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

Abstract

Provided is a radiation-sensitive or actinic ray-sensitive resin composition capable of forming a pattern having a rectangular cross-sectional shape. 【Solution means】A radiation-sensitive or actinic ray-sensitive resin composition containing a compound (N) represented by formula (1) and a resin. TIFF0007697126000069.tif2596

Description

Technical Field

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

Background Art

[0002] Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integration), microfabrication by lithography using a radiation-sensitive resin composition (hereinafter, also simply referred to as "resist composition") has been performed. In recent years, with the high integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron region or quarter-micron region has been required. Along with this, the exposure wavelength has also tended to shorten from g-line to i-line, and further to KrF excimer laser light, and currently, an exposure apparatus using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. In addition, as a technique for further improving the resolution, the development of the so-called immersion method, in which a liquid with a high refractive index (hereinafter, also referred to as "immersion liquid") is filled between a projection lens and a sample, has been progressing.

[0003] At present, in addition to excimer laser light, lithography using an electron beam (EB: Electron Beam), X-rays, extreme ultraviolet (EUV), etc. is also being developed. Along with this, resist compositions that are effectively sensitive to various actinic rays or radiations have been developed.

[0004] For example, in Patent Document 1, a resist composition containing a salt represented by the following formula (I) is disclosed as "a resist composition capable of obtaining a pattern having excellent line edge roughness". In formula (I), R 1 and R 2 represent a fluorine atom or a perfluoroalkyl group. R 3 represents a hydrogen atom. X 1represents a divalent saturated hydrocarbon group, and the hydrogen atoms contained in said group may be substituted with fluorine atoms, and the -CH2- contained in said group may be replaced with -O- or -CO-. X 2 represents a single bond or an alkylene group, and the -CH2- contained in said group may be replaced with -O-, -NH- or -CO-. R 4 represents a cyclic hydrocarbon group, and the hydrogen atoms contained in said group may be substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom or an amino group. Z 1+ represents an organic cation. [Chemical formula] [Prior art documents] [Patent documents]

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

[0006] When the present inventors studied the resist composition described in Patent Document 1, they found that there was a problem in the cross-sectional shape of the obtained resist pattern, and there was room for improvement in order to form a pattern closer to a rectangular shape.

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

[0008] As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, it has been found that the above problems are solved by the following configuration.

[0009] 〔1〕 A photoactive ray-sensitive or radiation-sensitive resin composition containing a compound (N) represented by formula (1) described later and a resin. 〔2〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to 〔1〕, wherein the compound (N) is a compound represented by formula (2) described later. 〔3〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to 〔1〕 or 〔2〕, wherein R 1 is a hydrogen atom. 〔4〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to 〔2〕, wherein m is 1 or more. 〔5〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to 〔4〕, wherein at least one of the m R 2 is -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 , and R 3 represents a monovalent organic group. 〔6〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to any one of 〔1〕 to 〔5〕, wherein Y is -(CR2) r -, and R and r have the same meanings as R and r in the above formula (1). 〔7〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to any one of 〔1〕 to 〔6〕, wherein Z is -SO3 - . 〔8〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to any one of 〔1〕 to 〔7〕, wherein X is a single bond. 〔9〕 The photoactive ray-sensitive or radiation-sensitive resin composition according to any one of 〔1〕 to 〔8〕, wherein M + is a sulfonium cation or an iodonium cation. 〔10〕 M +The radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], which is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms. 〔11〕 The radiation-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 radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , further comprising an acid diffusion control agent. 〔13〕 The radiation-sensitive or radiation-sensitive resin composition according to

[12] , wherein the acid diffusion control agent is selected from a basic compound (CA), a low molecular weight compound (CB) having a nitrogen atom and a group that dissociates by the action of an acid, and a compound (CC) whose acid diffusion control ability decreases or disappears upon irradiation with actinic rays or radiation. However, when the compound (CC) is an onium salt compound (CD) that is a relatively weak acid with respect to the compound (N), the onium salt (CD) is a compound containing an anion moiety represented by any of the following formulas (BB-1) to (BB-7). 〔14〕 A resist film formed using the radiation-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 radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to

[13] ; A step of exposing the resist film; A step of developing the exposed resist film with a developer, and a pattern forming method. 〔16〕 A method for manufacturing an electronic device, including the pattern forming method according to

[15] . 〔17〕 A compound represented by formula (21) described later.

Advantages of the Invention

[0010] According to the present invention, a radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern having a rectangular cross-sectional shape can be provided. In addition, the present invention can also provide a resist film, a patterning method, a method for manufacturing a device, and a compound.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, "actinic ray" or "radiation" means, for example, emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, electron beams (EB), and the like. In this specification, "light" means actinic ray or radiation. In this specification, "exposure" means, unless otherwise specified, not only exposure by emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also drawing by particle beams such as electron beams and ion beams.

[0013] In this specification, "~" is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value. In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0014] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene-converted values by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0015] Regarding the notation of groups (atomic groups) in this specification, unless it is contrary to the gist of the present invention, notations that do not indicate substitution or non-substitution include groups containing substituents as well as groups having no substituents. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred as substituents. Examples of substituents can include monovalent non-metal atomic groups excluding a hydrogen atom, and can be selected, for example, from the following substituent 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; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxysilyl group; sulfanyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkylsulfonyl group; arylsulfonyl group; alkyl group; alkenyl group; cycloalkyl group; aryl group; heteroaryl group; hydroxy group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; carbamoyl group; etc. Also, when these substituents can further have one or more substituents, groups having one or more substituents selected from the above-mentioned substituents (for example, monoalkylamino group, dialkylamino group, arylamino group, trifluoromethyl group, etc.) as the further substituents are also included in the examples of the substituent T.

[0017] In this specification, the bonding direction of the divalent groups described is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", when Y is -COO-, Y may be -CO-O- or -O-CO-. The above compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0018] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution. Specifically, it is a value obtained by calculation based on the Hammett substituent constant and the database of known literature values using the following software package 1. All the pKa values described in this specification indicate the values obtained by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0019] Also, pKa can be determined by the molecular orbital calculation method. As a specific method, there is a method of calculating by calculating the dissociation free energy in an aqueous solution based on a thermodynamic cycle. + Regarding the calculation method of the dissociation free energy, for example, it can be calculated by DFT (density functional theory), but various other methods have been reported in the literature and the like, and it is not limited to this. Although there are multiple software that can perform DFT, for example, Gaussian16 can be mentioned. + In this specification, as described above, pKa refers to a value obtained by calculation based on the Hammett substituent constant and the database of known literature values using software package 1. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional theory) shall be adopted.

[0020] In this specification, pKa refers to the value obtained by calculation based on the Hammett substituent constant and the database of known literature values using software package 1 as described above. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional theory) shall be adopted. In this specification, pKa refers to "pKa in an aqueous solution" as described above. However, when the pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0021] In this specification, "solid content" refers to the components contained in a radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "resist composition") and that form a resist film, and does not include solvents. Further, any component contained in the resist composition and that forms a resist film, even if its property is liquid, is regarded as a solid content.

[0022] [Radiation-sensitive or radiation-sensitive resin composition] Hereinafter, the radiation-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as "resist composition") will be described in detail. The resist composition of the present invention contains a compound (N) represented by formula (1) described later and a resin. The resist composition may be a positive resist composition or a negative resist composition, but is preferably a negative resist composition. Further, 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 configuration can solve the problems of the present invention is not necessarily clear, but the present inventors presume as follows. Note that the mechanism by which the effect is obtained is not limited by the following presumption. In other words, even if the effect is obtained by a mechanism other than the following, it is included in the scope of the present invention.

[0024] The resist composition of the present invention contains a compound (N). The compound (N) is characterized by having an iodine atom and an amide bond. When the resist composition of the present invention is used as a resist for EUV, for example, the absorption efficiency of EUV light is generally poor, and particularly the EUV light absorption at the bottom of the resist pattern is insufficient, leading to deterioration of the pattern shape, so it is difficult to obtain a pattern with high rectangularity. Here, since the compound (N) has an iodine atom as described above, the absorption efficiency of EUV light is increased. Furthermore, since the compound (N) has an amide bond, the dispersibility of the compound (N) in the resist composition is excellent, so the absorption of EUV light at the bottom of the resist pattern is likely to increase. Therefore, it is presumed that since the compound (N) has the above configuration, a pattern with a cross-sectional shape closer to a rectangular shape can be formed. Hereinafter, the ability to form a pattern with a cross-sectional shape closer to a rectangular shape using the resist composition of the present invention is also referred to as "the effect of the present invention is more excellent".

[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 simply referred to as "exposure". Among them, EUV light is preferable). In the resist pattern formed using the resist composition, by generating the above acid, a difference in solubility in the developer can be created between the location irradiated with actinic rays or radiation and the location not irradiated, and a resist pattern can be formed.

[0026] The compound (N) preferably generates an acid having a pKa of less than 0 upon exposure. The pKa of the acid generated from the compound (N) upon exposure is preferably -0.1 or less, more preferably -0.5 or less. Also, the pKa of the acid generated from the compound (N) upon exposure is preferably -4.5 or more, more preferably -3.5 or more. Also, the molecular weight of the compound (N) is not particularly limited, but is preferably 500 to 3000, more preferably 600 to 2500, and even more preferably 700 to 2000. Hereinafter, formula (1) will be described in detail.

