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

Abstract

To provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a rectangular cross-sectional shape.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) represented by Formula (1) and a resin.SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor devices such as integrated circuits (ICs) and large-scale integrated circuits (LSIs), microfabrication is performed by lithography using actinic ray- or radiation-sensitive resin compositions (hereinafter simply referred to as "resist compositions"). In recent years, the increasing integration density of integrated circuits has led to 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. 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 enhancing 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. X 1represents a divalent saturated hydrocarbon group, and a hydrogen atom contained in the group may be substituted with a fluorine atom, and -CH2- contained in the group may be substituted with -O- or -CO-. X 2 represents a single bond or an alkylene group, and -CH2- contained in the group 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. [ka] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-201859 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have investigated the resist composition described in Patent Document 1 and 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 that can form a pattern having a rectangular cross section. Another object of the present invention is to provide a resist film, a pattern forming method, a device manufacturing method, and a compound. [Means for solving the problem]

[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 [1] or [2], wherein is a hydrogen atom. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein m is 1 or more. [5] m R 2 At least one of the following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 and R 3 represents a monovalent organic group. [6] Y is -(CR2) r -, and R and r have the same meanings as R and r in the above formula (1). [7] Z is -SO3 - The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein [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 + is a sulfonium cation or an iodonium cation.

[10] M +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 a weaker acid than the compound (N), the onium salt (CD) is a compound containing an anion moiety represented by any one of the formulae (BB-1) to (BB-7) described below.

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

[13] .

[15] A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

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

[16] A method for manufacturing an electronic device, comprising the pattern forming method according to

[15] .

[17] A compound represented by the formula (21) described below. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern having a rectangular cross section. The present invention also provides a resist film, a pattern forming method, a device manufacturing method, and a compound. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on typical 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" means actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes 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.

[0013] In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0014] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (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: refractive index detector).

[0015] In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, which can be selected from the following substituents T.

[0016] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; cycloalkyloxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; cycloalkyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, meth Examples 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; and carbamoyl groups. Furthermore, 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 further substituents (for example, 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 "XYZ", Y may be -CO-O- or -O-CO-. The compound may be "X-CO-OZ" or "XO-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 based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. 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 calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + 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, such as Gaussian 16.

[0020] In this specification, as described above, pKa refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and known literature values. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[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-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as the "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 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 a chemically amplified resist composition or a non-chemically amplified resist composition, but is preferably a chemically amplified resist composition.

[0023] The reason why the resist composition having the above-described structure can solve the problems of the present invention is not entirely clear, but the present inventors speculate as follows. The mechanism by which the effects are obtained is not limited by the following speculation. 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 in that it contains 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 EUV light absorption is insufficient particularly at the bottom of the resist pattern, leading to deterioration of the pattern shape and making it difficult to obtain a pattern with high rectangularity. As described above, compound (N) contains an iodine atom, which increases the efficiency of EUV light absorption. Furthermore, compound (N) contains an amide bond, which improves the dispersibility of compound (N) in the resist composition, making it easier to increase the absorption of EUV light at the bottom of the resist pattern. Therefore, it is presumed that the compound (N) having the above structure enabled the formation of a pattern having a cross-sectional shape closer to a rectangle. Hereinafter, the ability to form a pattern having a cross-sectional shape closer to a rectangle using the resist composition of the present invention will also be referred to as "the effects of the present invention being superior."

[0025] [Compound (N)] The resist composition of the present invention contains a compound (N) represented by formula (1). The compound (N) can generate an acid upon irradiation with actinic rays or radiation (hereinafter also referred to simply as "exposure"; among these, EUV light is 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, thereby forming a resist pattern.

[0026] Upon exposure, compound (N) preferably generates an acid having a pKa of less than 0. The pKa of the acid generated from compound (N) upon exposure is preferably −0.1 or less, more preferably −0.5 or less. Furthermore, 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 the 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] [ka]

[0028] In formula (1), Z is -SO3 - , or -SO2-N- represents —SO2—Rf, where Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Z is -SO3 - is preferred. Rf is preferably an alkyl group having a fluorine atom. The alkyl group having a fluorine atom may be linear, branched, or cyclic, but is preferably linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The number of fluorine atoms contained in the alkyl group is not particularly limited, but the alkyl group is preferably a perfluoroalkyl group.

[0029] In formula (1), Y is -(CR2) r or an arylene group having the above substituent F. Each R independently represents a hydrogen atom or a monovalent substituent, and at least one R represents the above substituent F. Y is -(CR2) 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, -(CR2) r In -, it is preferred that all R's are fluorine atoms. Examples of the monovalent substituent represented by R include groups selected from the substituent T above. r represents an integer of 1 or greater. r is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, and further 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 fluorine atom-containing arylene group, the arylene group preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples of the arylene group include a phenylene group and a naphthylene group, with the phenylene group being preferred.

[0031] In formula (1), X represents a single bond or a divalent linking group, and 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 these groups represents the substituent F. r represents an integer of 1 or greater.) -CO-, -O-, -S-, -NH-, -SO-, -SO2-, -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 groups.

