be bonded to each other to form a ring.

[0126] It is also preferable that the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).

[0127] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0128] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0129] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A. ２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the formula ". １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0130] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having "two HAs １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0131] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to the acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0132] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0133] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0134] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0135] Anion site A１ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ － Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any of formulas (BB-1) to (BB-6), and even more preferably any of formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. Ａ The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0136]

[0137]

[0138] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge. ＋ Examples of the organic cation include those represented by the following formula:

[0139] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0140] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in compound (I) and A １ － and M １ ＋ The definition and preferred embodiments are also the same.

[0141] In the compound (II), the cation moiety M in the structural moiety X １ ＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (I) is the same as the acid dissociation constant a1 in the compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound that generates an acid having two HAs. １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0142] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. １ － and two or more of the above M １ ＋ may be the same or different.

[0143] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0144]

[0145] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary amine structure, a secondary amine structure, a tertiary ...

[0146] Examples of moieties other than cations that may be possessed by the compound (I) and the compound (II) include the anions described in paragraphs

[0277] to

[0280] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0147] The content of the photoacid generator in the resist composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of the resist composition. Furthermore, the content of the photoacid generator is preferably 50.0% by mass or less, more preferably 45.0% by mass or less, and even more preferably 40.0% by mass or less, based on the total solid content of the resist composition. Only one photoacid generator may be used, or two or more types may be used. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0148] [Acid Diffusion Controller] The resist composition of the present invention preferably further contains an acid diffusion controller. The acid diffusion controller is a compound different from the compound (N) and the photoacid generator. The acid diffusion controller can trap excess acid generated from at least one of the compound (N) and the photoacid generator upon irradiation (exposure) with actinic rays or radiation, and can act as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to the excess acid.

[0149] The type of acid diffusion controller is not particularly limited, and examples thereof include a compound selected from the group consisting of a basic compound (CA), a low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. The acid diffusion controller is also preferably a compound that generates an acid having a pKa of 0 or more by irradiation with actinic rays or radiation.

[0150] (Basic Compound (CA)) The basic compound (CA) is preferably a compound having a structure represented by any one of the following formulas (A) to (E): In formulas (B), (C), (D), and (E), * represents a bonding position.

[0151]

[0152] In formula (A), R ２００ ~R ２０２ R each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms).２００ ~R ２０２ At least two of R may be bonded to form a ring. ２０３ ~R ２０６ each independently represents an alkyl group having 1 to 20 carbon atoms.

[0153] R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by may have a substituent. With respect to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by is preferably unsubstituted.

[0154] Examples of the basic compound (CA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (CA) may be a compound having at least one selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (CA) may be an alkylamine derivative having at least one selected from the group consisting of a hydroxy group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxy group and an ether bond.

[0155] The difference between the pKa of the conjugate acid of the basic compound (CA) and the pKa of the acid generated from the compound (N) or the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the compound (N) or the photoacid generator from the pKa of the conjugate acid of the basic compound (CA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (CA) is, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0156] Specific examples of the basic compound (CA) include the compounds described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, the disclosure of which is incorporated herein by reference. Specific examples of the low molecular weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid include the compounds described in paragraphs

[0156] to

[0163] of WO 2020 / 066824, the disclosure of which is incorporated herein by reference.

[0157] (Compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation) Specific examples of the compound (CC) include onium salt compounds (CD) of acids that are relatively weaker acids than the compound (N) and the photoacid generator, and basic compounds (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.

[0158] Compound (CD) may be a compound that generates an acid upon exposure to light. Compound (CD) is preferably a compound that generates an acid having a pKa value 1.00 or more higher than that of the acid generated from compound (N) or the photoacid generator. The difference between the pKa of the acid generated from compound (CD) and the pKa of the acid generated from compound (N) or the photoacid generator (the value obtained by subtracting the pKa of the acid generated from compound (N) or the photoacid generator from the pKa of the acid generated from compound (CD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. The pKa of the acid generated from compound (CD) is, for example, preferably 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0159] The compound (CD) is preferably an onium salt compound consisting of an anion and a cation. Examples of the compound (CD) include "M ＋ X － Examples of compounds include compounds (onium salts) represented by the formula "M ＋ represents a cation, and preferably represents an organic cation. ＋ As the photoacid generator, M described above can be used. ＋ The same as above can be mentioned. － represents an anion, and preferably represents an organic anion. － Examples of the anions include those represented by the formulae (d1-1) to (d1-4) described above in the description of the photoacid generator.

[0160] Among these, when the compound (CC) is an onium salt compound (CD) that is a relatively weak acid compared to the compound (N), the onium salt compound (CD) is preferably a compound containing an anion moiety represented by any one of the following formulae (BB-1) to (BB-7):

[0161]

[0162] Specific examples of the onium salt compound (CD) include the compounds described in paragraphs

[0305] to

[0314] of WO 2020 / 158337, the disclosures of which are incorporated herein by reference. Specific examples of the basic compound (CE) include those described in paragraphs

[0137] to

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

[0164] of WO 2020 / 066824, the disclosures of which are incorporated herein by reference.

[0163] In addition to the above-mentioned compounds, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] , can also be suitably used as the acid diffusion controller, and the descriptions above are incorporated herein by reference.

[0164] The molecular weight of the acid diffusion controller is not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000.

[0165] When the resist composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the resist composition. Furthermore, the content of the acid diffusion controller is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 10.0% by mass or less, based on the total solid content of the resist composition. Only one acid diffusion controller may be used, or two or more may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0166] [Resin] The resist composition of the present invention contains a resin. Examples of resins include resins whose polarity increases under the action of acid (hereinafter simply referred to as "acid-decomposable resins"), and hydrophobic resins. The resist composition preferably contains an acid-decomposable resin, and more preferably contains an acid-decomposable resin and a hydrophobic resin. Acid-decomposable resins are described in detail below.

[0167] <Acid-Decomposable Resin> (Repeating Unit Having Acid-Decomposable Group) The acid-decomposable resin contains a repeating unit having an acid-decomposable group (hereinafter also simply referred to as "repeating unit A1"). The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity, and is typically a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a group that leaves under the action of an acid (leaving group). It is preferable that the polarity of the acid-decomposable resin increases under the action of an acid, and the solubility in organic solvents decreases. Examples of the polar group include a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (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, and an acidic group such as an alcoholic hydroxy group. Among these, the polar group is preferably a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0168] Examples of the group that is eliminated by the action of an acid include groups represented by any one of formulas (Y1), (Y2), and (Y3). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(R ３６ ) (R ３７ ) (OR ３８) Formula (Y3): -C(Rn)(H)(Ar)

[0169] In formula (Y1), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an alkynyl group, 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 ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx 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 alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group of Rx is preferably an ethynyl group or a propargyl group. １ ~Rx ３ The aryl group 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.