[0027] [Chemical formula]

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

[0029] In formula (1), Y represents -(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 of R represents the above substituent F. As Y, -(CR2) r - is preferred. R is preferably a hydrogen atom or the above substituent F, and preferably a hydrogen atom or a fluorine atom. Among them, it is preferable that all R are fluorine atoms in -(CR2) r -. Examples of the monovalent substituent represented by R include groups selected from the above substituent T. r represents an integer of 1 or more. r is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, and still more preferably 1 or 2.

[0030] The arylene group having the above 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, more preferably 1 to 4. In the arylene group having a fluorine atom, the number of carbon atoms of the arylene group is preferably 6 to 20, more preferably 6 to 10. Examples of the arylene group specifically 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. As X, a single bond is preferred. The divalent linking group represented by X is not particularly limited. For example, -(CR f 2) r -(R f each independently represents a hydrogen atom or a monovalent substituent, and at least one of R f represents the above substituent F. r represents an integer of 1 or more.). -CO-, -O-, -S-, -NH-, -SO-, -SO2-, -COO-, -CONH-, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 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 are exemplified.

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

[0033] L represents a single bond or an alkylene group. When the carbon number of the alkylene group is 2 or more, the methylene group in the alkylene group may be substituted with a divalent linking group selected from -O-, a carbonyl group, -S-, -NR N -, and a sulfonyl group. R N represents a hydrogen atom or an alkyl group. As L, a single bond is preferred. The alkylene group represented by L may be linear, branched, or cyclic. The number of carbon atoms of the linear alkylene group is preferably from 1 to 10, more preferably from 1 to 6, and still more preferably from 1 to 3. The number of carbon atoms of the branched alkylene group is preferably from 3 to 10, more preferably from 3 to 6. The number of carbon atoms of the cyclic alkylene group is preferably from 3 to 15, more preferably from 3 to 10. The methylene group in the alkylene group is preferably substituted with at least one of -O- and a carbonyl group.

[0034] W represents an (n + 1)-valent aromatic group which may have a substituent other than an iodine atom. n represents an integer of 1 or more. As n, an integer of 2 or more is preferable, and an integer of 3 or more is more preferable. 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. Further, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferable. The number of ring atoms of the aromatic ring is preferably from 5 to 20, more preferably from 5 to 15, and still more preferably from 6 to 10. When the aromatic ring is an aromatic heterocyclic ring, it preferably has a hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring atom. Among them, the aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0035] Examples of the substituent other than the iodine atom that W may have include substituents other than the iodine atom among the groups selected from the above substituent T. In formula (1), the group represented by "-L-W-(I) n " is preferably, among others, the group represented by the following formula (W).

[0036]

Chemical formula

[0037] In formula (W), L represents a single bond or an alkylene group. When the alkylene group has 2 or more carbon atoms, the methylene group in the alkylene group may be substituted with a divalent linking group selected from -O-, a carbonyl group, -S-, -NR N -, and a sulfonyl group. R N represents a hydrogen atom or an alkyl group. As L, a single bond is preferred. Specific examples and preferred embodiments of the alkylene group represented by L are as described above.

[0038] In formula (W), Ar represents an (n + m + 1)-valent aromatic group. m represents an integer of 0 or more. m is preferably 1 to 3, more preferably 1 or 2. The aromatic ring constituting the (n + m + 1)-valent aromatic group may be either a monocyclic or polycyclic ring. Further, the above aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. The number of ring atoms of the above aromatic ring is preferably 5 to 20, more preferably 5 to 15, and still more preferably 6 to 10. When the above aromatic ring is an aromatic heterocyclic ring, it preferably has a hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring atom. Among the above 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 excluding an iodine atom or a monovalent organic group. R 2 As the halogen atom represented by, a bromine atom is preferred. R 2 Examples of the monovalent organic group represented by include a group containing 1 or more carbon atoms among the groups selected from the above substituent T. R 2 is preferably an electron-withdrawing group. Among them, m R 2at least one of which is -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 is preferred. R 3 represents a monovalent organic group.

[0040] Examples of the electron-withdrawing group include those having a positive value as the substituent constant (σp value) of the Hammett rule. The substituent constant of the Hammett rule represents the effect of the substituent on the acid dissociation equilibrium constant of substituted benzoic acid numerically, and is a parameter indicating the strength of the electron-withdrawing property and electron-donating property of the substituent. The substituent constant of the Hammett rule in this specification means the substituent constant σ when the substituent is located at the para position of benzoic acid. The substituent constant (σp value) of the Hammett 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 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 using the software "ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08)".

[0041] Examples of the electron-withdrawing group include, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -CO2R EWG (σp: when R EWG is an ethyl group +0.45), -CONH2 (σp: +0.36), -COR EWG (σp: when R EWG is a methyl group +0.50), -CF3 (σp: +0.54), -SO2R EWG (σp: when R EWG is a methyl group +0.72), and -NO2 (σp: +0.78). R EWGEach independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and an aromatic ring group which may have a substituent. R EWG The aliphatic hydrocarbon group represented by may have an oxygen atom between carbon-carbon bonds, and one or more carbon atoms may be substituted with a carbonyl carbon (C=O). Examples of the substituent include a group selected from the above substituent T.

[0042] As described above, at least one of the m Rs 2 is preferably -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 . R 3 represents a monovalent organic group. Among them, all of the m Rs 2 are preferably -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 . Examples of the monovalent organic group represented by R 3 include substituents containing one or more carbon atoms among the groups selected from the above substituent T. Among them, R 3 is preferably an alkyl group having 1 to 10 carbon atoms, or an -alkylene group-aliphatic heterocyclic group.

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

[0044] In the above formula (1), M + represents a cation. Note that the cation represented by M + is a monovalent cation. The cation is not particularly limited, but preferably represents an organic cation. M + The cation represented by is preferably a cation having a fluorine atom. The number of fluorine atoms of the cation is not particularly limited, but 2 or more is preferable, 3 or more is more preferable, and 5 or more is still more preferable. As the upper limit, for example, 20 or less can be mentioned, and 15 or less is preferable. M + Among others, a sulfonium cation or an iodonium cation is preferable, a sulfonium cation having 3 or more fluorine atoms or an iodonium cation having 3 or more fluorine atoms is more preferable, and a sulfonium cation having 3 to 15 fluorine atoms or an iodonium cation having 3 to 15 fluorine atoms is still more preferable. As the above sulfonium cation, a cation represented by the formula (ZaI) described later is preferable, and the cation (ZaI-1) described later or the cation (ZaI-4b) described later is more preferable. Further, as the above iodonium cation, a cation represented by the formula (ZaII) described later is preferable.

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

[0046]

Chemical formula

[0047] In formula (2), Z, Y, X, R 1 , n, and M + The definitions and preferred embodiments of are the same as those of Y, X, R 1 , n, and M + in the above formula (1). In formula (2), Ar represents an (n + m + 1)-valent aromatic group. m represents an integer of 0 or more. The preferred embodiments of Ar and m are the same as those of Ar and m in the above formula (W). Among them, as m, an integer of 1 or more is preferable, 1 to 3 is more preferable, and 1 or 2 is still more preferable. In formula (2), R 2 represents a halogen atom excluding an iodine atom, or a monovalent organic group. R 2 The specific examples and preferred embodiments of are the same as the specific examples and preferred embodiments of R 2 in the above formula (W). Among them, at least one of the m R 2 is preferably -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 . The definition and preferred embodiment of R 3 are the same as the definition and preferred embodiment of R 3 in formula (W).

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

[0049]

Chemical formula

[0050] In formula (21), Z is -SO3 - , or -SO2-N -It represents -SO2-Rf. Rf represents a substituent F selected from a fluorine atom and an alkyl group having a fluorine atom. Y represents -(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 of the Rs represents the above substituent F. r represents an integer of 1 or more. X represents a single bond or a divalent linking group. n represents an integer of 1 or more. M + represents a cation. In formula (21), Z, Y, X, n and M + The specific examples and preferred embodiments of are the same as those of Y, X, n and M in the above formula (1). + are the same as the specific examples and preferred embodiments.

[0051] In formula (21), Ar represents an (n + q + 1)-valent aromatic group. q represents an integer of 1 or more. q is preferably an integer of 1 or more, more preferably 1 to 3, and even more preferably 1 or 2. In formula (21), R 21 represents a halogen atom other than an iodine atom or a monovalent organic group, and at least one of the q Rs 21 is -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 is. R 3 represents a monovalent organic group. R 3 The specific examples and preferred embodiments of are the same as those of R in formula (W). 3 In addition, it is preferable that all of the q Rs 21 are -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 is.

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

[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"), but 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. Also, 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 compound, or may be in a form incorporated into a part of the resin. Also, a form of a low-molecular compound and a form incorporated into a part of the resin may be used in combination. The photoacid generator is preferably in the form of a low-molecular compound. When the photoacid generator is in the form of a low-molecular compound, the molecular weight of the photoacid generator is not particularly limited, but is preferably 500 to 3000, more preferably 600 to 2500, and still more preferably 700 to 2000. When the photoacid generator is in a form incorporated into a part of the 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 the photoacid generator include "M" + X- Examples thereof include compounds (onium salts) represented by 「」, and it is preferable that the compound generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (such as aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acid), carboxylic acids (such as aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0056] 「M + X - 」, M + represents a cation, and preferably represents an organic cation. The valence of the cation may be monovalent or divalent or higher. As the cation, a cation represented by the formula (ZaI) (hereinafter also referred to as 「cation (ZaI)」) or a cation represented by the formula (ZaII) (hereinafter also referred to as 「cation (ZaII)」) is preferable.