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

[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 -NR N R may be substituted with a divalent linking group selected from -, and 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 carbon atoms, and even more preferably 1 to 3 carbon atoms. The branched alkylene group preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms. The cyclic alkylene group preferably has 3 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. 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, and n represents an integer of 1 or greater. n is preferably an integer of 2 or more, and more preferably an integer of 3 or more. The upper limit is, 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, but is preferably an aromatic hydrocarbon ring. The aromatic ring preferably has 5 to 20 ring-member atoms, more preferably 5 to 15 ring-member atoms, and even more preferably 6 to 10 ring-member atoms. When the aromatic ring is an aromatic heterocycle, it preferably has a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. Of the aromatic rings, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0035] Examples of the substituent other than an iodine atom that W may have include, among groups selected from the above-mentioned substituents T, substituents other than an iodine atom. "-LW-(I)" in formula (1) n Among these, the group represented by the following formula (W) is preferred as the group represented by the following formula:

[0036] [ka]

[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 R may be substituted with a divalent linking group selected from -, and 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, and 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, but is preferably an aromatic hydrocarbon ring. The aromatic ring preferably has 5 to 20 ring-member atoms, more preferably 5 to 15 ring-member atoms, and even more preferably 6 to 10 ring-member atoms. When the aromatic ring is an aromatic heterocycle, it preferably has a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. Of the aromatic rings, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0039] In the above formula (W), R 2 represents a halogen atom other than an iodine atom, or a monovalent organic group. R 2 The halogen atom represented by the formula (I) is preferably a bromine atom. R 2 Examples of the monovalent organic group represented by the formula include substituents containing one or more carbon atoms selected from the above-mentioned substituents T. R 2 Among them, m R 2At least one of the following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 It is preferable that R 3 represents a monovalent organic group.

[0040] Examples of electron-withdrawing groups include those whose Hammett's substituent constant (σp value) is a positive value. The Hammett's substituent constant is a numerical expression of the effect of a substituent on the acid dissociation equilibrium constant of a substituted benzoic acid, and is a parameter that indicates the strength of the electron-withdrawing and electron-donating properties of the substituent. In this specification, the Hammett's substituent constant refers to the substituent constant σ when the substituent is located at the para position of the benzoic acid. The substituent constants (σp values) of Hammett's rule 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 -CO2R. EWG (σp:R EWG is an ethyl group, +0.45), -CONH2 (σp: +0.36), -COR EWG (σp:R EWG is a methyl group (+0.50), -CF3 (σp: +0.54), -SO2R EWG (σp:R EWG is a methyl group), and -NO2 (σp: +0.78). R EWGR 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 following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 It is preferable that R 3 represents a monovalent organic group. 2 All of -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 It is preferable that: R 3 Examples of the monovalent organic group represented by 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 an -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. The number of ring atoms in the aliphatic heterocyclic group 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. Of the aliphatic heterocyclic groups, a tetrahydrofuran ring group or an ethylene carbonate ring group is preferred.

[0044] In the above formula (1), M + represents a cation. + The cation represented by is a monovalent cation. The cation is not particularly limited, but preferably represents an organic cation. M + 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. M + Among these, a sulfonium cation or an iodonium cation is preferred, a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms is more preferred, and a sulfonium cation having 3 to 15 fluorine atoms or an iodonium cation having 3 to 15 fluorine atoms is even more preferred. The sulfonium cation is preferably a cation represented by formula (ZaI) described later, more preferably cation (ZaI-1) described later or cation (ZaI-4b) described later. The iodonium cation is preferably a cation represented by the formula (ZaII) described below.

[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] [ka]

[0047] In formula (2), Z, Y, X, R 1 , n and M + The definition and preferred embodiments of Y, X, R in the above formula (1) are as follows: 1 , n and M + The definition and preferred embodiments are the same as those of the above. In formula (2), Ar represents an (n+m+1)-valent aromatic group, and m represents an integer of 0 or greater. Preferred embodiments of Ar and m are the same as those of Ar and m in the above 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. Among them, m R 2 At least one of the following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-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] [ka]

[0050] In formula (21), Z is -SO3 - , or -SO2-N -represents —SO2—Rf, where Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Y is -(CR2) r - or an arylene group having the above-mentioned substituent F. R each 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 greater. X represents a single bond or a divalent linking group. n represents an integer of 1 or more. M + represents a cation. In formula (21), Z, Y, X, n, and M + 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 (n+q+1)-valent aromatic group. q represents an integer of 1 or greater. q is preferably an integer of 1 or greater, 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 following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 R 3 represents a monovalent organic group. R 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 -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-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. The compound (N) may be used alone or in combination of two or more. When two or more compounds (N) are used, the total content thereof is preferably 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. 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 incorporated into a part of a resin. Alternatively, the form of a low molecular weight compound and the form of being 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 3,000, more preferably 600 to 2,500, and even more preferably 700 to 2,000. When the photoacid generator is in a form in which it is incorporated into a part of a resin, it may be incorporated into a part of the acid-decomposable resin, or may be incorporated into a resin different from the acid-decomposable resin.

[0055] Examples of photoacid generators include "M + X- The compound is preferably an onium salt that generates an organic acid upon exposure to light. Examples of organic acids 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 ", M + represents a cation, preferably an organic cation. The cation may have a valence of one, two, or more. 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] [ka]

[0058] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The 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 (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-. When the resist composition of the present invention is used as an EUV resist, R 201 ~R 205 preferably 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 explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. R 201 ~R 203 one of which 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 203 Examples of groups formed by combining two of these 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 -CH2-CH2-O-CH2-CH2-). 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, 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, etc. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. The alkyl group or cycloalkyl group that the arylsulfonium cation can have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0061] The aryl group may have a substituent, and the substituent is preferably an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom (for example, fluorine or iodine), a hydroxy group, a carboxy group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, or an alkyloxycarbonylalkyleneoxy group. The above-mentioned substituent may further have a substituent if possible, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any manner to form an acid-decomposable group. The acid-decomposable group is a group that decomposes under the action of an acid and increases its polarity, and preferably has a structure in which a polar group is protected by a group that is released under the action of an acid.

[0062] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is R in formula (ZaI). 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. R 201 ~R 203 The organic group not having an aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. R 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 203 Examples of the alkyl group and cycloalkyl group represented by the formula (I) include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, and a norbornyl group). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxy group, a cyano group, or a nitro group.