[0170] Rx１ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by bonding 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 ３ In the cycloalkyl group formed by bonding these two, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. 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) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0171] When the resist composition of the present invention is used as an EUV resist, Rx １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group represented by the formula: １ ~Rx ３ The ring formed by bonding these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0172] In formula (Y2), 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, an alkenyl group, and an alkynyl group. ３６is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl group may contain a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. When the resist composition of the present invention is used as an EUV resist, ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0173] In formula (Y3), 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 preferably an aryl group. When the resist composition of the present invention is used as an EUV resist, it is also preferable that the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0174] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the leaving group protecting the polar group, it is also preferable that the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0175] The group that is eliminated by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0176] The repeating unit A1 is also preferably a repeating unit represented by formula (A).

[0177]

[0178] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; R ２ represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. １ , R １ and R ２ At least one of L has a fluorine atom or an iodine atom. １ Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0179] R １ The alkyl group represented by R 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. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by the formula (I), is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by the formula (I) may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0180] R ２ Examples of the leaving group represented by the formula (Y1), (Y2), or (Y3) above, which may have a fluorine atom or an iodine atom, include leaving groups represented by the formula (Y1), (Y2), or (Y3) above, which have a fluorine atom or an iodine atom.

[0181] The repeating unit A1 is also preferably a repeating unit represented by formula (AI).

[0182]

[0183] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an alkynyl group, or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0184] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or a —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group. １１ Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0185] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH ２ -, -(CH ２ ) ２ - or -(CH ２ ) ３ - is more preferable.

[0186] Rx １ ~Rx３ The alkyl group of Rx 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. 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 alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group of Rx is preferably an ethynyl group or a propargyl group. １ ~Rx ３ The aryl group 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.

[0187] Rx １ ~Rx ３ As the cycloalkyl group formed by bonding the two above, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ In the cycloalkyl group formed by bonding the two above, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the formula (AI), for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0188] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0189] The repeating unit represented by formula (AI) may be an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa １ represents a hydrogen atom or a methyl group, and T represents a single bond).

[0190] The repeating unit A1 may have an acid-decomposable group containing an unsaturated bond. As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferred.

[0191]

[0192] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry １ ~Ry ３ each independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ At least one of R represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0193] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0194] Examples of the divalent linking group represented by L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group. Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. Rt may have a substituent such as a halogen atom, a hydroxy group, or an alkoxy group. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group.

[0195] Ry １ ~Ry ３ The alkyl group represented by the formula (I) 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. １ ~Ry ３ The cycloalkyl group represented by the formula (I) 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 ~Ry ３ The alkenyl group represented by Ry is preferably a vinyl group. １ ~Ry ３ The alkynyl group represented by the formula (I) is preferably an ethynyl group. １ ~Ry ３ The cycloalkenyl group represented by the formula (I) is preferably a cyclopentyl group or a monocyclic cycloalkyl group such as a cyclohexyl group, which has a double bond in part thereof. １ ~Ry３ The aryl group represented by the formula (I) 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.

[0196] Ry １ ~Ry ３ The cycloalkyl group formed by combining the above two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of the above is, for example, a group in which one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom, a carbonyl group, or —SO ２ - group and -SO ３ The repeating unit represented by formula (B) may be substituted with a group containing a hetero atom such as a - group, a vinylidene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinylene group. １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ and are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0197] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0198] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —CO— group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —Rt—CO— group (Rt is an aromatic group)).

[0199] Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond include the repeating units described in paragraphs

[0067] to

[0071] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0200] Specific examples of the repeating unit A1 (a repeating unit having an acid-decomposable group) are shown below, but are not limited to these. The repeating units having an acid-decomposable group described in the Examples below are also preferred. For specific examples of the repeating unit A1, see, for example, paragraphs

[0029] to

[0071] of WO 2022 / 024928, which is incorporated herein by reference.

[0201]

[0202] The content of the repeating unit A1 is preferably 15 mol% or more, more preferably 40 mol% or more, and even more preferably 60 mol% or more, based on the total repeating units in the acid-decomposable resin. The content of the repeating unit A1 is preferably less than 100 mol%, more preferably 95 mol% or less, and even more preferably 90 mol% or less, based on the total repeating units in the acid-decomposable resin. The repeating unit A1 contained in the acid-decomposable resin may be one type or two or more types. When the acid-decomposable resin contains two or more types of repeating units A1, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0203] (Repeating unit having an acid group) The acid-decomposable resin preferably contains a repeating unit having an acid group (hereinafter also simply referred to as "repeating unit A2"). The repeating unit A2 is preferably a repeating unit different from the repeating unit A1 (repeating unit having an acid-decomposable group). The repeating unit A2 may also contain a fluorine atom or an iodine atom. The acid group is preferably a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. Of these, the repeating unit A2 is preferably a repeating unit having a phenolic hydroxy group. In the hexafluoroisopropanol group, one or more fluorine atoms (preferably one to two) may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group may be a -C(CF ３ )(OH)—CF ２ In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom to form -C(CF ３ )(OH)—CF ２ A ring containing - may be formed.

[0204] The repeating unit A2 is preferably a repeating unit represented by the following formula (Pa1), and the acid-decomposable resin preferably contains a repeating unit represented by the following formula (Pa1).

[0205]

[0206] In formula (Pa1), R ａ１ and R ａ２ each independently represents a hydrogen atom or a substituent. ａ１ represents a single bond or a divalent linking group. ａ１ represents an (m+n+1)-valent aromatic ring group. ａ１ And, R ａ２ or L ａ１ may be bonded via a single bond or a linking group. Ｘ represents a substituent other than a hydroxy group. n represents an integer of 1 or more and 9 or less. m represents an integer of 0 or more and 8 or less.

[0207] In the above formula (Pa1), R ａ１ and R ａ２ R each independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituent represented by R is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ and R ａ２ The alkyl group represented by the formula (I) may be either linear or branched, and may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. R ａ１ and R ａ２ The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have a substituent. R ａ１ and R ａ２ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. ａ１ and R ａ２ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The alkoxycarbonyl group may have a substituent.