[0057]

Chemical formula

[0058] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represent an organic group. R 201 , R 202 , and R 203 preferably have 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, as the organic group. Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (such as a butylene group and a pentylene group), and -CH2-CH2-O-CH2-CH2-. When the resist composition of the present invention is used as a resist for EUV, R 201 ~R 205 preferably contains a fluorine atom or an iodine atom as a substituent. Preferable embodiments of the cation represented by the formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the cation (ZaI-3b), and the cation (ZaI-4b), which will be described later.

[0059] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 ~R 203 in the above formula (ZaI) is an aryl group. In the arylsulfonium cation, all of R 201 ~R 203 may be aryl groups, or a part of R 201 ~R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group. One of R 201 ~R 203 is an aryl group, and the remaining two of R 201 ~R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R 201 ~R 203 include an alkylene group (e.g., a butylene group, a pentylene group, and -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group. Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, a diarylcycloalkylsulfonium cation, an aryldialkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0060] As the aryl group contained in the arylsulfonium cation, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. 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 having an oxygen atom, a nitrogen atom, a sulfur atom or the like. 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 may have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group is more preferred.

[0061] The above aryl group may have a substituent, and examples of the substituent include 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 and 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 substituent may further have a substituent when possible, and it is also preferable that the above alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferable that the above substituents form an acid-decomposable group in any combination. Note that the acid-decomposable group is a group that decomposes by the action of an acid and increases in polarity, and preferably has a structure in which a polar group is protected by a group that desorbs by the action of an acid.

[0062] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is the R in formula (ZaI) 201 ~R 203 which are each independently a cation representing an organic group having no aromatic ring. The aromatic ring includes an aromatic ring containing a heteroatom. R 201 ~R 203 The carbon number of the organic group having no aromatic ring as R~R is preferably 1 to 30, more preferably 1 to 20. 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 R~R include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 may be further substituted by 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 described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0065]

Chemical formula

[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 (e.g., t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0067] R 1c ~R 5c any two or more of ~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 this ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. The ring may be a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0068] R 1c ~R 5c any two or more of ~R 6c and R 7c and R x and R yExamples of the group formed by the combination include alkylene groups such as a butylene group and a pentylene group. The 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 Examples of the group formed by the combination of and R include 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 Any two or more of, 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 the mutual connection of each may have a substituent.

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

[0071]

Chemical formula

[0072] In the formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. R 13represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), a hydroxy group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have substituents. R 14 represents a hydroxy group, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), 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 partially containing a cycloalkyl group). These groups may have substituents. R 14 When there are a plurality of them, they may be independent or different from each other. R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two Rs 15 may be bonded to each other to form a ring. When two Rs 15 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, it is preferable that two Rs 15 are an alkylene group and are bonded to each other to form a ring structure. The above alkyl group, the above cycloalkyl group, and the above naphthyl group, and the ring formed by two Rs 15 bonded to each other may have substituents.

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

[0074] Next, formula (ZaII) will be described. 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 As the aryl group of R and R, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Further, it may be an aryl group having a heterocycle having 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 As the alkyl group and cycloalkyl group of R and R, 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) is preferable.

[0075] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of R and R may each independently have a substituent. R 204 and R 205 Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R and R may have include 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 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group.

[0076] Specific examples of the organic cation are shown below, but the present invention is not limited thereto.

[0077]

Chemical formula

[0078]

Chemical formula

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

[0080] Examples of the non-nucleophilic anion include sulfonic acid anions (such as aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphorsulfonic acid anions), carboxylic acid anions (such as aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

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

[0082] As the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0083] The above-mentioned alkyl group, cycloalkyl group, and aryl group may have a substituent. Examples of the substituent include a nitro group, a halogen atom such as a fluorine atom and 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 a resist for EUV, it is also preferable that the substituent contains a fluorine atom or an iodine atom, and more preferably contains an iodine atom. Although there is no limitation on the number of fluorine atoms or iodine atoms, from the viewpoint of the absorption efficiency of EUV light, the larger the number, the more preferable.

[0084] As the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferable. 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] Examples of the sulfonylimide anion include a saccharin anion.

[0086] As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of the substituent of 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 preferable. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure.

[0087] Examples of other non-nucleophilic anions include fluorinated phosphorus (e.g., PF6 - ), fluorinated boron (e.g., BF4 - ), and fluorinated antimony (e.g., SbF6 - ).

[0088] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom. Among them, 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] Also preferred as non-nucleophilic anions are anions represented by the following formula (AN1).

[0090]

Chemical formula

[0091] In formula (AN1), R 1 and R 2 each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of the group that is not an electron-withdrawing group include a hydrocarbon group, a hydroxy group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group, and -R’, -OH, -OR’, -OCOR’, -NH2, -NR’2, -NHR’, or -NHCOR’ is preferable. 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 the above R’ include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; alkenyl groups such as an ethenyl group, a propenyl group, and a butenyl group; monovalent linear or branched hydrocarbon groups such as an ethynyl group, a propynyl group, and a butynyl group; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group; monovalent alicyclic hydrocarbon groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a norbornenyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a methylanthryl group; and monovalent aromatic hydrocarbon groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and an anthrylmethyl group.

[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. Among them, as the divalent linking group, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferable, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group- is more preferable.

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

[0095] In the formula (AN1-1), * a represents the bonding position with R in the formula (AN1). 3 * b represents the bonding position with -C(R 1 )(R 2 )- in the formula (AN1). X and Y each independently represent an integer from 0 to 10, and an integer from 0 to 3 is preferable. R 2a and R 2b each independently represent a hydrogen atom or a substituent. R 2a and R 2b When there are a plurality of each of R 2a and R 2b they may be the same or different from each other. However, when Y is 1 or more, R in CR 1 2 that directly bonds to -C(R 2 )(R 2b )- in the formula (AN1) 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, when X + Y in formula (AN1-1) is 1 or more, and both R 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 represents the bonding position on the R 3 side in formula (AN1), and B represents the bonding position on the -SO3 - side in formula (AN1).

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

[0097] As the organic group having the above-mentioned cyclic structure, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group is preferable, and a hydrocarbon group having a cyclic structure is more preferable. The hydrocarbon group having the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The above-mentioned 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 contains a halogen atom. The halogen atom contained in R 3 is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When it has an iodine atom, a structure directly bonded to a carbon atom on the aromatic ring is preferable. When the resist composition of the present invention is used as a resist for EUV, from the viewpoint of the absorption efficiency of EUV light, the larger the number of halogen atoms, the more preferable.

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

[0040] to

[0044] of JP-A-2018-155908,

[0184] to

[0185] ,

[0197] to

[0198] of JP-A-2021-128331,

[0124] to

[0125] ,

[0137] to

[0138] of WO2022 / 064863, and

[0056] to

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

[0100] As the non-nucleophilic anion, an anion represented by the following formula (AN2) is also preferable.

[0101]

Chemical formula

[0102] In formula (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10. L represents a divalent linking group. The definition of L is synonymous with 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 atom. The number of carbon atoms of this alkyl group is preferably from 1 to 10, more preferably from 1 to 4. As the alkyl group substituted with one or more fluorine atoms, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably all Xf are fluorine atoms.

[0104] R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms. R 4 and R 5 When there are a plurality of R 4 and R 5 may be the same or different from each other. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The above alkyl group may have a substituent. R 4 and R 5 are preferably hydrogen atoms.

[0105] W represents an organic group containing a cyclic structure. Among them, it is preferably a cyclic organic group. The carbon (the carbon contributing to ring formation) constituting the cyclic organic group 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 them, 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 preferable.

[0106] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable.

[0107] The above cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spiro, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 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 sulfonic acid ester group.

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

[0109] As the anion represented by formula (AN2), 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 preferable. q’ represents an integer from 0 to 10. L, q and W are the same as in formula (AN2).

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

[0076] of International Publication No. 2023 / 157455,

[0071] to

[0089] of JP-A No. 2021-081708,

[0033] to

[0045] of JP-A No. 2018-005224,

[0031] to

[0039] of JP-A No. 2018-025789,

[0176] to

[0183] ,

[0186] to

[0196] of JP-A No. 2021-128331,

[0116] to "0123",

[0126] to

[0136] of International Publication No. 2022 / 064863, and

[0076] of International Publication No. 2023 / 157455, and the above descriptions are incorporated herein.

[0111] As the non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferable.

[0112] [Chemical formula]

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

[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 composed of a combination of two or more of these.

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

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

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

[0029] to

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

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

[0037] to

[0055] , and

[0062] to

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

[0118] As the non-nucleophilic anion, a disulfonamide anion is also preferable. The disulfonamide anion is, for example, an anion represented by N - (SO2-R q )2. R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. The two Rs q may be bonded to each other to form a ring. The group formed by the two Rs q bonded to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. The carbon number of the above alkylene group is preferably 2 to 4.

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

[0120]

Chemical formula

[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 the anions described in paragraphs

[0041] to

[0047] of JP-A-2017-219836, paragraphs

[0026] to

[0028] of JP-A-2018-155902, paragraphs

[0040] to

[0041] ,

[0128] of JP-A-2020-154212, paragraphs

[0049] to

[0061] ,

[0278] to

[0279] of JP-A-2021-091666, paragraphs

[0150] to

[0154] of WO2022 / 064863, paragraphs

[0013] to

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

[0026] to

[0031] ,

[0050] to

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

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

[0088] of WO2023 / 157455. The above descriptions are incorporated herein.

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

[0123] The anion represented by formula (d1-2) is preferably different from the anions represented by the above-described formulas (AN1) to (AN3). For example, Z 2c is preferably other than an aryl group. Further, for -SO3 2c in Z, the atoms at the α-position and β-position relative to -SO3 - are preferably atoms other than carbon atoms having a fluorine atom as a substituent. Further, Z 2c is -SO3 -It is preferable that the atom at the α-position and / or the atom at the β-position with respect to [substance] is a ring member atom in the cyclic group.

