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

Abstract

The present invention addresses the problem of providing an actinic-ray-sensitive or radiation-sensitive resin composition that has exceptional PED stability. An actinic-ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin and at least one photoacid generator selected from the group consisting of a first compound and a second compound, wherein: the first compound is an onium salt that contains an anion represented by formula (1); and the second compound contains a betaine structure that includes a −SO3 − group and an S+ atom, and contains an N atom to which two or more aromatic rings are bonded.

Description

Photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, method for manufacturing electronic devices

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

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

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

[0004] In resist compositions, photoacid generators may be used for photosensitive or radiation-sensitive properties. For example, Patent Document 1 discloses a photoacid generator having a predetermined structure.

[0005] Chinese Patent Application Publication No. 112920098

[0006] In lithography processes, it is preferable that the resulting pattern shape has low PED (Post Exposure Delay) dependence, i.e., excellent PED stability, from the viewpoint of microfabrication accuracy and process window. Note that the above PED refers to the length of the waiting time from exposure to development. When the inventors investigated the resist composition containing the photoacid generator disclosed in the above-mentioned literature, they found that there is room for further improvement in PED stability.

[0007] Therefore, the present invention aims to provide a photosensitive or radiation-sensitive resin composition with excellent PED stability. Furthermore, the present invention also aims to provide a resist film, a pattern formation method, and a method for manufacturing an electronic device related to the above-mentioned photosensitive or radiation-sensitive resin composition.

[0008] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0009] [1] A photosensitive or radiation-sensitive resin composition comprising a resin and at least one photoacid generator selected from the group consisting of a first compound and a second compound, wherein the first compound is an onium salt containing an anion represented by formula (1) described later, and the second compound is -SO ３ － Base and S ＋[1] A photosensitive or radiation-sensitive resin composition comprising a betaine structure containing atoms and comprising an N atom to which two or more aromatic rings are bonded. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the resin comprises repeating units having groups that decompose upon the action of an acid and increase in polarity. [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin comprises repeating units having phenolic hydroxyl groups. [4] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the photoacid generator is a sulfonium salt compound. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the second compound is a compound represented by formula (2) described later or a compound represented by formula (3) described later. [6] The photosensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit having a group that decomposes and increases in polarity due to the action of the above acid includes a repeating unit represented by formula (B1) described later. [7] In formula (1) above, L １ is an n+1 valent aromatic ring group, L ２ [1] to [6] any one of the following: [1] to [6] The active photosensitive or radiation-sensitive resin composition wherein the bond is a single bond. [8] The active photosensitive or radiation-sensitive resin composition further comprising an acid diffusion control agent. [9] The active photosensitive or radiation-sensitive resin composition according to [8], wherein the acid diffusion control agent is an onium salt.

[10] The active photosensitive or radiation-sensitive resin composition according to any one of the following: [1] to [9], wherein the molecular weight of the anion represented by formula (1) and the molecular weight of the second compound are 400 or more.

[11] A resist film formed using the active photosensitive or radiation-sensitive resin composition according to any one of the following: [1] to

[10] .

[12] A pattern forming method comprising the steps of: forming a resist film on a substrate with a photosensitive or radiation-sensitive resin composition according to any one of [1] to

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

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

[12] .

[0010] According to the present invention, a photosensitive or radiation-sensitive resin composition with excellent PED stability can be provided. Furthermore, according to the present invention, a resist film relating to the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device can also be provided.

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

[0012] In this specification, a numerical range expressed using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits. Also in this specification, if there are two or more types of a component, the "content" of that component means the total content of those two or more types of components. In this specification, in numerical ranges described in steps, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the value shown in the example. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure with emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, and X-rays, but also drawing with particle beams such as electron beams and ion beams.

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

[0015] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, specifically, a value obtained using the following software package 1, based on a database of Hammett substituent constants and publicly available literature values, as well as a value calculated by calculation. All pKa values ​​described herein are calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0016] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate it by calculating the dissociation free energy. ＋ The dissociation free energy can be calculated using, for example, the Density Functional Theory (DFT), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT, such as Gaussian 16.