[0208] In the above formula (Pa1), L ａ１ represents a single bond or a divalent linking group. ａ１ Examples of the divalent linking group represented by the formula: ａ３ -, an alkylene group, or a group formed by combining two or more of these groups.ａ３ represents a hydrogen atom or an alkyl group. The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. The alkylene group may have a substituent. R ａ３ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0209] In the above formula (Pa1), Ar ａ１ represents an (m+n+1)-valent aromatic ring group. ａ１ The aromatic ring group represented by the formula (I) may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic hydrocarbon group is preferably a group containing an aromatic hydrocarbon having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. The aromatic heterocyclic group preferably contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group is preferably a group containing an aromatic heterocycle having 4 to 20 ring atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0210] Ar ａ１ And, R ａ２ or L ａ１ may be bonded to via a single bond or a linking group. Examples of the linking group include —O—, —S—, —CO—, and —CO ２ -, -SO-, -SO ２ -, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have a substituent.

[0211] In the above formula (Pa1), R Ｘ represents a substituent other than a hydroxy group. ＸExamples of the substituent represented by R include a carboxy group, a sulfo group, a cyano group, a halogen atom, a hydrocarbon group, an amino group, a nitro group, and a group formed by combining two or more of these. Ｘ Examples of the hydrocarbon group represented by R include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 15 carbon atoms), and an alkenyl group (preferably having 2 to 10 carbon atoms). Ｘ The hydrocarbon group represented by R may have a substituent. Ｘ The hydrocarbon group represented by is -CH ２ When it contains -, -CH ２ At least one of - is -O-, -CO-, -S- and -SO ２ - may be replaced with at least one selected from the group consisting of Ｘ The substituent represented by the formula (I) preferably has a halogen atom, and the halogen atom is preferably a fluorine atom or an iodine atom.

[0212] In the above formula (Pa1), n ​​represents an integer of 1 or more and 9 or less, preferably an integer of 1 or more and 5 or less, and more preferably an integer of 1 or more and 4 or less. m represents an integer of 0 or more and 8 or less, preferably an integer of 0 or more and 4 or less, and more preferably an integer of 0 or more and 3 or less.

[0213] The repeating unit A2 is also preferably a repeating unit represented by the following formula (Pa2), and the acid-decomposable resin preferably contains a repeating unit represented by the following formula (Pa2).

[0214]

[0215] In formula (Pa2), R ａ４ represents a hydrogen atom or an alkyl group. ａ２ represents a single bond or —COO—. r represents an integer of 0 or more and 3 or less. R Ｘ１ represents a halogen atom or a hydrocarbon group. n1 represents an integer of 1 or more and 5 or less. m1 represents an integer of 0 or more and 4 or less.

[0216] In the above formula (Pa2), R ａ４ represents a hydrogen atom or an alkyl group.ａ４ The alkyl group represented by the formula (I) may be either linear or branched, and may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

[0217] In the above formula (Pa2), L ａ２ represents a single bond or -COO-, with a single bond being preferred. r represents an integer of 0 or more and 3 or less, with an integer of 0 or more and 2 or less being preferred, 0 or 1 being more preferred, and 0 being even more preferred. The aromatic ring in formula (Pa2) becomes benzene when r represents 0, naphthalene when r represents 1, anthracene when r represents 2, and naphthacene when r represents 3. n1 represents an integer of 1 or more and 5 or less, with an integer of 1 or more and 4 or less being preferred. m1 represents an integer of 0 or more and 4 or less, with an integer of 0 or more and 3 or less being preferred.

[0218] In the above formula (Pa2), R Ｘ１ represents a halogen atom or a hydrocarbon group. Ｘ１ The halogen atom represented by R is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom or an iodine atom. Ｘ１ Examples of the hydrocarbon group represented by R include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 15 carbon atoms), and an alkenyl group (preferably having 2 to 10 carbon atoms). Ｘ１ The hydrocarbon group represented by R may have a substituent. Ｘ１ The hydrocarbon group represented by -CH ２ When it contains -, -CH ２ At least one of - is -O-, -CO-, -S- and -SO ２ - may be replaced with at least one selected from the group consisting of Ｘ１ The hydrocarbon group represented by the formula (I) preferably has a halogen atom, and the halogen atom is preferably a fluorine atom or an iodine atom.

[0219] Specific examples of the repeating unit A2 (a repeating unit having an acid group) are shown below, but are not limited to these. １ and G ２ each independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group. f1 represents an integer of 1 to 3. The repeating unit A2 described in the examples below is also preferred. Specific examples of the repeating unit A2 include the repeating units described in paragraphs

[0079] to

[0110] of WO 2022 / 024928, and the above descriptions are incorporated herein.

[0220] When the acid-decomposable resin contains the repeating unit A2, the content of the repeating unit A2 is preferably 10 mol % or more, more preferably 15 mol % or more, based on the total repeating units in the acid-decomposable resin, and is preferably less than 40 mol %, more preferably 35 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0221] (Repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the repeating unit A1 and the repeating unit A2, the acid-decomposable resin may have a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter, also simply referred to as "repeating unit X"). The repeating unit X is preferably different from the repeating unit Y and the repeating unit P described below. The repeating unit X is preferably a repeating unit represented by formula (C).

[0222]

[0223] In formula (C), L ５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0224] The content of the repeating unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units in the acid-decomposable resin, and the upper limit thereof is preferably less than 40 mol% and more preferably 35 mol% or less, based on the total repeating units in the acid-decomposable resin.

[0225] The acid-decomposable resin may also have a repeating unit having at least one of a fluorine atom, a bromine atom, and an iodine atom. Examples of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom. Of the repeating units of the acid-decomposable resin, the total content of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the acid-decomposable resin. The upper limit is not particularly limited, but is, for example, 100 mol% or less based on the total repeating units of the acid-decomposable resin.

[0226] Specific examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs

[0116] to

[0117] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[0227] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The acid-decomposable resin may have a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, also simply referred to as "repeating unit Y"). It is also preferable that the repeating unit Y does not have a hydroxy group or an acid group such as a hexafluoropropanol group.

[0228] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, is more preferred. For units containing a lactone group or a sultone group, see, for example, paragraphs

[0119] to

[0126] and

[0132] to

[0133] of WO 2022 / 024928, and the above descriptions are incorporated herein.