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

[0040] to

[0046] of JP-A-2019-211751, [paragraph numbers]

[0039] to

[0047] of JP-A-2021-128331, [paragraph numbers]

[0043] to

[0060] of JP-A-2021-165824, and [paragraph numbers]

[0062] ,

[0075] of International Publication No. 2023 / 119910, and the above descriptions are incorporated herein.

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

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

[0127] (Compound (I)) Compound (I) is a compound having one or more of the following structural moieties X and one or more of the following structural moieties Y, and generates an acid containing the following first acidic moiety derived from the following structural moiety X and the following second acidic moiety derived from the following structural moiety Y upon irradiation with actinic rays or radiation. Structural moiety X: Anion moiety A1 - and cation moiety M1 + and forms a first acidic moiety represented by HA1 upon irradiation with actinic rays or radiation. Structural moiety Y: Anion moiety A2 - and cation moiety M2+ comprises, and is a structural site 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 above compound (I), the cationic site M1 in the above structural site X + and the cationic site M2 in the above structural site Y + are replaced with H + to form a compound PI, and the acid dissociation constant a1 derived from the acidic site represented by HA1 in which the cationic site M1 in the above structural site X + is replaced with H + and the acid dissociation constant a2 derived from the acidic site represented by HA2 in which the cationic site M2 in the above structural site Y + is replaced with H + have the property that the acid dissociation constant a2 is larger than the acid dissociation constant a1.

[0129] Hereinafter, Condition I will be described in more detail. When the compound (I) is, for example, a compound that generates an acid having one first acidic site derived from the above structural site X and one second acidic site derived from the above structural site Y, the compound PI corresponds to "a compound having HA1 and HA2". The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are, more specifically, when determining the acid dissociation constant of the compound PI, the pKa when the compound PI becomes "a compound having A1 - and HA2" is the acid dissociation constant a1, and the pKa when the above "a compound having A1 - and HA2" becomes "a compound having A1 - and A2 - and" is the acid dissociation constant a2.

[0130] When the compound (I) is, for example, a compound that generates an acid having two first acidic sites derived from the above structural site X and one second acidic site derived from the above structural site Y, the compound PI corresponds to "a compound having two HA1 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 "one A1 - and one HA1 and one HA2" becomes "a compound having two A1 - and one HA2" correspond to the above-mentioned 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. In addition, 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 above-mentioned method for measuring the acid dissociation constant. 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. In compound (I), the above A1 - and the above A2 - , and the above M1 + and the above M2 +may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

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

[0133] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. The lower limit value of the acid dissociation constant a2 is preferably -4.0 or more.

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

[0135] Anionic site A1 - and anionic site A2 - are structural sites containing a negatively charged atom or atomic group, and examples thereof include structural sites selected from the group consisting of the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). Anionic site A1 - is preferably one that can form an acidic site with a small acid dissociation constant, and among them, any one of the formulas (AA-1) to (AA-3) is more preferable, and any one of the formulas (AA-1) and (AA-3) is still more preferable. Also, anionic site A2 - is preferably one that can form an acidic site with a larger acid dissociation constant than anionic site A1 - and is more preferably any one of the formulas (BB-1) to (BB-6), and still more preferably any one of the formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R A represents a monovalent organic group. The monovalent organic group represented by R A is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0136]

Chemical formula

[0137]

Chemical formula

[0138] Cationic site M1 + and cationic site M2 + are structural sites containing an atom or atomic group with a positive charge, and examples thereof include a monovalent organic cation. The organic cation includes, for example, the aforementioned M + represented organic cation.

[0139] (Compound (II)) Compound (II) is a compound having two or more of the above structural sites X and one or more of the following structural sites Z, and by irradiation with actinic rays or radiation, two or more of the above first acidic sites derived from the structural site X and the above structural site Z are generated. It is a compound that generates an acid containing. Structural site Z: A non-ionic site capable of neutralizing an acid

[0140] In compound (II), the definition of the structural site X, and A1 - and M1 + are the same as the definition of the structural site X in the aforementioned compound (I), and A1 - and M1 + and have the same preferred embodiments.

[0141] In the above compound (II), the cationic site M1 in the above structural site X + is replaced with H + In the compound PII formed by replacement, the cationic site M1 in the above structural site X + is replaced with H + Regarding the preferred range of the acid dissociation constant a1 derived from the acidic site represented by HA1 formed by replacement, it is the same as the acid dissociation constant a1 in the above compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the above first acidic sites derived from the above structural site X and the above structural site Z, the compound PII corresponds to a "compound having two HA1s". When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII becomes a "compound having one A1 - and one HA1", and the acid dissociation constant when the "compound having one A1 - and one HA1" becomes a "compound having two A1s - correspond to the acid dissociation constant a1.

[0142] The acid dissociation constant a1 is determined by the measurement method of the acid dissociation constant described above. The above compound PII corresponds to the acid generated when the compound (II) is irradiated with actinic rays or radiation. In addition, the two or more above structural sites X may be the same or different from each other. Two or more of the above A1 - , and two or more of the above M1 + may be the same or different from each other.

[0143] The nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited, and for example, it is preferably a group capable of electrostatically interacting with a proton or a site containing a functional group having electrons. Examples of the group that can interact electrostatically 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 a non-bonding electron pair that does not contribute to π-conjugation. The nitrogen atom with a non-bonding electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[0144]

Chemical formula

[0145] Examples of the partial structure of the group that can interact electrostatically with a proton or the functional group having an electron 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. Among them, a primary to tertiary amine structure is preferable.

[0146] Examples of the site other than the cation that the above compound (I) and compound (II) can have include the anions described in

[0277] to

[0280] of International Publication No. 2022 / 024928, and the above description is incorporated herein.

[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 still more preferably 5.0% by mass or more with respect to the total solid content of the resist composition. Also, the content of the photoacid generator is preferably 50.0% by mass or less, more preferably 45.0% by mass or less, and still more preferably 40.0% by mass or less with respect to the total solid content of the resist composition. Only one type of photoacid generator may be used, or two or more types may be used. When two or more types of photoacid generators are used, it is preferable that the total content thereof is within the range of the above preferred content.

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

[0149] The type of the acid diffusion control agent 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 dissociates by the action of an acid, and compounds (CC) whose acid diffusion control ability decreases or disappears upon irradiation with actinic rays or radiation. It is also preferable that the acid diffusion control agent is a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0150] (Basic compound (CA)) As the basic compound (CA), compounds having a structure represented by any of the following formulas (A) to (E) are preferable. In formulas (B), (C), (D) and (E), * represents the bonding position.

[0151] [Chemical formula]

[0152] In formula (A), R 200 ~R 202 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 (having 6 to 20 carbon atoms). At least two of R 200 ~R 202 may combine 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 200 , R 201 , R 202, R 203 , R 204 , R 205 and R 206 The alkyl group or cycloalkyl group represented by R may have a substituent. Regarding the above alkyl group, as the alkyl group having a substituent, 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 is preferable. 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 R is preferably unsubstituted.

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

[0155] The difference between the pKa of the conjugate acid of the basic compound (CA) and the pKa of the acid generated from the above compound (N) or the above photoacid generator (the value obtained by subtracting the pKa of the acid generated from the above compound (N) or the above 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 still more preferably 2.00 to 13.00. In addition, the pKa of the conjugate acid of the basic compound (CA) is preferably, for example, from 1.00 to 14.00, more preferably from 3.00 to 13.00, and still 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, and the above description is incorporated herein. Specific examples of the low-molecular compound (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include the compounds described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824, and the above description is incorporated herein.

[0157] (Compound (CC) whose acid diffusion control ability decreases or disappears upon irradiation with actinic rays or radiation) Specific examples of the compound (CC) include, specifically, an onium salt compound (CD) of an acid that is a relatively weak acid with respect to the above compound (N) and the above photoacid generator, and a basic compound (CE) whose basicity decreases or disappears upon irradiation with actinic rays or radiation.

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

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

[0160] Among them, when the above compound (CC) is an onium salt compound (CD) that is relatively a weak acid with respect to the above compound (N), the above onium salt (CD) is preferably a compound containing an anion part represented by any of the following formulas (BB-1) to (BB-7).

[0161]

Chemical formula

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

[0305] to

[0314] of International Publication No. 2020 / 158337, and the above description is incorporated herein. In addition, specific examples of the basic compound (CE) include those described in paragraphs

[0137] to

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

[0164] of International Publication No. 2020 / 066824, and the above description is incorporated herein.

[0163] In addition to the above-described compounds, as the acid diffusion controller, for example, the known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] of US Patent Application Publication No. 2016 / 0274458A1 can also be preferably used, and the above description is incorporated herein.

[0164] The molecular weight of the acid diffusion controller is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and still more preferably 200 to 2000.

[0165] When the resist composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more with respect to the total solid content of the resist composition. Also, the content of the acid diffusion controller is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and still more preferably 10.0% by mass or less with respect to the total solid content of the resist composition. Only one kind of acid diffusion controller may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total content thereof is within the range of the above preferred content.

[0166] [Resin] The resist composition of the present invention contains a resin. Examples of the resin include a resin whose polarity increases by the action of an acid (hereinafter, also simply referred to as "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. Hereinafter, the acid-decomposable resin will be described in detail.