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

[0065] [ka]

[0066] In formula (ZaI-3b), R1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxy group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[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 y may 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 yExamples of the group formed by bonding 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. R 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 explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0071] [ka]

[0072] In formula (ZaI-4b), l represents an integer of 0 to 2; r represents an integer of 0 to 8; R 13represents 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 a plurality of groups are present, they may be independent or different from each other. R 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 they are bonded to each other to form a ring, the ring may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R 15 are preferably alkylene groups and bond together 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 explained. In formula (ZaII), R204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, 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. R 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 (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0075] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have a substituent. R 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] [ka]

[0078] [ka]

[0079] "M + X - In the compound represented by ", 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 having a significantly low ability to cause a nucleophilic reaction, and more preferably a non-nucleophilic anion. The organic anions may be used alone or in combination of two or more.

[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 group, cycloalkyl group, and aryl group mentioned 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 preferably contains fluorine atoms or iodine atoms as a substituent, and more preferably iodine atoms. There is no limitation on the number of fluorine atoms or iodine atoms, but from the viewpoint of EUV light absorption efficiency, 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. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure.

[0087] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are mentioned.

[0088] Preferred non-nucleophilic anions are 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, or 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) or benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, or 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

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

[0090] [ka]

[0091] In formula (AN1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group. 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', -NH2, -NR'2, -NHR', or -NHCOR' is preferred. R' is a monovalent hydrocarbon group. Among them, 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 monovalent aromatic hydrocarbon groups such as 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-, -SO2-, 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 formed by combining a plurality of these groups. Among these, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0094] L is preferably, for example, a group represented by the following formula (AN1-1). * 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 is -C(R 1 )(R 2 )- represents the bonding position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, there are multiple instances of 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 2b R in 2 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 -SO2-* B Represents. 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 -SO2-* B Represents. * A is R in formula (AN1) 3 represents the bond position on the side, and * B is -SO3 in formula (AN1) - 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 and may have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). Among them, R 3 is 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), which 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, which may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as 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, more preferably an iodine atom. When an iodine atom is contained, it is preferably a structure in which the iodine atom is directly bonded to a carbon atom on the aromatic ring. When the resist composition of the present invention is used as an EUV resist, the greater the number of halogen atoms, the more preferable it is from the standpoint of EUV light absorption efficiency.

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

[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

[0056] to

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

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

[0101] [ka]

[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, and is defined as 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 alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. 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, more preferably a fluorine atom or CF3, and further preferably 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. R 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 them, a cyclic organic group is preferable. The carbon constituting the cyclic organic group (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, and 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, and may or may not have aromaticity. Examples of aromatic heterocyclic rings 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 non-aromatic heterocyclic rings 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 W contains an iodine atom, it is preferable that the iodine atom be directly bonded to a carbon atom on the aromatic ring. When the resist composition of the present invention is used as an EUV resist, the greater the number of halogen atoms, the more preferable it is from the standpoint of EUV light absorption efficiency.

[0109] The anion represented by formula (AN2) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. 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 2018-025789 A, and Examples include anions described in

[0176] to

[0183] ,

[0186] to

[0196] in WO 2022 / 064863,

[0116] to

[0123] ,

[0126] to

[0136] in WO 2023 / 157455, and

[0076] in WO 2023 / 157455, the above descriptions are incorporated herein.

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

[0112] [ka]

[0113] In formula (AN3), Ar represents an aryl group (e.g., a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom or a hydroxy group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 or 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, 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 2018-159744 A,

[0045] of JP 2018-155908 A, and

[0037] to

[0055] and

[0062] to

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

[0118] The non-nucleophilic anion is also preferably a disulfonamide anion. Disulfonamide anions are, for example, N - (SO2-R q )2 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. 2 R's 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] [ka]

[0121] In formula (d1-1), R 51 represents 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

[0041] to

[0047] in JP 2017-219836 A,

[0026] to

[0028] in JP 2018-155902 A,

[0040] to

[0041] and

[0128] in JP 2020-154212 A,

[0049] to

[0061] and

[0278] to

[0279] in JP 2021-091666 A, and Examples include anions described in

[0150] to

[0154] of JP-A-064863,

[0013] to

[0015] of JP-A-2022-077505,

[0026] to

[0031] ,

[0050] to

[0051] of JP-A-2022-141598,

[0147] of JP-A-2023-108593, and

[0088] of WO 2023 / 157455, the above descriptions are incorporated herein by reference.

[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). Z 2c The hydrocarbon group in may be linear or branched, or may have a cyclic structure. Furthermore, the carbon atom in the hydrocarbon group (preferably, when the hydrocarbon group has a cyclic structure, a carbon atom that is a member of the ring) may be a carbonyl carbon (—CO—). Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent, wherein 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 the above formulae (AN1) to (AN3). For example, Z 2c is preferably other than an aryl group. 2c In -SO3 - 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 -SO3 -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] The photoacid generator is also preferably 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, upon irradiation with actinic rays or radiation, generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y: Structural site X: Anion site A1 - and cationic moiety M1 + and a structural moiety that forms a first acidic moiety represented by HA1 upon irradiation with actinic rays or radiation. Structural site Y: Anionic site A2 - and cationic moiety M2+ and a structural portion that forms a second acidic site represented by HA2 upon irradiation with actinic rays or radiation. The above compound (I) satisfies the following condition I.