[0229] The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928, which is incorporated herein by reference.

[0230] When the acid-decomposable resin contains the repeating unit Y, the content of the repeating unit Y is preferably 1 mol % or more, more preferably 10 mol % or more, based on the total repeating units in the acid-decomposable resin, and the upper limit thereof is preferably less than 40 mol %, more preferably 35 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0231] (Repeating unit having a photoacid generating group) The acid-decomposable resin may contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). However, it is also preferable that the acid-decomposable resin does not contain a repeating unit having a photoacid generating group (hereinafter simply referred to as a "repeating unit P"). Examples of the repeating unit P include a repeating unit represented by formula (4).

[0232]

[0233] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０ represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0234] L ４１ represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—). ４２ represents an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —S—, —SO—, —SO ２ Preferably, the linking group is at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but preferably 3 to 20, more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but preferably 6 to 20, more preferably 6 to 10. The alkylene group, cycloalkylene group, and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0235] R ４０ is preferably a group represented by the following formula (S4-1).

[0236]

[0237] In formula (S4-1), Q － represents an acid residue, M ＋ represents a cation. * represents L ４１ The bond position of the acid residue is a group formed by dissociating a proton from an acid. － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１ represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. ＋ The explanation, specific examples and preferred ranges of M ＋ is the same as

[0238] Specific examples of the repeating unit P include the repeating units described in

[0094] to

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

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

[0138] of WO 2022 / 024928 A, the above descriptions are incorporated herein. Further, examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of WO 2018 / 193954 A, the above descriptions are incorporated herein.

[0239] When the acid-decomposable resin contains the repeating unit P, the content of the repeating unit P is preferably 1 mol % or more, more preferably 3 mol % or more, and even more preferably 5 mol % or more, based on the total repeating units in the acid-decomposable resin. The content of the repeating unit P is preferably less than 40 mol %, more preferably 30 mol % or less, and even more preferably 20 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0240] (Repeating unit represented by formula (V-1) or formula (V-2)) The acid-decomposable resin may have a repeating unit represented by the following formula (V-1) or formula (V-2). The repeating units represented by formula (V-1) and formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0241]

[0242] In formula (V-1) and the following formula (V-2), R ６ and R ７ each independently represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxy group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954, the description of which is incorporated herein by reference.

[0243] (Repeating unit for reducing the mobility of the main chain) The acid-decomposable resin preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of the generated acid or pattern collapse during development. Regarding the repeating unit for reducing the mobility of the main chain, the contents of

[0144] to

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

[0244] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group) The acid-decomposable resin may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the acid-decomposable resin include the repeating units described above for repeating unit Y. The preferred content is also as described for repeating unit Y.

[0245] The acid-decomposable resin may have a repeating unit having a hydroxy group or a cyano group. This improves substrate adhesion. The repeating unit having a hydroxy group or a cyano group is preferably a repeating unit having a saturated hydrocarbon group having a hydroxy group or a cyano group (substituted with a hydroxy group or a cyano group). Alternatively, it may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group. The repeating unit having a hydroxy group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxy group or a cyano group include repeating units described in paragraphs

[0081] to

[0084] of JP 2014-098921 A, and the above descriptions are incorporated herein by reference.

[0246] The acid-decomposable resin may have a repeating unit having an alkali-soluble group. When the acid-decomposable resin contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxy group being preferred. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs

[0085] and

[0086] of JP 2014-098921 A, the disclosures of which are incorporated herein by reference.

[0247] (Repeating Unit Having an Alicyclic Hydrocarbon Structure and Not Exhibiting Acid Decomposability) The acid-decomposable resin may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[0248] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxy Group nor a Cyano Group) The acid-decomposable resin may have a repeating unit represented by formula (III) having neither a hydroxy group nor a cyano group.

[0249]

[0250] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group, and Ra represents a hydrogen atom, an alkyl group, or —CH ２ -O-Ra ２ represents a group. ２represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxy group or a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of JP 2014-098921 A, the descriptions of which are incorporated herein by reference.

[0251] (Other Repeating Units) Furthermore, the acid-decomposable resin may have other repeating units in addition to the repeating units described above. For example, see paragraphs

[0141] to

[0143] and

[0169] to

[0170] of WO 2022 / 024928, which are incorporated herein by reference.

[0252] In addition to the above repeating structural units, the acid-decomposable resin may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0253] In a preferred embodiment of the present invention, the acid-decomposable resin has at least one group selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a saturated hydrocarbon group having a hydroxy group, which further improves etching resistance and LWR performance.

[0254] In a preferred embodiment of the present invention, the acid-decomposable resin contains a repeating unit having an iodine atom, which increases the absorption rate of EUV light and the like, reduces the effect of shot noise, and further improves LWR performance.

[0255] The acid-decomposable resin can be synthesized according to a conventional method (e.g., radical polymerization). The weight-average molecular weight (Mw) of the acid-decomposable resin, 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, Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5. 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.

[0256] The content of the acid-decomposable resin in the resist composition is preferably 30.0 to 99.9 mass%, more preferably 40.0 to 99.9 mass%, and even more preferably 60.0 to 90.0 mass%, based on the total solids content of the resist composition. The acid-decomposable resin may be used alone, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0257] <Hydrophobic Resin> The resist composition may contain a hydrophobic resin different from the acid-decomposable resin. The hydrophobic resin is preferably designed so that it is unevenly distributed on the surface of the resist film. However, unlike surfactants, the hydrophobic resin does not necessarily have to have a hydrophilic group in its molecule, and does not necessarily have to contribute to uniform mixing of the polar substance and the non-polar substance.

[0258] The hydrophobic resin 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. In addition, 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 hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306, and the above descriptions are incorporated herein.

[0259] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 10.0 mass%, and even more preferably 0.1 to 5.0 mass%, relative to the total solids content of the resist composition. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0260] [Surfactant] The resist 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.

[0261] When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solids content of the resist composition. One type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0262] [Solvent] The resist 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). Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference. The content of the solvent in the resist composition is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. 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.

[0263] [Other Additives] The resist composition of the present invention may further contain, as other additives, at least one selected from the group consisting of a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxy group). The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less that decomposes under the action of an acid and thereby reduces its solubility in an organic developer.

[0264] The content of the other additives is not particularly limited, but may be 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, based on the total solid content of the resist composition. Only one type of other additive may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0265] The resist composition of the present invention may also contain water as an impurity. When water is contained as an impurity, the lower the content of water, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the entire resist composition. The resist composition may also contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are contained as impurities, the lower the content of residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition.