[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 by the action of an acid and increases in polarity, and is typically a group that decomposes by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group that is eliminated by the action of an acid (leaving group). The acid-decomposable resin preferably increases in polarity by the action of an acid and decreases in solubility in an organic solvent. 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 phosphoric acid 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, and an alcoholic hydroxy group. Among them, as the polar group, a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

[0168] Examples of the group that is eliminated by the action of an acid include a group represented by any one of 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. Among them, Rx1 to Rx3 each preferably independently represent a linear or branched alkyl group, and more preferably each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring. As the alkyl group of Rx1 to Rx3, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group is preferable. As the cycloalkyl group of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable. As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable. As the alkynyl group of Rx1 to Rx3, an ethynyl group or a propargyl group is preferable. As the aryl group of Rx1 to Rx3, an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0170] As the ring formed by bonding two of Rx1 to Rx3, a cycloalkyl group is preferable. As the cycloalkyl group formed by bonding two of Rx1 to Rx3, 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 is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. One or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be replaced by a vinylene group. For the group represented by the formula (Y1), for example, a mode in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are combined to form the above-mentioned cycloalkyl group is preferable.

[0171] When the resist composition of the present invention is used as a resist for EUV, the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the combination of two of Rx1 to Rx3 preferably further have a fluorine atom or an iodine atom as a substituent.

[0172] In the formula (Y2), R 36 ~R 38 each independently represents a hydrogen atom or a monovalent organic group. R 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. It is also preferable that R 36 is a hydrogen atom. The above 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 above alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more of the methylene groups may be replaced by a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. R 38 may be bonded to another substituent of the main chain of the repeating unit to form a ring. The group formed by the bonding of R 38 and another substituent of 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 a resist for EUV, R 36 ~R 38 The monovalent organic group represented by, and R 37 And R 38 The ring formed by bonding with each other preferably further has a fluorine atom or an iodine atom as a substituent.

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

[0174] From the viewpoint of excellent acid-decomposability of the repeating unit, in the leaving group that protects the polar group, when a non-aromatic ring is directly bonded to the polar group (or its residue), the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring preferably does not have a halogen atom such as a fluorine atom as a substituent.

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

[0176] As the repeating unit A1, a repeating unit represented by the formula (A) is also preferable.

[0177]

Chemical formula

[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. However, at least one of L1, R1 and R2 has a fluorine atom or an iodine atom. Examples of the divalent linking group which may have a fluorine atom or an iodine atom represented by L1 include -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group which may have a fluorine atom or an iodine atom (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group formed by linking a plurality of these. Among them, as L1, -CO-, an arylene group, or - an arylene group - an alkylene group having a fluorine atom or an iodine atom - is preferable, and -CO- or - an arylene group - an alkylene group having a fluorine atom or an iodine atom - is more preferable. As the arylene group, a phenylene group is preferable. The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable. 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 2 or more is preferable, 2 to 10 is more preferable, and 3 to 6 is still more preferable.

[0179] The alkyl group represented by R1 may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable. 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 1 or more is preferable, 1 to 5 is more preferable, and 1 to 3 is still more preferable. The alkyl group represented by R1 may contain a heteroatom such as an oxygen atom other than a halogen atom.

[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-described formulas (Y1), (Y2), and (Y3) and having a fluorine atom or an iodine atom.

[0181] As the repeating unit A1, a repeating unit represented by the formula (AI) is also preferable.

[0182]

Chemical formula

[0183] In the 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 (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). However, 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. Two of Rx1 to Rx3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0184] Examples of the alkyl group which may have a substituent and is represented by Xa1 include a methyl group or a group represented by -CH2-R 11 and the like. R 11 represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group. Examples of the monovalent organic group represented by R 11 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. An alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xa1, a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.

[0185] Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably -CH2-, -(CH2)2-, or -(CH2)3-.

[0186] As the alkyl group of Rx1 to Rx3, 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 is preferable. As the cycloalkyl group of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable. As the alkynyl group of Rx1 to Rx3, an ethynyl group or a propargyl group is preferable. As the aryl group of Rx1 to Rx3, an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0187] As the cycloalkyl group formed by bonding two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferable. Also, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may be, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Further, one or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be replaced by a vinylene group. In formula (AI), for example, a mode in which Rx1 is a methyl group or an ethyl group and Rx2 and Rx3 are combined to form the above cycloalkyl group is preferable.

[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 carbon number of the substituent is preferably 8 or less.

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

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

[0191]

Chemical formula

[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. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry1 to Ry3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group, a cycloalkenyl group, etc.).

[0193] Examples of the alkyl group which may have a substituent represented by Xb include a methyl group or a -CH2-R 11 group represented by the formula. R 11 represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group. Examples include an alkyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, and an alkoxy group having 5 or fewer carbon atoms which may be substituted by a halogen atom. An alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[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 an -O-Rt- group. Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferred. Rt may have a substituent such as a halogen atom, a hydroxy group, or an alkoxy group. As L, a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group is preferred.

[0195] As the alkyl group represented by Ry1 to Ry3, 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 is preferable. As the cycloalkyl group represented by Ry1 to Ry3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. As the alkenyl group represented by Ry1 to Ry3, a vinyl group is preferable. As the alkynyl group represented by Ry1 to Ry3, an ethynyl group is preferable. As the cycloalkenyl group represented by Ry1 to Ry3, a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferable. As the aryl group represented by Ry1 to Ry3, an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0196] As the cycloalkyl group formed by bonding two of Ry1 to Ry3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. The cycloalkyl group or cycloalkenyl group formed by bonding two of Ry1 to Ry3 may be replaced, for example, by one of the methylene groups constituting the ring with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof. Further, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring of these cycloalkyl groups or cycloalkenyl groups may be replaced by a vinylene group. The repeating unit represented by formula (B) preferably has, for example, a mode in which Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an 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 of the substituent is preferably 8 or less.

[0198] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based 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-based 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 styrenecarboxylic acid tertiary ester-based repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

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

[0067] to

[0071] of International Publication No. 2022 / 024928, and the above description is incorporated herein.

[0200] Specific examples of the repeating unit A1 (repeating unit having an acid-decomposable group) are shown below, but are not limited thereto. The repeating units having an acid-decomposable group described in the examples described later are also preferred. In addition, as specific examples of the repeating unit A1, for example, the descriptions in

[0029] to

[0071] of International Publication No. 2022 / 024928 can also be referred to, and the above description is incorporated herein.

[0201]

Chemical formula

[0202] The content of the repeating unit A1 is preferably 15 mol% or more, more preferably 40 mol% or more, and still more preferably 60 mol% or more with respect to all the repeating units in the acid-decomposable resin. Also, the content of the repeating unit A1 is preferably less than 100 mol%, more preferably 95 mol% or less, and still more preferably 90 mol% or less with respect to all the repeating units in the acid-decomposable resin. The repeating unit A1 contained in the acid-decomposable resin may be one kind or two or more kinds. When there are two or more kinds of the repeating unit A1 contained in the acid-decomposable resin, it is preferable that their total content is within the range of the above-mentioned preferred content.

[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 above-mentioned repeating unit A1 (repeating unit having an acid-decomposable group). Also, the repeating unit A2 may have a fluorine atom or an iodine atom. As the acid group, 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 is preferable. Among them, the repeating unit A2 is preferably a repeating unit having a phenolic hydroxy group. One or more (preferably 1 to 2) of the above-mentioned hexafluoroisopropanol groups may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As the acid group, -C(CF3)(OH)-CF2- formed in this way is also preferable. Also, one or more of the fluorine atoms may be substituted with 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]

Chem.

[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 substituents represented by are not particularly limited, but are 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 may be either linear or branched and may have a substituent. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and still 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, a t-butyl group and the like. R a1 and R a2The number of carbon atoms of the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, 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 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 may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, 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 include, for example, -COO-, -CONR a3 -, an alkylene group, or a group formed by combining two or more of these groups. R a3 represents a hydrogen atom or an alkyl group. As the above alkylene group, 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, and an octylene group is preferred. The alkylene group may have a substituent. R a3 Examples of the alkyl group when R

[0209] In the above formula (Pa1), Ara1 represents an (m + n + 1)-valent aromatic ring group. Ar a1 The aromatic ring group represented by may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. As the aromatic hydrocarbon group, a group containing an aromatic hydrocarbon having 6 to 18 carbon atoms such as benzene, naphthalene, anthracene, and naphthacene is preferable. The aromatic heterocyclic group preferably contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring members. As the aromatic heterocyclic group, a group containing an aromatic heterocycle having 4 to 20 ring member atoms such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole is preferable.

[0210] Ar a1 and R a2 or L a1 may be bonded via a single bond or a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO2-, -SO-, -SO2-, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these. The alkylene group and the alkenylene group may have a substituent.

[0211] In the above formula (Pa1), R X represents a substituent other than a hydroxy group. Examples of the substituent represented by R X 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 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 may have a substituent. Also, R XWhen the hydrocarbon group represented by -CH2- is included, at least one of -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 is preferably a halogen atom. As the halogen atom, a fluorine atom or an iodine atom is preferable.

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

[0213] The repeating unit A2 is 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]

Chemical formula

[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 of 1 or more and 5 or less. m1 represents an integer of 0 or more and 4 or less.

[0216] In the above formula (Pa2), R a4 represents a hydrogen atom or an alkyl group. R a4The alkyl group represented by [alkyl group] 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. When r represents 0 in formula (Pa2), the aromatic ring is benzene; when r represents 1, it is naphthalene; when r represents 2, it is anthracene; and when r represents 3, it is naphthacene. n1 represents an integer of 1 or more and 5 or less, and 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 As the halogen atom represented by [halogen atom], a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, and a fluorine atom or an iodine atom is more preferred. R X1 Examples of the hydrocarbon group represented by [hydrocarbon group] 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 [hydrocarbon group] may have a substituent. Further, when the hydrocarbon group represented by [hydrocarbon group] contains -CH2-, at least one of -CH2- may be replaced by at least one selected from the group consisting of -O-, -CO-, -S-, and -SO2-. X1 R X1The hydrocarbon group represented by is preferably a hydrocarbon group having a halogen atom. As the halogen atom, a fluorine atom or an iodine atom is preferable.