[0128] Condition I: In the compound (I), the cation moiety M1 in the structural moiety X + and the cationic moiety M2 in the structural moiety Y. + H + The compound PI in which the cationic moiety M1 in the structural moiety X is replaced by + H + and the cationic moiety M2 in the structural moiety Y. + H + and an acid dissociation constant a2 derived from the acidic site represented by HA2 in which the acid dissociation constant a1 is replaced by the acid dissociation constant a2, which 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 moieties derived from the structural moiety X and one of the second acidic moieties derived from the structural moiety Y, compound PI corresponds to a "compound having HA1 and HA2." More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined by determining the acid dissociation constant of the compound PI. - The pKa at which the compound is formed is the acid dissociation constant a1, and the above "A1 - and HA2" is "A1 - and A2 - The pKa at which the compound becomes "a compound having the above formula" 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 structural moiety X and one of the second acidic sites derived from structural moiety Y, compound PI corresponds to a "compound having two HA1s and one HA2." When determining the acid dissociation constant of compound PI, the acid dissociation constant when compound PI becomes "a compound having one A1 - and one HA1 and one HA2", and "a compound having one A1 - and one HA1 and one HA2" becomes "a compound having two A1 - and one HA2" correspond to the aforementioned acid dissociation constant a1. The acid dissociation constant when "a compound having two A1 - and one HA2" becomes "a compound having two A1 - and A2 - " corresponds to the acid dissociation constant a2. That is, in the case of compound PI, when there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 in which the cationic site M1 + in the above structural site X is replaced by H + , the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. When the acid dissociation constant when compound PI becomes "a compound having one A1 - and one HA1 and one HA2" is aa, and the acid dissociation constant when "a compound having one A1 - and one HA1 and one HA2" becomes "a compound having two A1 - and one HA2" is ab, the relationship between aa and ab satisfies aa < ab.

[0131] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant described above. The above 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 sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - , and two or more of the above M1 + may be the same or different from each other. [[ID=​​​​​​​may be the same or different, but - and A2 above - 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 not more than 2.0, more preferably not more than 0. The lower limit of the acid dissociation constant a1 is preferably not less than −20.0.

[0135] Anionic site A1 - and anionic site A2 - 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. Anionic site A1 - As the acid group, those capable of forming an acidic site 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. In addition, the anionic site A2 - As the anion moiety A1 - Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following formulae (AA-1) to (AA-3) and (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] [ka]

[0137] [ka]

[0138] Cationic moiety M1 + and cationic moiety M2 + is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. + 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 structural moieties X described above and one or more of the structural moieties Z described below, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation. Structural site Z: a ​​non-ionic site capable of neutralizing acids

[0140] In compound (II), the definition of the structural moiety X and A1 - and M1 + The definition of the structural moiety X in the compound (I) and A1 - and M1 + The definition and preferred embodiments are also the same.

[0141] In the compound (II), the cation moiety M1 in the structural moiety X + H + In the compound PII, the cationic moiety M1 in the structural moiety X is replaced by + H + The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the acid dissociation constant a1 is substituted with HA1 is the same as the acid dissociation constant a1 in the compound PI. In addition, when compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, it is considered that compound PII has "one A1 - and one HA1" and the acid dissociation constant when "a compound having one A1" - and one HA1" is "a compound with two A1 - 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 an 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. - , and two or more of the above M1 + 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 an electron. Examples of the group capable of electrostatically interacting with a proton or the functional group having an electron include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group 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] [ka]

[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 to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary to tertiary amine structure is preferred.

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

[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. 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. The photoacid generator may be used alone or in combination of two or more. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned suitable 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 compounds selected from basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. The acid diffusion controller is also preferably a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0150] (Basic Compounds (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] [ka]

[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 these may be bonded to form a ring. In formula (E), R 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 regard 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. 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 is preferably unsubstituted.

[0154] The basic compound (CA) also includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (CA) may be a compound having at least one structure 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 from 1.00 to 14.00, more preferably from 3.00 to 13.00, and even more preferably from 3.50 to 12.50.

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

[0132] to

[0136] of International Publication No. 2020 / 066824, the disclosures of which are incorporated herein by reference. Specific examples of low molecular weight compounds (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 disclosures of which are incorporated herein by reference.

[0157] (Compounds (CC) whose acid diffusion control ability is reduced or lost by exposure to 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] The compound (CD) may be a compound that generates an acid upon exposure to light. The compound (CD) is preferably a compound that generates an acid having a pKa that is at least 1.00 higher than that of the acid generated from the 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 from 0.50 to 10.00, more preferably from 0.80 to 5.00, and even more preferably from 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 in the description of the photoacid generator is + The same can be mentioned. X - 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] In particular, when the compound (CC) is an onium salt compound (CD) that is a relatively weak acid compared to the compound (N), the onium salt (CD) is preferably a compound containing an anion moiety represented by any one of the following formulae (BB-1) to (BB-7):

[0161] [ka]

[0162] Specific examples of the onium salt compound (CD) include, for example, 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 compounds described in paragraph

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

[0163] In addition to the compounds described above, 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 thereof 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 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total solid content of the resist composition, and preferably 30.0 mass% or less, more preferably 20.0 mass% or less, and even more preferably 10.0 mass% or less, based on the total solid content of the resist composition. The acid diffusion controller may be used alone or in combination of two or more. 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 the resin include a resin whose polarity increases under the action of acid (hereinafter simply referred to as an "acid-decomposable resin") and a hydrophobic resin. The resist composition preferably contains an acid-decomposable resin, and more preferably contains an acid-decomposable resin and a hydrophobic resin. The acid-decomposable resin will be described in detail below.