[0017] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett substituent constants and known literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above. However, if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0018] In this specification, when there are multiple substituents and linking groups (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc. In this specification, the bonding direction of a divalent group (e.g., -COO-) as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -COO-, the compound may be "X-O-CO-Z" or "X-CO-O-Z".

[0019] In this specification, unless otherwise specified, monovalent substituents are preferred. Examples of substituents include monovalent nonmetallic groups excluding hydrogen atoms, and can be selected from the following substituent T, for example. In this specification, when referring to an aromatic ring group, for example, a group obtained by removing one or more hydrogen atoms from an aromatic ring is included. For example, an n-valent aromatic ring group is a group obtained by removing n hydrogen atoms from an aromatic ring. In this specification, when referring to an aromatic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from the above aromatic hydrocarbon ring is included, and when referring to an aromatic heterocyclic group, a group obtained by removing one or more hydrogen atoms from the above aromatic heterocyclic ring is included.

[0020] (Substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, and metactyl groups. Examples of substituents include acyl groups such as liloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfonic acid groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; and so on. Furthermore, if these substituents can have one or more substituents, groups having one or more substituents selected from the substituents listed above as further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) are also included as examples of substituent T.

[0021] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Also, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0022] In this specification, "solids" refers to the components that form the resist film and does not include solvents. Furthermore, any component that forms the resist film is considered a solid, even if its state is liquid.

[0023] [Photo-sensitive or radiation-sensitive resin composition] Hereinafter, the photo-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") will be described in detail. The resist composition of the present invention contains a resin and at least one photoacid generator selected from the group consisting of the first compound and the second compound described later. Although the reason why the resist composition having the above configuration can solve the problems of the present invention is not necessarily clear, 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 when the effect is obtained by a mechanism other than the following, it is included in the scope of the present invention. The photoacid generator contained in the resist composition of the present invention is an onium salt containing a predetermined anion structure in which at least two or more aromatic rings are bonded to a nitrogen atom or a betaine compound having a predetermined structure. The above photoacid generator has low crystallinity due to a predetermined structure around the nitrogen atom and can be uniformly dispersed in the resist film. At the same time, since the steric structure is large, diffusion in the resist film formed using the resist composition is suppressed. By these actions, local reaction and acid diffusion according to the passage of time from exposure to development (PED) are suppressed while maintaining the performance as a photoacid generator, and as a result, it is presumed that the PED stability is excellent.

[0024] [Photoacid generator] The resist composition contains at least one photoacid generator selected from the group consisting of the first compound and the second compound. Hereinafter, the first compound and the second compound will be described in detail.

[0025] <First compound>The first compound is an onium salt containing an anion represented by formula (1). In other words, the first compound is an onium salt composed of an anion represented by formula (1) and a cation. The resist composition preferably contains the first compound in terms of excellent resolution.

[0026] (Anion represented by formula (1))

[0027]

[0028] In formula (1), Ar １ represents a monovalent aromatic ring group which may have a substituent. R ａ１Ar represents a hydrogen atom or substituent. １ and R ａ１ Ar １ and L １ , and R ａ１ and L １ These may each be bonded to one another via single bonds or divalent linking groups to form a ring which may have substituents. １ This represents an n+1 valent linking group. ２ represents a single bond or a divalent linking group. n represents an integer of 1 or more. However, R ａ１ L represents a monovalent aromatic ring group which may have substituents, or １ This represents an n+1 valent aromatic ring group which may have substituents. n is 1, L １ The phenylene group is L ２ It is a single bond, and L １ -SO bonded to the phenylene group represented by ３ － Furthermore, when the N atom is at position 1 and position 4, the phenylene group has further substituents.