[0219] Specific examples of the repeating unit A2 (repeating unit having an acid group) are shown below, but are not limited thereto. In the following structural formulas, G 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 described later is also preferable. In addition, specific examples of the repeating unit A2 include, for example, the repeating units described in

[0079] to

[0110] of International Publication No. 2022 / 024928, and the above description is incorporated herein.

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

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

[0222]

Chemical formula

[0223] In formula (C), L5 represents a single bond or an ester group. R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R 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 combining these.

[0224] The content of the repeating unit X is preferably 0 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, with respect to all the repeating units in the acid-decomposable resin. Further, as the upper limit value, it is preferably less than 40 mol%, more preferably 35 mol% or less, with respect to all the 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 the repeating unit having at least one of a fluorine atom, a bromine atom and an iodine atom include a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom or an iodine atom. Among the repeating units of the acid-decomposable resin, the total content of the repeating units having at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 40 mol% or more, with respect to all the repeating units of the acid-decomposable resin. The upper limit value is not particularly limited, but is, for example, 100 mol% or less with respect to all the repeating units of the acid-decomposable resin.

[0226] Specific examples of the repeating unit having a fluorine atom or an iodine atom include, for example, the repeating units described in

[0116] to

[0117] of International Publication No. 2022 / 024928, and the above description is incorporated herein.

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

[0228] As the lactone group or sultone group, it is only necessary to have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among them, those in which another ring structure is fused to the 5- to 7-membered lactone structure in the form of forming a bicyclic structure or a spiro structure, or those in which another ring structure is fused to the 5- to 7-membered sultone structure in the form of forming a bicyclic structure or a spiro structure are more preferable. For the unit containing a lactone group or a sultone group, for example, reference can be made to the descriptions in

[0119] to

[0126] , and

[0132] to

[0133] of International Publication No. 2022 / 024928, and the above descriptions are incorporated herein.

[0229] As the carbonate group, a cyclic carbonate ester group is preferable. For the repeating unit having a cyclic carbonate ester group, for example, reference can be made to the descriptions in

[0127] to

[0133] of International Publication No. 2022 / 024928, and the above descriptions are incorporated herein.

[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 all the repeating units in the acid-decomposable resin. Further, as the upper limit value, it is preferably less than 40 mol%, more preferably 35 mol% or less, based on all the repeating units in the acid-decomposable resin.

[0231] (Repeating unit having a photoacid generator 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 generator group"), but it is also preferable that the acid-decomposable resin does not contain a repeating unit having a photoacid generator group (hereinafter, also simply referred to as "repeating unit P"). Examples of the repeating unit P include the repeating unit represented by formula (4).

[0232] [Chemical formula]

[0233] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linking group. L 42 represents a divalent linking group. R 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 a linking group composed of at least one 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, an aryl group, etc.). The alkylene group may be either linear or branched. The number of carbon atoms of 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 of the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The number of carbon atoms of 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 above-mentioned substituent T.

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

[0236]

Chemical formula

[0237] In formula (S4-1), Q - represents the residue of an acid, and M + represents a cation. * represents the bonding position with L 41 . The residue of an acid is a group formed by dissociation of a proton from an acid. Q - is a carboxylate anion group (COO - ), a sulfonate anion group (SO3 - ), or a sulfonamide group (N - -SO2R N1 ). R N1 represents an organic group, examples of which include an organic group having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferable. ) is preferable, and a sulfonate anion group is more preferable. Regarding the description, specific examples, and preferable range of M + , they are the same as those of M + in the description of the above photoacid generator.

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

[0094] to

[0105] of JP-A No. 2014-041327, the repeating units described in

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

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

[0094] to

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

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

[0239] When the acid-decomposable resin contains the repeating unit P, the content of the repeating unit P is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more with respect to all the repeating units in the acid-decomposable resin. Also, the content of the repeating unit P is preferably less than 40 mol%, more preferably 30 mol% or less, and still more preferably 20 mol% or less with respect to all the 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 the following formula (V-2) are preferably different from the above-described repeating units.

[0241] [Chemical formula]

[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 having 1 to 6 carbon atoms or a fluorinated alkyl group), 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 for reducing the mobility of the main chain) The acid-decomposable resin preferably has a high glass transition temperature (Tg) in that it can suppress excessive diffusion of the generated acid or pattern collapse during development. Regarding the repeating unit for reducing the mobility of the main chain, the contents of

[0144] to

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

[0244] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group) The acid-decomposable resin may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group in the acid-decomposable resin include the repeating units described for the repeating unit Y above. 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. This improves the 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). Further, it may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group. The repeating unit having a hydroxy group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxy group or a cyano group include the repeating units described in paragraphs

[0081] to

[0084] of JP-A-2014-098921, the disclosure of which is incorporated herein by reference.

[0246] The acid-decomposable resin may have a repeating unit having an alkali-soluble group. By including a repeating unit having an alkali-soluble group in the acid-decomposable resin, 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 bis-sulfonylimide group, and an aliphatic alcohol group in which the α-position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group), and a carboxy group is preferred. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs

[0085] and

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

[0247] (A repeating unit having an alicyclic hydrocarbon structure and not showing acid-decomposability) The acid-decomposable resin may have a repeating unit having an alicyclic hydrocarbon structure and not showing acid-decomposability. Thereby, elution of low molecular components from the resist film into the immersion liquid during immersion exposure can be reduced. Examples of the repeating unit having an alicyclic hydrocarbon structure and not showing acid-decomposability include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0248] (A repeating unit represented by formula (III) having neither a hydroxy group nor a cyano group) The acid-decomposable resin may have a repeating unit represented by formula (III) having neither a hydroxy group nor a cyano group.

[0249] [Chemical formula]

[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. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that has neither a hydroxy group nor a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of JP-A-2014-098921, the above description being incorporated herein.

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

[0141] to

[0143] ,

[0169] to

[0170] of WO 2022 / 024928, the above description being incorporated herein.

[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, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0253] A preferred embodiment of the present invention is that the acid-decomposable resin has at least one selected from the group consisting of saturated hydrocarbon groups having a lactone group, a carbonate group, a sultone group, and a hydroxy group. By the acid-decomposable resin having at least one selected from the group consisting of saturated hydrocarbon groups having a lactone group, a carbonate group, a sultone group, and a hydroxy group, the etching resistance and LWR performance are further improved.

[0254] It is a preferred embodiment of the present invention that the acid-decomposable resin contains a repeating unit having an iodine atom. By including a repeating unit having an iodine atom in the acid-decomposable resin, the absorption rate of EUV light or the like increases, the influence of shot noise can be reduced, and the LWR performance is further improved.

[0255] The acid-decomposable resin can be synthesized according to a conventional method (for example, radical polymerization). In terms of polystyrene conversion value by the GPC method, the weight average molecular weight (Mw) of the acid-decomposable resin 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 1.0 to 5.0, more preferably 1.0 to 3.0, still more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the side wall of the resist pattern is smoother and the roughness property is also better.

[0256] The content of the acid-decomposable resin in the resist composition is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 99.9% by mass, and still more preferably 60.0 to 90.0% by 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 are used, it is preferable that the total content is within the range of the above-mentioned suitable content.

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

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

[0275] to

[0279] of International Publication No. 2020 / 004306, the description of which is incorporated herein.

[0259] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and still more preferably 0.1 to 5.0% by mass based on the total solid content of the resist composition. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0260] [Surfactant] The resist composition of the present invention may contain a surfactant. When a surfactant is included, 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 the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

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

[0261] When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and still more preferably 0.1 to 1.0% by mass based on 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 are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0262] [Solvent] The resist composition of the present invention preferably contains a solvent. The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and at least one selected from the group consisting of (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The above solvent may further contain components other than components (M1) and (M2). Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein. The content of the solvent in the resist composition is preferably determined so that the solid content concentration is 0.5 to 30% by mass, and more preferably determined so that it is 1 to 20% by mass. When the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.

[0263] [Other Additives] The resist composition of the present invention may further contain at least one selected from the group consisting of a dissolution inhibitor compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group) as other additives. The above "dissolution inhibitor compound" is a compound having a molecular weight of 3000 or less that decomposes 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% by mass or less, 10.0% by mass or less, or 5.0% by mass or less based on the total solid content of the resist composition. As for other additives, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total content thereof is within the range of the above-mentioned preferred content.

[0265] In addition, the resist composition of the present invention may contain water as an impurity. When water is contained as an impurity, the content of water is preferably as small as possible, but it may be contained in an amount of 1 to 30,000 mass ppm with respect to the entire resist composition. In addition, the resist composition may contain a residual monomer (for example, a monomer (monomer) derived from a raw material monomer used in the synthesis of the resin) as an impurity. When a residual monomer is contained as an impurity, the content of the residual monomer is preferably as small as possible, but it may be contained in an amount of 1 to 30,000 mass ppm with respect to the total solid content of the resist composition.

[0266] [Pattern formation method] The pattern formation method of the present invention includes a step (1) of forming a resist film on a substrate using the photosensitive 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. Hereinafter, each of the above steps will be described in detail.