[0167] <Acid decomposable resin> (Repeating unit having an 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 acidic groups such as a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxy groups. 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 formula (Y1), formula (Y2), and formula (Y3). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(R 36 )(R 37 )(OR 38 ) Formula (Y3):-C(Rn)(H)(Ar)

[0169] In formula (Y1), Rx1 to Rx3 each independently represent 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). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. The alkyl groups of Rx1 to Rx3 are preferably alkyl groups 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, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The alkynyl group of Rx1 to Rx3 is preferably an ethynyl group or a propargyl group. The aryl group of Rx1 to Rx3 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] The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by bonding two of Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0171] When the resist composition of the present invention is used as an EUV resist, it is also preferable that the alkyl group, cycloalkyl group, alkenyl group, or aryl group represented by Rx1 to Rx3, and the ring formed by bonding two of Rx1 to Rx3, further have 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. R 36 is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl group may contain a group containing a heteroatom such as an oxygen atom and / or 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 group containing a heteroatom such as an oxygen atom and / or 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 the repeating unit and another substituent carried by 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, R 36 ~R 38 and 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] Other groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

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

[0177] [ka]

[0178] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom, provided that at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. Examples of the divalent linking group represented by L1 which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. Among these, L1 is preferably -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom-. The arylene group is preferably a phenylene group. 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] The alkyl group represented by R1 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R1, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by R1 may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0180] Examples of the leaving group represented by R2 which may have a fluorine atom or an iodine atom include leaving groups represented by any of the above-mentioned formulae (Y1), (Y2), and (Y3) and 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] [ka]

[0183] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight-chain or branched), an alkynyl group, or an aryl group (monocyclic or polycyclic). However, when all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0184] Examples of the alkyl group represented by Xa1 which may have a substituent include a methyl group or -CH2-R 11 Examples of the group include a group represented by the following formula: 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. Xa1 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 an -O-Rt- group, where 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, more preferably -CH2-, -(CH2)2- or -(CH2)3-.

[0186] The alkyl group of Rx1 to Rx3 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, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The alkynyl group of Rx1 to Rx3 is preferably an ethynyl group or a propargyl group. The aryl group of Rx1 to Rx3 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] The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Also preferred are polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In the cycloalkyl group formed by bonding two of Rx1 to Rx3, 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 formula (AI), for example, it is preferable that Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are 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 in the substituent is preferably 8 or less.

[0189] The repeating unit represented by formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

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

[0191] [ka]

[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. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, with the proviso that at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry1 to Ry3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0193] Examples of the alkyl group represented by Xb, which may have a substituent, include a methyl group or -CH-R 11 Examples of the group include a group represented by the following formula: R 11 represents 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, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being 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] The alkyl group represented by Ry1 to Ry3 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. The cycloalkyl groups represented by Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The alkenyl group represented by Ry1 to Ry3 is preferably a vinyl group. The alkynyl group represented by Ry1 to Ry3 is preferably an ethynyl group. The cycloalkenyl group represented by Ry1 to Ry3 is preferably a structure containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. The aryl group represented by Ry1 to Ry3 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] The cycloalkyl group formed by combining two of Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, among others. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. In the cycloalkyl group or cycloalkenyl group formed by combining two of Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or a -SO3- group, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group. In the repeating unit represented by formula (B), for example, Ry1 is a methyl group, ethyl group, vinyl group, allyl group, or aryl group, and Ry2 and Ry3 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 in 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 repeating units having an acid-decomposable group containing an unsaturated bond include the repeating units described in

[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. Further, for specific examples of the repeating unit A1, reference can be made to the descriptions of

[0029] to

[0071] in WO 2022 / 024928, which are incorporated herein by reference.

[0201] [ka]

[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, and 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, the total content thereof is preferably within the above-mentioned suitable 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 (a repeating unit having an acid-decomposable group). The repeating unit A2 may have 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 (preferably one to two) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Additionally, one or more of the fluorine atoms may be replaced by a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-.

[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] [ka]

[0206] In formula (Pa1), R a1 and R a2 each independently represents a hydrogen atom or a substituent. L a1 represents a single bond or a divalent linking group. Ar a1 represents an (m+n+1)-valent aromatic ring group. Ar a1 and R a2 or L a1 may be bonded via a single bond or a linking group. R 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 each independently represents a hydrogen atom or a substituent. R a1 and R a2 The substituent represented by the formula (I) is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R 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 a2The number of carbon atoms in the cycloalkyl group represented by the formula (I) 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 the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. R 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. L a1 Examples of the divalent linking group represented by the formula include -COO- and -CONR 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, an octylene group, etc. 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), Ara1 represents an (m+n+1)-valent aromatic ring group. Ar 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. Preferred examples of the aromatic heterocyclic group include groups containing an aromatic heterocycle having 4 to 20 ring atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and 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-, -CO2-, -SO-, -SO2-, 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. X Examples of the substituent represented by the formula (I) 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. R X Examples of the hydrocarbon group represented by the formula 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). R X The hydrocarbon group represented by R may have a substituent. XWhen the hydrocarbon group represented by contains -CH2-, at least one of the -CH2- may be replaced by at least one selected from the group consisting of -O-, -CO-, -S- and -SO2-. R 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] [ka]

[0215] In the formula (Pa2), R a4 represents a hydrogen atom or an alkyl group. L 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 between 1 and 5. 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. R a4The 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—, and a single bond is preferred. r represents an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and still more preferably 0. The aromatic ring in formula (Pa2) is 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, and is preferably an integer of 1 or more and 4 or less. m1 represents an integer of 0 or more and 4 or less, and preferably an integer of 0 or more and 3 or less.

[0218] In the above formula (Pa2), R X1 represents a halogen atom or a hydrocarbon group. R X1 The halogen atom represented by the formula (I) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or an iodine atom. R X1 Examples of the hydrocarbon group represented by the formula 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). R X1 The hydrocarbon group represented by R may have a substituent. X1 When the hydrocarbon group represented by the formula (I) contains -CH2-, at least one of the -CH2- may be replaced by at least one selected from the group consisting of -O-, -CO-, -S- and -SO2-. R X1The 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

[0079] to

[0110] of WO 2022 / 024928, the descriptions of which are incorporated herein by reference.

[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 % or more, more preferably 35 mol % or less, based on the total repeating units in the acid-decomposable resin.