[0029] In formula (1), Ar １ represents a monovalent aromatic ring group which may have substituents. The aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with aromatic hydrocarbon being preferred. Examples of the aromatic hydrocarbon group include groups containing aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. The aromatic heterocyclic group preferably contains at least one heteroatom selected from nitrogen, oxygen, and sulfur atoms as a ring member. Examples of the aromatic heterocyclic group include groups containing aromatic heterocyclic rings with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0030] Ar １Examples of substituents that the monovalent aromatic ring group represented by may have include the substituent T mentioned above, and preferred substituents are alkyl groups (e.g., C1 to C15, preferably C1 to C6), cycloalkyl groups (e.g., C3 to C15, preferably C3 to C6), aromatic ring groups (e.g., C3 to C12), alkoxy groups (e.g., C1 to C15, preferably C1 to C6), aryloxy groups (e.g., C6 to C14), halogen atoms (preferably fluorine or iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or arylthio groups. The groups exemplified above as substituents may have further substituents if possible, for example, an alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group.

[0031] In formula (1), R ａ１ R represents a hydrogen atom or a substituent. Examples of the substituents include a substituted monovalent aromatic ring group, a substituted alkyl group, a substituted alkylcarbonyl group, a substituted arylcarbonyl group, a substituted heteroarylcarbonyl group, a substituted alkoxycarbonyl group, a substituted aryloxycarbonyl group, and a substituted heteroaryloxycarbonyl group. A substituted monovalent aromatic ring group is preferred in terms of superior LWR (Line Width Roughness) and resolution. ａ１ Examples and preferred embodiments of a monovalent aromatic ring group which may have the above substituent represented by Ar １It is the same as a monovalent aromatic ring group which may have substituents represented by . The alkyl group, and the alkyl group in the alkylcarbonyl group and alkoxycarbonyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10. The number of carbon atoms in the alkylcarbonyl group and alkoxycarbonyl group is preferably 2 to 16, more preferably 2 to 11. Examples of substituents that each of the groups exemplified above may have include the substituent T mentioned above, and a preferred embodiment is Ar １ These are the same substituents that may be present on a monovalent aromatic ring group represented by .

[0032] Ar １ and R ａ１ Ar １ and L １ , and R ａ１ and L １ These may each be bonded to one another via single bonds or divalent linking groups to form a ring which may have substituents. Examples of the divalent linking groups are -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene and alkenylene groups may have substituents. Ar １ and R ａ１ An example of a configuration in which these elements are bonded to each other via single bonds or divalent linking groups to form a ring which may have substituents is the configuration represented by formula (101).

[0033]

[0034] In formula (101), L １ , L ２ , and n is L in equation (1) １ , L ２ , and is synonymous with n. R ａ１０１ R represents a divalent linking group. ａ１０１ The divalent linking group represented by the above-mentioned R is ａ１Examples of groups obtained by removing one hydrogen atom from a substituent represented by L include L. １０１ Ar represents a single bond or a divalent linking group. Examples of divalent linking groups are as described above. １０１ Ar represents a divalent aromatic ring group which may have substituents. １０１ As a divalent linking group represented by the above Ar １ Examples include a group obtained by removing one hydrogen atom from a monovalent aromatic ring group which may have substituents represented by .

[0035] In formula (1), L １ This represents an n+1 valent linking group. Examples of n+1 valent linking groups include an n+1 valent aromatic ring group which may have substituents, and an n+1 valent aliphatic group which may have substituents, with an n+1 valent aromatic ring group which may have substituents being preferred.

[0036] L １ The aromatic ring group represented above may be monocyclic or polycyclic, with monocyclic being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with aromatic hydrocarbon groups being preferred. Examples of the aromatic hydrocarbon group include groups containing aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. The aromatic heterocyclic group preferably contains at least one heteroatom selected from nitrogen, oxygen, and sulfur atoms as a ring member. Examples of the aromatic heterocyclic group include groups containing aromatic heterocyclic rings having 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0037] L １ Examples of the aliphatic group represented by include an aliphatic hydrocarbon group which may have substituents. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 15, and more preferably 1 to 6. ２ If it contains -, -CH２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - may be replaced by at least one selected from the group consisting of -.