[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] Examples of the method of forming a resist film on a substrate using the resist composition include a method of applying the resist composition on the substrate. If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, still 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 it may be 0.001 μm or more. The material of the filter is not particularly limited. When it is a polymer, it preferably includes polyolefins such as polyethylene (PE) and polypropylene (PP) (including high density and ultra-high molecular weight); polyamides such as nylon 6 and nylon 66; polyimide (PI); polyamideimide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane; derivatives of the above polymers; etc. More preferably, it is composed of at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons and their derivatives. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0269] One filter may be used for filtering the resist composition, or two or more filters may be used in combination. When using two or more filters, they may be the same filter or different filters. Also, the resist composition may be circulated and filtered repeatedly with the same filter.

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

[0271] Examples of the drying method include a method of drying by heating. The heating can be carried out by means provided in at least one of a normal exposure machine and a developing machine, and it may also be carried out using a hot plate or the like. The heating temperature is not particularly limited, but 80 to 150 °C is preferable, 80 to 140 °C is more preferable, and 80 to 130 °C is even more preferable. The heating time is not particularly limited, but 30 to 1000 seconds is preferable, 60 to 800 seconds is more preferable, and 60 to 600 seconds is even more preferable.

[0272] The present invention also includes the resist film obtained in step (1). The film thickness of the resist film is not particularly limited, but 10 to 120 nm is preferable from the viewpoint of forming a more highly accurate fine pattern. Among them, in the case of EUV exposure, the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Further, in the case of ArF immersion exposure, the film 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 upper layer of the resist film using a top coat composition. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-61648 on the resist film. Specific examples of the basic compound that the top coat may contain include the basic compounds that the resist composition may contain.

[0274] 〔Step (2)〕 Step (2) is a step of exposing the resist film formed in step (1). Examples of the exposure method include a method of irradiating actinic rays or radiation through a predetermined mask onto the formed resist film. Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, the wavelength is 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm. Specifically, examples include 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] It is preferable to perform baking (heating) before development after exposure. This step is also referred to as post-exposure bake. Baking promotes the reaction in the exposed area, 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 normal exposure machine and a developing machine, or may 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-based developer). Examples of the developing method include a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of raising the developer on the substrate surface by surface tension and allowing it to stand for a certain period of time for development (paddle method), a method of spraying the developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method). The development time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50 °C, more preferably 15 to 35 °C. In step (3), a step of stopping development while substituting with another solvent may be carried out.

[0277] For the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited, and examples thereof include alkaline aqueous solutions containing a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0278] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent.

[0279] The above organic solvents may be mixed in plural, or may be mixed with a solvent other than the above organic solvents or water. The water content of the entire organic developer is preferably less than 50% by mass, more preferably less than 20% by mass, still 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 with respect to the total amount of the organic developer.

[0280] The organic developing solution preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having 9 to 12 carbon atoms. The hydrocarbon having 9 to 12 carbon atoms contained in the organic processing solution may be only one kind or two or more kinds. 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 developing solution 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 still more preferably 75% by mass or more and 90% by mass or less, based on 100% by mass of the total organic developing solution. The content of the hydrocarbon having 9 to 12 carbon atoms in the organic developing solution (the total amount when a plurality of hydrocarbons having 9 to 12 carbon atoms are contained) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and still more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the total organic developing solution.

[0282] The mass ratio of butyl acetate to the hydrocarbon having 9 to 12 carbon atoms in the organic developing solution (content of butyl acetate / content of hydrocarbon 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 developing solution may contain other components in addition to butyl acetate and the hydrocarbon having 9 to 12 carbon atoms. Examples of other components include water, butyl acetate, organic solvents other than hydrocarbons having 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, and the like.

[0284] 〔Rinse step〕 After performing step (3), rinsing may be performed. The rinse liquid is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general solvent can be used. The rinse liquid 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 method of rinsing is not particularly limited, and examples include a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time (dip method), and a method of spraying the rinse liquid onto the substrate surface (spray method).

[0286] Further, the pattern forming method of the present invention may include a post-bake step after step (3). By this step, the developer and the rinse liquid remaining between and inside the patterns are removed. In addition, this step also has the effect of softening the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250 ° C (preferably 90 to 200 ° C) for, for example, 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0287] Further, the formed pattern may be used as a mask to perform an etching process on the substrate. That is, the substrate (or the underlying 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 underlying film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the underlying 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] In the pattern forming method of the present invention, the developer, resist composition, and other various materials (for example, solvents, rinse liquids, compositions for forming an antireflection film, compositions for forming a top coat, etc.) used are preferably free of 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, still 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 content of impurities is not particularly limited and may be 0 mass ppt or more. Here, examples of the 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] Examples of methods for reducing impurities such as metals contained in various materials include a method of selecting raw materials with a low metal content as raw materials constituting the various materials, a method of performing filter filtration on the raw materials constituting the various materials, and a method of performing distillation under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). Details of the filtration using a filter are described in paragraph

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

[0290] In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. 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 can be used. In order to reduce impurities such as metals contained in the above various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. Whether the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal components contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of the metal components contained in the cleaning liquid after use is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and still more preferably 1 mass ppt or less. The lower limit is not particularly limited, and preferably 0 mass ppt or more.

[0291] [Method for manufacturing an electronic device] This specification also relates to a method for manufacturing an electronic device including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method. Preferable embodiments of the electronic device in this specification include embodiments mounted on electric and electronic devices (such as home appliances, OA (Office Automation), media-related devices, optical devices, and communication devices).

Examples

[0292] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0293] [Each component of the resist composition] Each component used for preparing the resist composition used in the examples and comparative examples is shown below.

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

[0295]

Chem.

[0296]

Chem.

[0297]

Chem.

[0298]

Chem.

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

[0300]

Chem.

[0301] In a three-necked flask, under a nitrogen atmosphere, 8.2 g of 4-dimethylaminopyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation), 51.0 g of triethylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation), 107.6 g of methanol (ultra-dehydrated, manufactured by FUJIFILM Wako Pure Chemical Corporation), 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. After cooling the obtained reaction solution to 0 °C, 550 mL of 1 mol / L hydrochloric acid and 600 mL of ethyl acetate were added, and the aqueous layer was removed with a separatory funnel. The obtained organic layer was washed three times with 300 mL of ion-exchanged water. After distilling off the solvent from the washed organic layer under reduced pressure, 110 g of acetone was added to dissolve the content, and crystallization was carried out with 160 g of ion-exchanged water to obtain 40 g of (I)-1-A.

[0302] In a three-necked flask, under a nitrogen atmosphere, 15.0 g of (I)-1-A, 90 mL of tetrahydrofuran (ultra-dehydrated, manufactured by FUJIFILM Wako Pure Chemical Corporation), and 3.9 g of triethylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were mixed, and then cooled to -10 °C. Subsequently, 7.6 g of (I)-1-B obtained by the method described in JP-A-2022-110777 was added dropwise to the obtained mixture, and the mixture was stirred at -5 °C for 4 hours. To the obtained 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 with a separatory funnel. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain a crude product of (I)-1-C. The obtained (I)-1-C was used in the next reaction without purification.

[0303] To a three-necked flask, the total 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 Corporation) were added, and the mixture was stirred at 60 °C for 4 hours. To the obtained 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 with a separatory funnel. Then, 1 mol / L hydrochloric acid was added to the obtained aqueous layer until the pH reached 5. Subsequently, 100 mL of ethyl acetate was added, the aqueous layer was removed with a separatory funnel, and the solvent was distilled off from the organic layer under reduced pressure to obtain 9.9 g of (I)-1-D.

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

[0305] [Acid-decomposable resin] The content ratios of the respective repeating units in the resins (A-1 to A-37) are shown in Table 1. The synthesis methods of Resin A-1 and Resin A-37 are shown. In addition, the other resins were synthesized according to known methods in the same manner as Resin A-1 and Resin A-37. In Table 1, the "mol%" column indicates the content (mol%) of each repeating unit with respect to all repeating units. In Table 1, the "Mw" column indicates the weight-average molecular weight. In Table 1, the "Mw / Mn" column indicates the dispersity. 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 in terms of polystyrene). Also, the composition ratio (molar ratio) of the resin was 13 measured by 13C-NMR (Nuclear Magnetic Resonance).

[0306] <Synthesis Example 1: Synthesis of Resin A-1> Propylene glycol monomethyl ether acetate (28 g) was heated to 80 °C under a nitrogen stream. While stirring this solution, a mixed solution of a monomer represented by MA-16 (30 g), a monomer represented by MB-10 (38 g), propylene glycol monomethyl ether acetate (112 g), and 2,2'-azobisisobutyric acid dimethyl [V-601, manufactured by Fuji Film Wako Pure Chemical Corporation] (5.7 g) was added dropwise over 6 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was stirred at 80 °C for an additional 2 hours. After allowing the obtained reaction solution to cool, it was reprecipitated with a large amount of a mixed solvent of heptane and ethyl acetate (heptane:ethyl acetate = 9:1, mass ratio), filtered, and the obtained solid was dried under vacuum to obtain 58 g of resin A-1. The weight-average molecular weight (Mw: polystyrene conversion) determined from the GPC (carrier: tetrahydrofuran (THF)) of the obtained resin A-1 was 8500, and the dispersity (Mw / Mn) was 1.60. 13 The molar ratio of the repeating units measured by C-NMR (nuclear magnetic resonance) was MB-10 / MA-16 = 50 / 50.