[0221] (Repeating units 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 that has neither an acid-decomposable group nor an acid group but has 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] [ka]

[0223] In formula (C), L5 represents a single bond or an ester group, and R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. 10 represents 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. The total content of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom in the acid-decomposable resin 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

[0116] to

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

[0227] (Repeating units having a lactone group, a sultone group, or a carbonate group) The acid-decomposable resin may have a repeating unit (hereinafter simply referred to as "repeating unit Y") having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferred 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 sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among these, a 5- to 7-membered cyclic lactone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure, or a 5- to 7-membered cyclic sultone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure. For units containing a lactone group or a sultone group, see, for example, paragraphs

[0119] to

[0126] and

[0132] to

[0133] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

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

[0127] to

[0133] of International Publication No. 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 also referred to simply as a "repeating unit P"). Examples of the repeating unit P include a repeating unit represented by formula (4).

[0232] [ka]

[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—). L 42 is preferably at least one linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -S-, -SO-, -SO2-, 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 is 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 is preferably 3 to 20, and more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and 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] [ka]

[0237] In equation (S4-1), Q - represents the residue of an acid, and M + represents a cation. * represents L 41 represents the bonding position with The acid residue is a group formed by dissociating a proton from an acid. Q - is a carboxylate anion group (COO - ), sulfonate anion group (SO3 - ), or a sulfonamide group (N - -SO2R 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. M + The explanation, specific examples and preferred ranges for M in the explanation of the photoacid generator above are + 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 unit described in

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

[0138] of WO 2022 / 024928 A, and the above descriptions are incorporated herein by reference. 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 unit described in paragraph

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

[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 different from the repeating units described above.

[0241] [ka]

[0242] In formula (V-1) and the following formula (V-2), R6 and R7 each independently represent 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. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X4 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 disclosure of which is incorporated herein by reference.

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

[0144] to

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

[0244] (Repeating units 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 type of 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 the repeating unit Y. The preferred content is also as described for the repeating unit Y.

[0245] The acid-decomposable resin may have a repeating unit having a hydroxy group or a cyano group, which improves adhesion to the substrate. 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), or 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 the repeating unit having a hydroxy group or a cyano group include the repeating units described in paragraphs

[0081] to

[0084] of JP 2014-098921 A, the disclosure of which is 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 increased. Examples of the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted at the α-position with an electron-withdrawing group (for example, a hexafluoroisopropanol group), with the carboxy group being preferred. Examples of repeating units having an alkali-soluble group include repeating units described in paragraphs

[0085] and

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

[0247] (Repeating units that have an alicyclic hydrocarbon structure and are not acid decomposable) The acid-decomposable resin may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposition. This reduces the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[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) that has neither a hydroxy group nor a cyano group.

[0249] [ka]

[0250] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group, where Ra2 represents 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 JP2014-098921A, the disclosures of which are incorporated herein by reference.

[0251] (Other repeating units) Furthermore, the acid-decomposable resin may have repeating units other than the repeating units described above. For example, see the descriptions in

[0141] to

[0143] and

[0169] to

[0170] of International Publication No. 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 selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a saturated hydrocarbon group having a hydroxyl 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 effects of shot noise, and further improves LWR performance.

[0255] The acid-decomposable resin can be synthesized by a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the acid-decomposable resin, as calculated as polystyrene by GPC, is preferably 30,000 or less, more preferably 1,000 to 30,000, still 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 from 1.0 to 5.0, more preferably from 1.0 to 3.0, even more preferably from 1.1 to 2.0, and particularly preferably from 1.1 to 1.5. The smaller the dispersity, the better the resolution and resist shape, and further 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 solid content of the resist composition. The acid-decomposable resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

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

[0258] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin, and more preferably has two or more of these. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306, the disclosures of which are incorporated herein by reference.

[0259] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably from 0.01 to 20.0 mass %, more preferably from 0.1 to 10.0 mass %, and even more preferably from 0.1 to 5.0 mass %, relative to the total solid content of the resist composition. The hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably 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 excellent adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include 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 from 0.0001 to 2.0 mass %, more preferably from 0.0005 to 1.0 mass %, and even more preferably from 0.1 to 1.0 mass %, relative to the total solid content of the resist composition. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably 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, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2). Details of the 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 mass %, and more preferably 1 to 20 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 % relative to 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 dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in a developer (for example, phenolic compounds having a molecular weight of 1,000 or less, or alicyclic or aliphatic compounds containing a carboxy group). The "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0264] The content of other additives is not particularly limited, but may be 20.0 mass % or less, 10.0 mass % or less, or 5.0 mass % or less relative to the total solid content of the resist composition. The other additives may be used alone or in combination of two or more. When two or more additives are used, the total content thereof is preferably 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 water content, the better, but the resist composition may contain 1 to 30,000 ppm by mass of water. Furthermore, the resist composition may contain residual monomers as impurities (for example, monomers derived from the raw material monomers used in the synthesis of the resin). When residual monomers are contained as impurities, the lower the content of the residual monomers, the better, but the resist composition may contain 1 to 30,000 ppm by mass of the total solid content of the resist composition.

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

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

[0268] An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto the substrate. If necessary, the resist composition is preferably filtered before application. 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 filter material 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 also be circulated and repeatedly filtered through the same filter.

[0270] The resist composition can be applied to a substrate (e.g., silicon, silicon dioxide-coated silicon, etc.) used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spinning using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After coating the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic films, organic films, anti-reflective films, 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 1000 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, since this allows for the formation of finer patterns 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. Specific examples of the basic compound that the top coat may contain 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). The exposure method may be a method in which the formed resist film is irradiated 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, preferably far ultraviolet light having 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), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0275] After exposure, it is preferable to bake (heat) the film before development. 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 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out by means provided in at least one of a conventional exposure machine and a developing machine, and may also be carried out 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 in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispense method). The developing time is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C. In step (3), a step of stopping the development while replacing the solvent with another solvent may be carried out.