[0266] [Pattern Forming Method] The pattern forming method of the present invention is a pattern forming method comprising the steps of: (1) forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) of the present invention; (2) exposing the resist film to light; and (3) developing the exposed resist film using a developer. Each of the steps will be described in detail below.

[0267] [Step (1)] Step (1) is a step of forming a resist film on a substrate using a resist composition of the present invention. Details of the resist composition of the present invention used in step (1) are as described above.

[0268] As a method for forming a resist film on a substrate using a resist composition, for example, a method of coating the resist composition on a substrate can be mentioned. If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but when it is a polymer, it preferably includes polyolefins (including high density and ultra-high molecular weight) such as polyethylene (PE) and polypropylene (PP); polyamides such as nylon 6 and nylon 66; polyimides (PI); polyamideimides; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0269] The resist composition may be filtered using one filter or a combination of two or more filters. When two or more filters are used, they may be the same or different. The resist composition may be circulated and repeatedly filtered using the same filter.

[0270] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film, etc.) may be formed below the resist film.

[0271] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in at least one of a normal exposure machine and a developing machine, and may be performed using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0272] The present invention also includes the resist film obtained in step (1). The thickness of the resist 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 resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, when ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0273] A top coat may be formed on the resist film using a top coat composition. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that may be contained in the top coat include basic compounds that may be contained in the resist composition.

[0274] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). Examples of exposure methods include irradiating the formed resist 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 preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam.

[0275] After exposure, it is preferable to bake (heat) the film before developing. This step is also called post-exposure baking. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature for baking is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time for baking is not particularly limited, but 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 a means provided in at least one of a conventional exposure machine and a developing machine, and may be performed using a hot plate or the like.

[0276] [Step (3)] Step (3) is a step of developing the resist film exposed in step (2) using a developer. By performing step (3), a resist pattern (also simply referred to as a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer). Examples of development methods include a method of immersing a substrate in a tank filled with the developer for a certain period of time (dip method), a method of piling the developer on the surface of the substrate by surface tension and leaving it to stand for a certain period of time (puddle method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method). The development time 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. In step (3), a step of stopping development by replacing the solvent with another solvent may be performed.

[0277] 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.

[0278] 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.

[0279] The organic solvents may be mixed in plural, or may be mixed with a solvent other than the organic solvents or water. The water content of the organic 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 organic developer.

[0280] The organic developer preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms. The organic treatment liquid may contain only one or more hydrocarbons having from 9 to 12 carbon atoms. The hydrocarbon having from 9 to 12 carbon atoms is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes, and cycloalkanes, more preferably an alkane, still more preferably at least one selected from the group consisting of nonane, decane, undecane, and dodecane, particularly preferably at least one selected from the group consisting of undecane and dodecane, and most preferably undecane. The hydrocarbon having from 9 to 12 carbon atoms may contain a structural isomer.

[0281] The content of butyl acetate in the organic developer is preferably 65% ​​by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less, based on 100% by mass of the entire organic developer. The content of hydrocarbons having 9 to 12 carbon atoms in the organic developer (the total amount when multiple hydrocarbons having 9 to 12 carbon atoms are contained) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire organic developer.

[0282] The mass ratio of butyl acetate to hydrocarbon having from 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having from 9 to 12 carbon atoms) is preferably from 60 / 40 to 95 / 5, more preferably from 70 / 30 to 95 / 5, still more preferably from 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0283] The organic developer may contain other components in addition to butyl acetate and hydrocarbons having from 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having from 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, and the like.

[0284] [Rinsing Step] After step (3) is performed, rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common solvent can be used. The rinsing solution preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0285] The rinsing method is not particularly limited, and examples thereof include a method in which a rinse liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinse liquid for a certain period of time (dip method), and a method in which a rinse liquid is sprayed onto the surface of the substrate (spray method).

[0286] The pattern formation method of the present invention may also include a heating step (post-bake) after step (3). This step removes the developer and rinse solution remaining between and within the pattern. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0287] 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 not particularly limited, but oxygen plasma etching is preferred.

[0288] The developer, resist composition, and other various materials (e.g., solvent, rinse, anti-reflective coating-forming composition, top coat-forming composition, etc.) used in the pattern formation method of the present invention 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 (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 mass ppt or more. 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.

[0289] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions that minimize contamination. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0290] 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 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 a content of 0 ppt by mass or more is preferred.

[0291] [Method for Manufacturing an Electronic Device] This specification also relates to a method for manufacturing an electronic device, including the pattern formation method of the present invention described above, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0292] 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 changed as appropriate 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.

[0293] <Components of Resist Composition> The components used to prepare the resist compositions used in the examples and comparative examples are listed below.

[0294] [Compound (N)] The structures of compounds (N) ((I)-1 to (I)-18) are shown below. In addition, compounds (Z)-1 to (Z)-5 were used as comparative compounds.

[0295]

[0296]

[0297]

[0298]

[0299] (Synthesis Example: Synthesis of (I)-1) As a synthesis example of compound (N), the synthesis method of (I)-1 is shown below. (I)-2 to (I)-18 were synthesized according to the synthesis method of (I)-1.

[0300]

[0301] In a three-neck flask under a nitrogen atmosphere, 8.2 g of 4-dimethylaminopyridine (FUJIFILM Wako Pure Chemical Industries, Ltd.), 51.0 g of triethylamine (FUJIFILM Wako Pure Chemical Industries, Ltd.), 107.6 g of methanol (ultra-dehydrated, FUJIFILM Wako Pure Chemical Industries, Ltd.), and 50.0 g of 5-amino-2,4,6-triiodoisophthaloyl dichloride (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 60°C for 6 hours. The resulting reaction solution was cooled to 0°C, and then 550 mL of 1 mol / L hydrochloric acid and 600 mL of ethyl acetate were added, and the aqueous layer was removed using a separatory funnel. The resulting organic layer was washed three times with 300 mL of ion-exchanged water. The solvent was distilled off from the washed organic layer under reduced pressure, and 110 g of acetone was added to dissolve the contents. The mixture was then crystallized from 160 g of ion-exchanged water to obtain 40 g of (I)-1-A.