[0307] <Synthesis Example 2: Synthesis of Resin A-37> Propylene glycol monomethyl ether acetate (22 g) was heated to 85 °C under a nitrogen stream. While stirring this solution, a mixed solution of a monomer represented by MB-3 (6 g), a monomer represented by MB-20 (35 g), a monomer represented by MA-2 (27 g), propylene glycol monomethyl ether acetate (84 g), 2,2'-azobisisobutyric acid dimethyl [V-601, manufactured by Fuji Film Wako Pure Chemical Corporation] (1.2 g), and methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate [manufactured by Fuji Film Wako Pure Chemical Corporation] (4.4 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85 °C for an additional 2 hours to obtain a polymerization solution. To the obtained polymerization solution, methanol (100 g) and triethylamine (16 g) were added, and the mixture was stirred at 50 °C for 5 hours. After completion of the stirring, the solution was allowed to cool to room temperature, then ethyl acetate (650 g) and 0.2 mol / L hydrochloric acid aqueous solution (400 mL) were added and stirred for 30 minutes, and the organic layer was extracted. The extracted organic layer was washed 5 times with distilled water (400 mL). The washed organic layer was reprecipitated with a mixed solution of heptane / ethyl acetate = 9 / 1 (mass ratio), and then filtered. The obtained solid was dried under vacuum to obtain 38 g of resin A-37. The weight average molecular weight (Mw: polystyrene conversion) determined from the GPC (carrier: tetrahydrofuran (THF)) of resin A-37 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 structures of the respective repeating units in the acid-decomposable resin shown in Table 1 are shown below.

[0310]

Chemical formula

[0311]

Chemical formula

[0312]

Chemical formula

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

[0314] [Chemistry]

[0315] [Chemistry]

[0316] [Chemistry]

[0317] [Chemistry]

[0318] [Chemistry]

[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] [Chemistry]

[0321] [Chemistry]

[0322] [Chemistry]

[0323] [Chemistry]

[0324] [Chemistry]

[0325] [Hydrophobic resin] The structures of hydrophobic resins E (E-1 to E-8) are shown below. Also, Table 2 shows the content ratios of each repeating unit in the hydrophobic resin. In Table 2, the column "Molar ratio of repeating unit" indicates the content (mol%) of each repeating unit with respect to all repeating units. The types and molar ratios of the repeating units correspond in order from the left. In Table 2, the column "Mw" indicates the weight-average molecular weight. In Table 2, the column "Mw / Mn" indicates the dispersity. Note that 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 in terms of polystyrene). Also, the composition ratio (molar ratio) of the resin was 13 measured by C-NMR.

[0326] [Chemical formula]

[0327] [Table 2]

[0328] [Surfactant] Surfactants (F-1 to F-3) are shown below. F-1: Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant) F-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicon-based surfactant) F-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[0329] [Solvent] Solvents (G-1 to G-9) used for preparing the resist composition 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 the preparation of the resist compositions used in the examples and comparative examples are shown below. The components shown in Tables 3 to 6, Table 101, and Table 102 below were mixed so that the solid content concentration became 2% by mass. The obtained mixed solution was passed through a polyethylene filter with a pore size of 0.02 μm for filtration to prepare the resist compositions of the respective examples and comparative examples. "Solid content" refers to the components excluding the solvent. In Tables 3 to 6, Table 101, and Table 102, the description separated by " / " in the "Type" column indicates that the substance contains a plurality of compounds, and the description separated by " / " in the "% by mass" column indicates the contents of the plurality of compounds in order. In Tables 3 to 6, Table 101, and Table 102, the "% by mass" column indicates the content (% by mass) of each solid content component with respect to the total solid content. In Tables 3 to 6, Table 101, and Table 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 compound (N) and E-1 as a hydrophobic resin. Also, Table 6 is a continuation of Table 5. For example, Re-31 is a resist composition containing (I)-4 as compound (N) and E-2 as a 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 onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater “Mark8” manufactured by Tokyo Electron, and dried on a hot plate at 130° C. for 300 seconds to obtain a resist film with a film thickness of 45 nm. Here, 1 inch is 0.0254 m.

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

[0339] [Alkali Development (Examples 1-1 to 1-66, and Comparative Examples 1-1 to 1-2)] The exposed wafer was heated on a hot plate at 100 °C for 90 seconds, then immersed in a 2.38 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 shapes of the line patterns with an average line width of 20 nm in each example and comparative example obtained were observed with a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured. Using the value of Lb / La as an index, the cross-sectional rectangularity of the pattern shape was evaluated according to the following criteria. S is the best and G is the worst. The results are shown in Tables 7 to 8 and 103 below.

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

[0342] <Evaluation of LWR (Part 1)> For the pattern obtained by alkali 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, 3.5 mm in the vertical (y-axis direction) and 6.5 mm in the horizontal (x-axis direction) were defined as one shot, and exposure was performed on the wafer in 8 columns in the x direction and 29 rows in the y direction, for a total of 232 shots. For each shot, 10 length measurement photos (5 lines per photo) were measured, and the average of the 10 length measurement values was taken as the length measurement value for that shot. The standard deviation of the length measurement values for 232 shots was multiplied by 3 to obtain 3σ. Based on the obtained 3σ value, LWR was evaluated according to the following evaluation criteria. S is the best and E is the worst.

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

[0344] The evaluation results of the resist patterns of each example and comparative example (Examples 1-1 to 1-66 and Comparative Examples 1-1 to 1-2) obtained by alkali development 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 wafers exposed by the method described in the above [EUV Lithography] were heated on a hot plate at 90 °C for 60 seconds, and then developed for 30 seconds with the following developer J-1 or J-2, and spin-dried to obtain a negative resist pattern. J-1: n-Butyl Acetate J-2: n-Butyl Acetate / Undecane = 90 / 10 (mass ratio) In this way, the resist patterns of Examples 2-1 to 2-66, Comparative Examples 2-1 to 2-2, Examples 3-1 to 3-66, and Comparative Examples 3-1 to 3-2 were obtained. The resist compositions and developers used are shown in Tables 9 to 10 and Tables 11 to 12, and Tables 104 to 105 in the following section.

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

[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] [Table 17]

[0358] From the results of Tables 7 to 12 and Tables 103 to 105, it was confirmed that the resist composition (photosensitive or radiation-sensitive resin composition) of the present invention can form a pattern having a rectangular cross-sectional shape. On the other hand, the resist composition used in the comparative example did not contain the above compound (N), and a pattern having a rectangular cross-sectional shape could not be obtained.

[0359] Also, from the comparison between Example 1-12 and Example 1-36, etc., 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 the comparison between Example 1-11 and Example 1-36, etc., in the above compound (N), in formula (1), R 1 is a hydrogen atom, and it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Example 1-9 and Example 1-36, etc., when the above compound (N) is a compound represented by the above formula (2) and m in formula (2) is 1 or more, it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Example 1-7 and Example 1-34, etc., when the above compound (N) is a compound represented by the above formula (2) and at least one of the m R 2 is -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO2-R 3 , or -SO3-R 3 and R 3 represents a monovalent organic group, it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Example 1-1 to 1-7, etc., in the above compound (N), in formula (1), when Y is -(CR2) r -, it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Example 1-36 and Example 1-37, etc., in the above compound (N), in formula (1), when Z is -SO3 - , it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Examples 1-10 and other examples, etc., in the above compound (N), when X in formula (1) is a single bond, it was confirmed that the pattern shape (cross-sectional rectangularity) is more excellent. From the comparison between Examples 1-7 and Examples 1-35, etc., in the above compound (N), when n in formula (1) is an integer of 3 or more, it was confirmed that the LWR is more excellent. From the comparison between Examples 1-7 and Examples 1-8, etc., in the above compound (N), in formula (1), M + When it is a sulfonium cation having 3 or more fluorine atoms or an iodonium cation having 3 or more fluorine atoms, it was confirmed that the LWR is more excellent. From the comparison between each example described in Tables 9 to 10 and each example described in Tables 11 to 12, etc., when the developer contains butyl acetate and a hydrocarbon having 9 or more and 12 or less carbon atoms, at least one of the pattern shape (cross-sectional rectangularity) and the LWR was confirmed to be more excellent.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) represented by formula (2) and a resin: 【Chemistry 1】 In formula (2), Z is -SO ３ Represents -. Y is -(CR ２ ) ｒ - or an arylene group having a substituent F. The substituent F represents a substituent selected from a fluorine atom and an alkyl group having a fluorine atom. R each independently represents a hydrogen atom or a monovalent substituent, and at least one of R represents the substituent F. r represents an integer of 1 or more. X represents a single bond or a divalent linking group. R １ represents a hydrogen atom or a monovalent organic group. Ar represents an aromatic group having a valence of (n+m+1). n represents an integer of 1 or more. m represents an integer of 1 or more. R 2 represents a halogen atom excluding iodine atom, or a monovalent organic group, provided that at least one of the m R 2 s is -CO-O-R 3 , -O-CO-R 3 , -O-CO-O-R 3 , -SO 2 -R 3 , or -SO 3 -R 3 . R 3 represents a monovalent organic group. M ＋ represents a sulfonium cation or an iodonium cation.

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

3. Y is -(CR ２ ) ｒ 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R and r are defined as R and r in formula (2).

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein X is a single bond.

5. M ＋ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein is a sulfonium cation having three or more fluorine atoms or an iodonium cation having three or more fluorine atoms.

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

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

8. 8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, 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 eliminated by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation. However, when the compound (CC) is an onium salt compound (CD) which is a relatively weak acid compared to the compound (N), the onium salt compound (CD) is a compound containing an anion moiety represented by any one of the following formulas (BB-1) to (BB-7). 【Chemistry 2】

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

10. A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2; exposing the resist film to light; and developing the exposed resist film with a developer.

11. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 10.

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