[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 quaternary ammonium salts such as tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among 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 preferably 0.1 to 20% by mass. The pH of the alkaline developer is 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 solvent may be mixed with a plurality of the organic solvents, or may be mixed with a solvent other than the organic solvent 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, still 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 a carbon number of 9 to 12. The organic treatment liquid may contain only one type of hydrocarbon having a carbon number of 9 to 12, or two or more types of hydrocarbons. The hydrocarbon having 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 9 to 12 carbon atoms may contain structural isomers.

[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, with the entire organic developer being 100% by mass. 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 to 35% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, with the entire organic developer being 100% by mass.

[0282] The mass ratio of butyl acetate to hydrocarbon having 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having 9 to 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, still more preferably 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 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, and the like.

[0284] [Rinse process] After step (3) is performed, rinsing may be performed. The rinse 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 rinse 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 rinsing 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 rinsing liquid for a certain period of time (dip method), and a method in which the rinsing liquid is sprayed onto the surface of the substrate (spray method).

[0286] The pattern formation method of the present invention may also include a post-bake step 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 carried out, for example, at 40 to 250°C (preferably 90 to 200°C) for, for example, 10 seconds to 3 minutes (preferably 30 seconds 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 materials (e.g., solvent, rinse, anti-reflective coating composition, top coat 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 the raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the equipment with Teflon (registered trademark). Details of filtration using a filter are described in paragraph

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

[0290] In addition to filtration, impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used. As the adsorbent, known adsorbents can be used, for example, 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 above-mentioned various materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components 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 mass ppt or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred.

[0291] [Electronic device manufacturing method] The present specification also relates to a method for manufacturing an electronic device, which includes the above-described pattern formation method of the present invention, and an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present specification is one that is installed in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0292] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. 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 the Resist Composition> The components used in preparing the resist compositions used in the examples and comparative examples are shown below.

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

[0295] [ka]

[0296] [ka]

[0297] [ka]

[0298] [ka]

[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] [ka]

[0301] In a three-neck flask under a nitrogen atmosphere, 8.2 g of 4-dimethylaminopyridine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 51.0 g of triethylamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 107.6 g of methanol (ultra-dehydrated, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 50.0 g of 5-amino-2,4,6-triiodoisophthaloyl dichloride (manufactured by 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. 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 removed from the washed organic layer under reduced pressure, and 110 g of acetone was added to dissolve the contents. The contents were 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 stirred at -5 ° C. for 4 hours. To the resulting reaction solution, 40 mL of ethyl acetate, 40 mL of hexane, and 60 mL of ion-exchanged water were added, and the aqueous layer was removed using a separatory funnel. The solvent was removed 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 further purification.

[0303] The entire amount of (I)-1-C, 100 mL of tetrahydrofuran, 100 mL of ion-exchanged water, and 9 g of sodium hydrogen carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to 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, yielding 9.9 g of (I)-1-D.

[0304] In a three-neck 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 removing 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 identification of the obtained (I)-1 was 1 H-NMR (nuclear magnetic resonance), and 19 F-NMR was used. 1 H-NMR (400MHz, acetone-d6): δ (ppm) = 10.00 (br s, 1H), 8.38 (d, 6H), 8.23 ​​(d, 6H), 3.97 (s, 6H). 19 F-NMR (376.6MHz, acetone-d6): δ(ppm)=-63.9, -110.5.

[0305] [Acid decomposable resin] The content ratio of each repeating unit in the resins (A-1 to A-37) is shown in Table 1. The synthesis methods of resins A-1 and A-37 are shown below. Note that the other resins were synthesized according to known methods, similar to resins A-1 and A-37. In Table 1, the "mol %" column indicates the content (mol %) of each repeating unit relative to all repeating units. In Table 1, the column "Mw" indicates the weight average molecular weight. In Table 1, the column "Mw / Mn" indicates the dispersity. 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 ratio (molar ratio) of the resins was 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, a mixed solution of 30 g of a monomer represented by MA-16, 38 g of a monomer represented by MB-10, 112 g of propylene glycol monomethyl ether acetate, and 5.7 g of dimethyl 2,2'-azobisisobutyrate (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 6 hours to obtain a reaction solution. After the addition was completed, the reaction solution was stirred at 80°C for an additional 2 hours. The resulting reaction solution 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). The solution was then filtered, and the resulting solid was vacuum dried to obtain 58 g of Resin A-1. The weight average molecular weight (Mw: polystyrene equivalent) of the resulting 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 monomer MB-3 (6 g), monomer MB-20 (35 g), monomer MA-2 (27 g), propylene glycol monomethyl ether acetate (84 g), dimethyl 2,2'-azobisisobutyrate (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) (1.2 g), and methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate (Fujifilm Wako Pure Chemical Industries, Ltd.) (4.4 g) was added dropwise over 6 hours. After the dropwise addition was completed, 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 polymerization solution and stirred at 50°C for 5 hours. After stirring, the solution was allowed to cool to room temperature, and then ethyl acetate (650 g) and 0.2 mol / L aqueous hydrochloric acid (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 resulting solid was dried under 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] [Table 1]

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

[0310] [ka]

[0311] [ka]

[0312] [ka]

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

[0314] [ka]

[0315] [ka]

[0316] [ka]

[0317] [ka]

[0318] [ka]

[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] [ka]

[0321] [ka]

[0322] [ka]

[0323] [ka]

[0324] [ka]

[0325] [Hydrophobic resin] The structures of the 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 indicates the content (mol %) of each repeating unit relative to all repeating units. The type and molar ratio of each repeating unit correspond from left to right. In Table 2, the column "Mw" indicates the weight average molecular weight. In Table 2, the column "Mw / Mn" indicates 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 ratio (molar ratio) of the resins was 13 Measurement was performed by C-NMR.