[0302] In a three-neck flask, 15.0 g of (I)-1-A, 90 mL of tetrahydrofuran (ultra-dehydrated, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 3.9 g of triethylamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were mixed under a nitrogen atmosphere and then cooled to -10°C. Subsequently, 7.6 g of (I)-1-B obtained by the method described in JP 2022-110777 A was added dropwise to the resulting mixture, and the mixture was stirred at -5°C for 4 hours. 40 mL of ethyl acetate, 40 mL of hexane, and 60 mL of ion-exchanged water were added to the resulting reaction solution, and the aqueous layer was removed using a separatory funnel. The solvent was distilled off from the resulting organic layer under reduced pressure to obtain crude (I)-1-C. The resulting (I)-1-C was used in the next reaction without purification.

[0303] The entire amount of (I)-1-C, 100 mL of tetrahydrofuran, 100 mL of ion-exchanged water, and 9 g of sodium hydrogencarbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and stirred at 60°C for 4 hours. To the resulting reaction solution, 60 mL of ethyl acetate, 40 mL of hexane, and 100 mL of ion-exchanged water were added, and the organic layer was removed using a separatory funnel. 1 mol / L hydrochloric acid was then added to the resulting aqueous layer until the pH reached 5. Subsequently, 100 mL of ethyl acetate was added, and the aqueous layer was removed using a separatory funnel. The solvent was then distilled off from the organic layer under reduced pressure to obtain 9.9 g of (I)-1-D.

[0304] In a three-necked flask, 9.0 g of (I)-1-D, 5.3 g of (I)-1-E, 160 g of distilled water, and 160 g of methylene chloride were mixed under a nitrogen atmosphere and stirred at 20°C for 3 hours. After removing the aqueous layer using a separatory funnel, the organic layer was washed twice with 50 mL of ion-exchanged water. After distilling off the solvent from the washed organic layer under reduced pressure, crystallization was performed using diisopropyl ether to obtain 9.1 g of (I)-1 as a white solid. The resulting (I)-1 was identified as follows: １ H-NMR (nuclear magnetic resonance), and １９ F-NMR was used. １ H-NMR (400 MHz, acetone-d6): δ (ppm) = 10.00 (br s, 1H), 8.38 (d, 6H), 8.23 ​​(d, 6H), 3.97 (s, 6H). １９ F-NMR (376.6 MHz, acetone-d6): δ (ppm) = -63.9, -110.5.

[0305] [Acid-decomposable resin] The content ratio of each repeating unit in resins (A-1 to A-37) is shown in Table 1. The synthesis methods for resin A-1 and resin A-37 are shown below. Note that, like resin A-1 and resin A-37, other resins were synthesized in accordance with known methods. In Table 1, the "mol %" column indicates the content (mol %) of each repeating unit relative to all repeating units. In Table 1, the "Mw" column indicates the weight average molecular weight. In Table 1, the "Mw / Mn" column indicates the dispersity. Note that the weight average molecular weight (Mw) and dispersity (Mw / Mn) of resins A-1 to A-37 were measured by GPC (carrier: tetrahydrofuran (THF)) (values ​​converted into polystyrene). The composition ratios (molar ratios) of the resins are １３ Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0306] Synthesis Example 1: Synthesis of Resin A-1 Propylene glycol monomethyl ether acetate (28 g) was heated to 80°C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by MA-16 (30 g), a monomer represented by MB-10 (38 g), propylene glycol monomethyl ether acetate (112 g), and dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.7 g) was added dropwise over 6 hours to obtain a reaction liquid. After completion of the dropwise addition, the reaction liquid was stirred at 80°C for an additional 2 hours. The resulting reaction liquid was allowed to cool and then reprecipitated with a large amount of a mixed solvent of heptane and ethyl acetate (heptane:ethyl acetate = 9:1, mass ratio), followed by filtration. The resulting solid was vacuum dried to obtain 58 g of Resin A-1. The weight average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 8,500, and the dispersity (Mw / Mn) was 1.60. １３ The molar ratio of the repeating units measured by C-NMR (nuclear magnetic resonance) was MB-10 / MA-16=50 / 50.

[0307] Synthesis Example 2: Synthesis of Resin A-37 Propylene glycol monomethyl ether acetate (22 g) was heated to 85°C under a nitrogen stream. While stirring this solution, a mixed solution of a monomer represented by MB-3 (6 g), a monomer represented by MB-20 (35 g), a monomer represented by MA-2 (27 g), propylene glycol monomethyl ether acetate (84 g), dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (1.2 g), and methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (4.4 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 2 hours to obtain a polymerized solution. Methanol (100 g) and triethylamine (16 g) were added to the resulting polymerized solution, and the mixture was stirred at 50°C for 5 hours. After stirring was completed, the solution was allowed to cool to room temperature, and then ethyl acetate (650 g) and a 0.2 mol / L aqueous hydrochloric acid solution (400 mL) were added and stirred for 30 minutes to extract the organic layer. The extracted organic layer was washed five times with distilled water (400 mL). The washed organic layer was reprecipitated in a mixed solution of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. The obtained solid was dried in vacuum to obtain 38 g of resin A-37. The weight average molecular weight (Mw: polystyrene equivalent) of resin A-37 determined by GPC (carrier: tetrahydrofuran (THF)) was 10,000, and the dispersity (Mw / Mn) was 1.35. １３ The molar ratio of the repeating units measured by C-NMR (nuclear magnetic resonance) was MB-3 / MB-20 / MA-2=10 / 30 / 60.

[0308]

[0309] The structure of each repeating unit in the acid-decomposable resin shown in Table 1 is shown below.

[0310]

[0311]

[0312]

[0313] [Photoacid Generator] The structures of the photoacid generators (B-1 to B-36) are shown below.

[0314]

[0315]

[0316]

[0317]

[0318]

[0319] [Acid Diffusion Controller] The structures of the acid diffusion controllers (C-1 to C-23 and D-1 to D-5) are shown below.

[0320]

[0321]

[0322]

[0323]

[0324]

[0325] [Hydrophobic Resin] The structures of hydrophobic resins E (E-1 to E-8) are shown below. Table 2 shows the content ratio of each repeating unit in the hydrophobic resin. In Table 2, the "molar ratio of repeating units" column shows the content (mol %) of each repeating unit relative to all repeating units. The type and molar ratio of each repeating unit correspond in order from left to right. In Table 2, the "Mw" column shows the weight average molecular weight. In Table 2, the "Mw / Mn" column shows the dispersity. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of resins E-1 to E-8 were measured by GPC (carrier: tetrahydrofuran (THF)) (values ​​converted into polystyrene). The composition ratios (molar ratios) of the resins are as follows: １３ Measurement was performed by C-NMR.

[0326]

[0327]

[0328] [Surfactants] The surfactants (F-1 to F-3) are as follows: F-1: Megafac F176 (manufactured by DIC Corporation, fluorochemical surfactant) F-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicon surfactant) F-3: PF656 (manufactured by OMNOVA, fluorochemical surfactant)

[0329] [Solvents] The solvents (G-1 to G-9) used in preparing the resist compositions are as follows: G-1: Propylene glycol monomethyl ether acetate (PGMEA) G-2: Propylene glycol monomethyl ether (PGME) G-3: Propylene glycol monoethyl ether (PGEE) G-4: Cyclohexanone G-5: Cyclopentanone G-6: 2-heptanone G-7: Ethyl lactate G-8: γ-butyrolactone G-9: Propylene carbonate

[0330] <Preparation and Coating of Resist Compositions> The components used in preparing the resist compositions used in the Examples and Comparative Examples are listed below. The components shown in Tables 3 to 6, 101, and 102 below were mixed to a solids concentration of 2% by mass. The resulting mixture was filtered through a polyethylene filter with a pore size of 0.02 μm to prepare the resist compositions of the Examples and Comparative Examples. "Solids" refers to the components excluding the solvent. In Tables 3 to 6, 101, and 102, entries separated by " / " in the type column indicate that the substance contains multiple compounds, and entries separated by " / " in the mass% column indicate the content of multiple compounds in order. In Tables 3 to 6, 101, and 102, the "mass%" column indicates the content (mass%) of each solid component relative to the total solids content. In Tables 3 to 6, 101, and 102, the "mixing ratio" column for "solvent" indicates the mixing ratio (mass ratio) of each solvent. Table 4 is a continuation of Table 3. For example, Re-1 is a resist composition that contains (I)-1 as the compound (N) and E-1 as the hydrophobic resin. Table 6 is a continuation of Table 5. For example, Re-31 is a resist composition that contains (I)-4 as the compound (N) and E-2 as the hydrophobic resin. Table 102 is a continuation of Table 101.

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337] The resist compositions of each of the Examples and Comparative Examples prepared by the above procedure were 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 for 300 seconds on a hot plate at 130°C to obtain a resist film with a thickness of 45 nm. Here, 1 inch is 0.0254 m.

[0338] <Exposure and Development> [EUV Exposure] The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) manufactured by Exitech Corp. An exposure mask with a line width of 20 nm and a 1:1 line and space pattern was used.

[0339] [Alkali Development (Examples 1-1 to 1-66 and Comparative Examples 1-1 to 1-2)] The exposed wafer was heated on a hot plate at 100°C for 90 seconds, then 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 to obtain a positive resist pattern. In this manner, the resist patterns of Examples 1-1 to 1-66 and Comparative Examples 1-1 to 1-2 were obtained. The resist compositions used are shown in Tables 7, 8, and 103 below.

[0340] <Evaluation of Pattern Shape (Cross-Sectional Rectangularity) (Part 1)> The resist patterns of each Example and Comparative Example obtained by alkali development were evaluated according to the following procedure. The cross-sectional shape of the resulting line pattern of each Example and Comparative Example, with an average line width of 20 nm, was observed using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured. Using the value of Lb / La as an index, the cross-sectional rectangularity of the pattern shape was evaluated according to the following criteria: S is the best, and G is the worst. The results are shown in Tables 7 to 8 and 103 below.

[0341] (Evaluation criteria) S: 1.00≦(Lb / La)≦1.01 A: 1.01<(Lb / La)≦1.02 B: 1.02<(Lb / La)≦1.03 C: 1.03<(Lb / La)≦1.04 D: 1.04<(Lb / La)≦1.05 E: 1.05<(Lb / La)≦1.06 F:1.06<(Lb / La)≦1.07 G:1.07<(Lb / La)

[0342] <Evaluation of LWR (Part 1)> For a pattern obtained by alkaline development of a 1:1 line and space with a line width of 20 nm, 3σ (nm), which is three times the standard deviation (σ) of the measured line width, was calculated and used as an index of LWR (Line Width Roughness). Specifically, a shot of 3.5 mm vertically (y-axis direction) and 6.5 mm horizontally (x-axis direction) was defined as one shot, and exposure was performed on the wafer with 8 columns in the x direction and 29 rows in the y direction, for a total of 232 shots. Ten length measurement photographs (5 lines per photograph) were measured for each shot, and the average of the 10 measurement values ​​was used as the measurement value for that shot. The standard deviation of the measurement values ​​for the 232 shots was tripled to obtain 3σ. From the obtained 3σ value, LWR was evaluated according to the following evaluation criteria. S is the best and E is the worst.

[0343] (Evaluation criteria) S: 3σ of variation is 2.4 nm or less. A: 3σ of variation is more than 2.4 nm and less than 2.8 nm. B: 3σ of variation is more than 2.8 nm and less than 3.2 nm. C: 3σ of variation is more than 3.2 nm and less than 3.6 nm. D: 3σ of variation is more than 3.6 nm and less than 4.0 nm. E: 3σ of variation is greater than 4.0 nm.

[0344] The evaluation results of the resist patterns obtained by alkali development in each of the Examples and Comparative Examples (Examples 1-1 to 1-66 and Comparative Examples 1-1 and 1-2) are shown in Tables 7 to 8 and 103 below.

[0345]

[0346]

[0347]

[0348] [Organic Solvent Development (Examples 2-1 to 2-66, Comparative Examples 2-1 to 2-2, Examples 3-1 to 3-66, and Comparative Examples 3-1 to 3-2)] A wafer exposed by the method described in [EUV Exposure] above was heated on a hot plate at 90°C for 60 seconds, and then developed for 30 seconds with developer J-1 or J-2 shown below. This was then spin-dried to obtain a negative resist pattern. J-1: n-butyl acetate J-2: n-butyl acetate / undecane = 90 / 10 (mass ratio) In this way, the resist patterns of Examples 2-1 to 2-66, Comparative Examples 2-1 to 2-2, Examples 3-1 to 3-66, and Comparative Examples 3-1 to 3-2 were obtained. The resist compositions and developers used are shown in Tables 9 to 10, Tables 11 and 12, and Tables 104 and 105 below.