[0326] [ka]

[0327] [Table 2]

[0328] [Surfactants] The surfactants (F-1 to F-3) are shown below. F-1: Megafac F176 (DIC Corporation, fluorine-based surfactant) F-2: Megafac R08 (DIC Corporation, fluorine and silicone surfactant) F-3: PF656 (OMNOVA, fluorine-based surfactant)

[0329] [solvent] The solvents (G-1 to G-9) used in preparing the resist compositions are shown below. 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 Composition> The components used in preparing the resist compositions used in the examples and comparative examples are shown 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 passed through a polyethylene filter with a pore size of 0.02 μm and filtered to prepare resist compositions for each of the Examples and Comparative Examples. "Solid content" 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 solid content. In Tables 3 to 6, 101 and 102, the "mixing ratio" column of "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 containing (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. Also, Table 102 is a continuation of Table 101.

[0331] [Table 3]

[0332] [Table 4]

[0333] [Table 5]

[0334] [Table 6]

[0335] [Table 7]

[0336] [Table 8]

[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 on a hot plate at 130°C for 300 seconds 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 Exitech EUV exposure system (Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). The exposure mask used had a line width of 20 nm and a 1:1 line and space pattern.

[0339] [Alkaline 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 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds, and then baked at 95 °C for 60 seconds to dry, obtaining a positive resist pattern. In this way, 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 to 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 line pattern with an average line width of 20 nm of each example and comparative example obtained was observed with a length measurement 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, one shot was defined as 3.5 mm vertically (in the y-axis direction) and 6.5 mm horizontally (in the x-axis direction), with 8 columns in the x-direction and 29 rows in the y-direction, for a total of 232 shots of exposure. Ten length measurement photographs (five lines per photograph) were taken for each shot, and the average of the 10 measurement values ​​was used as the length measurement value for that shot. The standard deviation of the length measurement values ​​for the 232 shots was multiplied by three to obtain 3σ. From the obtained 3σ value, the LWR was evaluated according to the following evaluation criteria, where S is the best and E is the worst.

[0343] (Evaluation criteria) S: 3σ of variation is 2.4 nm or less. A: The 3σ of variation is greater than 2.4 nm and equal to or less than 2.8 nm. B: 3σ of variation is greater than 2.8 nm and equal to or less than 3.2 nm. C: 3σ of variation is greater than 3.2 nm and equal to or less than 3.6 nm. D: 3σ of variation is greater than 3.6 nm and equal to or 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] [Table 9]

[0346] [Table 10]

[0347] [Table 11]

[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)] The 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 manner, 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 9-10, 11-12, and 104-105 below.

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

[0352] [Table 12]

[0353] [Table 13]

[0354] [Table 14]

[0355] [Table 15]

[0356] [Table 16]

[0357] <​​​​​​​The results in Tables 7 to 12 and Tables 103 to 105 confirm that the resist composition (actinic ray-sensitive or radiation-sensitive resin composition) of the present invention can form a pattern with a rectangular cross-sectional shape. On the other hand, the resist composition used in the comparative example did not contain the compound (N), and no pattern with a rectangular cross section was obtained.

[0359] Furthermore, by comparing Example 1-12 with Example 1-36, it was 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. From a comparison between Example 1-11 and Example 1-36, in the compound (N), R 1 It was confirmed that when is a hydrogen atom, the pattern shape (cross-sectional rectangularity) is more excellent. Comparison between Example 1-9 and Example 1-36 etc. confirmed that when the compound (N) is a compound represented by the formula (2) above, and in the formula (2), m is 1 or more, the pattern shape (cross-sectional rectangularity) is more excellent. From a comparison between Example 1-7 and Example 1-34, it is clear that the compound (N) is a compound represented by the formula (2), in which m R 2 At least one of the following is -CO-OR 3 , -O-CO-R 3 , -O-CO-OR 3 , -SO2-R 3 , or -SO3-R 3 and R 3 It was confirmed that when represents a monovalent organic group, the pattern shape (cross-sectional rectangularity) is more excellent. Comparison with Examples 1-1 to 1-7 etc. reveals that in the compound (N), Y in formula (1) is -(CR2) r It was confirmed that the pattern shape (cross-sectional rectangularity) was better when the thickness was -. From a comparison between Examples 1-36 and 1-37, it is clear that in the compound (N), Z in formula (1) is -SO3 - It was confirmed that the pattern shape (cross-sectional rectangularity) was more excellent when the above formula was used. Comparison of Examples 1-10 with other Examples confirmed that when X in formula (1) of the compound (N) is a single bond, the pattern shape (cross-sectional rectangularity) is more excellent. Comparison between Example 1-7 and Example 1-35 and the like confirmed that when n in formula (1) of the compound (N) is an integer of 3 or more, the LWR is more excellent. From a comparison between Examples 1-7 and 1-8, it is clear that in the compound (N), M + It has been confirmed that when is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms, the LWR is more excellent. By comparing the examples in Tables 9 and 10 with the examples in Tables 11 and 12, it was confirmed that when the developer contains butyl acetate and a hydrocarbon having 9 to 12 carbon atoms, at least one of the pattern shape (cross-sectional rectangularity) and LWR is superior.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) represented by formula (1) and a resin: 【Chemistry 1】 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 is -(CR ２ ) ｒ - or an arylene group having the substituent F. R's each independently represent 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, and 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): 【Chemistry 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 ＋ is synonymous with. Ar represents an (n+m+1)-valent aromatic group, and m represents an integer of 0 or greater. R 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. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, 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. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, 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. 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. However, when the compound (CC) is an onium salt compound (CD) that is a weaker acid than the compound (N), the onium salt compound (CD) is a compound containing an anion moiety represented by any one of the following formulae (BB-1) to (BB-7): 【Transformation 3】

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

15. forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1; exposing the resist film to light; 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): 【Chemistry 4】 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 is -(CR ２ ) ｒ - or an arylene group having the substituent F. R's each independently represent 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. Ar represents an (n+q+1)-valent aromatic group, and n and q each independently represent an integer of 1 or greater. 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. M ＋ represents a cation.

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