[0349] <Evaluation of Pattern Shape (Cross-Sectional Rectangularity) (Part 2)> The resist patterns of each Example and Comparative Example obtained by organic solvent development were evaluated according to the following procedure. The La and Lb values ​​were measured using the same procedure as in <Evaluation of Pattern Shape (Cross-Sectional Rectangularity) (Part 1)> above. Using the La / Lb value as an index, the cross-sectional rectangularity of the pattern shape was evaluated according to the following criteria: S is the best, and G is the worst. The results are shown in Tables 9-10, 11-12, and 104-105 below.

[0350] (Evaluation criteria) S: 1.00≦(La / Lb)≦1.01 A: 1.01<(La / Lb)≦1.02 B: 1.02<(La / Lb)≦1.03 C: 1.03<(La / Lb)≦1.04 D: 1.04<(La / Lb)≦1.05 E: 1.05<(La / Lb)≦1.06 F:1.06<(La / Lb)≦1.07 G:1.07<(La / Lb)

[0351] <Evaluation of LWR (Part 2)> The LWR of the resist patterns of each Example and Comparative Example obtained by organic solvent development was evaluated using the same procedures and evaluation criteria as those described in <Evaluation of LWR (Part 1)> above. The evaluation results of the resist patterns of each Example and Comparative Example obtained by organic solvent development (Examples 2-1 to 2-66, Comparative Examples 2-1 to 2-2, Examples 3-1 to 3-66, and Comparative Examples 3-1 to 3-2) are shown in Tables 9 to 10, 11 and 12, and 104 to 105 below.

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358] The results in Tables 7 to 12 and 103 to 105 confirm that the resist compositions (actinic ray- or radiation-sensitive resin compositions) of the present invention are capable of forming patterns having a rectangular cross-sectional shape. On the other hand, the resist compositions used in the comparative examples did not contain the compound (N), and therefore no patterns having a rectangular cross-sectional shape were obtained.

[0359] Furthermore, a comparison between Example 1-12 and Example 1-36 and the like confirmed that when the compound (N) in the resist composition is a compound represented by the above formula (2), the pattern shape (cross-sectional rectangularity) is more excellent. A comparison between Example 1-11 and Example 1-36 and the like confirmed that when the compound (N) in the above formula (1) is a compound represented by the above formula (2), the pattern shape (cross-sectional rectangularity) is more excellent. １ is a hydrogen atom, the pattern shape (cross-sectional rectangularity) was confirmed to be more excellent. From a comparison between Example 1-9 and Example 1-36, it was confirmed that when the compound (N) is a compound represented by the formula (2) and in formula (2), m is 1 or more, the pattern shape (cross-sectional rectangularity) was confirmed to be more excellent. From a comparison between Example 1-7 and Example 1-34, it was confirmed that when the compound (N) is a compound represented by the formula (2) and in formula (2), m R ２ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ and R ３ It was confirmed that when Y represents a monovalent organic group, the pattern shape (cross-sectional rectangularity) is more excellent. ２ ) ｒ It was confirmed that when Z is —SO 2 in the formula (1), the pattern shape (cross-sectional rectangularity) is more excellent. ３ －It was confirmed that the pattern shape (cross-sectional rectangularity) was more excellent when X in formula (1) was a single bond, and ... ＋ is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms, the LWR is confirmed to be better. From a comparison between the Examples shown in Tables 9 and 10 and the Examples shown in Tables 11 and 12, it was confirmed that when the developer contains butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms, at least one of the pattern shape (cross-sectional rectangularity) and the LWR is better.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) represented by formula (1) and a resin. In formula (1), Z is —SO ３ － , or -SO ２ -N － -SO ２ Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Y represents -(CR ２ ) ｒ - or an arylene group having the substituent F. Each R independently represents a hydrogen atom or a monovalent substituent, and at least one R represents the substituent F. r represents an integer of 1 or greater. X represents a single bond or a divalent linking group. R １ represents a hydrogen atom or a monovalent organic group. L represents a single bond or an alkylene group. When the alkylene group has two or more carbon atoms, the methylene group in the alkylene group may be substituted with —O—, a carbonyl group, —S—, or —NR Ｎ -, and a divalent linking group selected from a sulfonyl group. Ｎ represents a hydrogen atom or an alkyl group. W represents an (n+1)-valent aromatic group which may have a substituent other than an iodine atom. n represents an integer of 1 or more. M ＋ represents a cation.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (N) is a compound represented by formula (2). In formula (2), Z, Y, X, R １ , n and M ＋ represents Z, Y, X, and R in the formula (1). １ , n and M ＋ Ar represents an aromatic group having a valence of (n+m+1), and m represents an integer of 0 or more. ２ represents a halogen atom other than an iodine atom, or a monovalent organic group.

3. R １ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein is a hydrogen atom.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein m is 1 or more.

5. m R ２ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ and R ３ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4 , wherein represents a monovalent organic group.

6. Y is -(CR ２ ) ｒ 5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein R and r have the same meanings as R and r in formula (1).

7. Z is -SO ３ － 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein 8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein X is a single bond.

9. M ＋ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein is a sulfonium cation or an iodonium cation.

10. M ＋ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9, wherein is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein n is an integer of 3 or more.

12. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, further comprising an acid diffusion controller.

13. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 12, wherein the acid diffusion controller is a compound selected from the group consisting of a basic compound (CA), a low-molecular-weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation, provided that when compound (CC) is an onium salt compound (CD) that is a relatively weaker acid than compound (N), the onium salt compound (CD) is a compound containing an anion moiety represented by any of the following formulas (BB-1) to (BB-7):

14. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2.

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

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

17. A compound represented by formula (21). In formula (21), Z is —SO ３ － , or -SO ２ -N － -SO ２ Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Y represents -(CR ２ ) ｒ - or an arylene group having the substituent F. Each R independently represents a hydrogen atom or a monovalent substituent, and at least one R represents the substituent F. r represents an integer of 1 or more. X represents a single bond or a divalent linking group. Ar represents an aromatic group having a valence of (n+q+1). n and q each independently represent an integer of 1 or more. R ２１ represents a halogen atom other than an iodine atom or a monovalent organic group, and q R ２１ At least one of the groups is —CO—O—R ３ , —O—CO—R ３ , -O-CO-OR ３ , -SO ２ -R ３ , or -SO ３ -R ３ It is. ３ represents a monovalent organic group. ＋ represents a cation.

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