[0038] Examples of substituents that the above aromatic ring group and aliphatic group may have include the substituent T described above, and preferred substituents are alkyl groups (e.g., C1 to C15, preferably C1 to C6), cycloalkyl groups (e.g., C3 to C15, preferably C3 to C6), aromatic ring groups (e.g., C3 to C12), alkoxy groups (e.g., C1 to C15, preferably C1 to C6), aryloxy groups (e.g., C6 to C14), halogen atoms (preferably fluorine or iodine atoms), amino groups, hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or arylthio groups, with aromatic ring groups being more preferred. The groups exemplified above as substituents may have further substituents if possible, for example, the alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group, and the aryl group may further have an alkoxy group.

[0039] In formula (1), L ２ L represents a single bond or a divalent linking group. ２ Examples of divalent linking groups represented by include divalent aromatic ring groups which may have substituents, divalent aliphatic groups which may have substituents, and groups which are combinations thereof. ２ The definitions and preferred embodiments of the above-mentioned divalent aromatic ring group and divalent aliphatic group are as follows: １ It is the same as the group with n=1 among the groups listed as n+1 valent linking groups represented by L. ２ The divalent linking group represented by -L ２１ -L ２２ The group represented by - is also preferred. L ２１ is -O-, -CO-, -S-, -SO ２ - or a combination of these forms a base. L ２２This represents an alkylene group which may have substituents, or an arylene group which may have substituents. Examples of substituents include the substituent T mentioned above, preferably a halogen atom or an alkyl halide, and more preferably a fluorine atom or an alkyl fluoride. ２２ Among these, alkylene groups which may have a fluorine atom or an alkyl fluoride, or arylene groups which may have a fluorine atom or an alkyl fluoride, are preferred. In terms of the superior effects of the present invention, L ２ Examples include single bonds, divalent aromatic ring groups which may have substituents, or -L ２１ -L ２２ A group represented by - is preferred, and a single bond is more preferred.

[0040] In formula (1), n ​​represents an integer of 1 or more, and is preferably an integer of 2 or more, more preferably an integer between 2 and 4, and even more preferably 2 or 3, in terms of having superior LWR. When n represents an integer of 2 or more, there are multiple R ａ１ and Ar １ These elements may be identical or different from one another.

[0041] In formula (1), R ａ１ L represents a monovalent aromatic ring group which may have substituents, or １ However, it represents an n+1 valent aromatic ring group which may have substituents. ａ１ R represents an aromatic ring group which may have substituents, and the above R ａ１ and Ar １ A configuration in which R forms a ring which may have substituents via a single bond or a divalent linking group, and ａ１ R represents an aromatic ring group which may have substituents, and the above R ａ１ and L １ In some embodiments, R forms a ring which may have substituents via a single bond or a divalent linking group. ａ１ This is included in embodiments that represent a monovalent aromatic ring group which may have substituents. In terms of superior LWR and resolution, ａ１ L represents a monovalent aromatic ring group which may have substituents, and １Preferably represents an optionally substituted (n + 1)-valent aromatic ring group.

[0042] In formula (1), n is 1, and L １ is a phenylene group, L ２ is a single bond, and for the phenylene group represented by L １ bonded to -SO ３ － and when the N atom is in the 1-position and 4-position, the phenylene group further has a substituent. As the above-mentioned substituent, the groups exemplified as the optionally substituted groups of the aromatic ring group represented by L １ are mentioned, and an optionally substituted aromatic ring group is preferred.

[0043] In formula (1), n is 1, L １ is a phenylene group, and when L ２ is a single bond, -SO ３ － bonded to the phenylene group and the N atom are preferably in the 1-position and 2-position or the 1-position and 3-position. When n is 1 and L １ is a phenylene group, L ２ is preferably a divalent linking group.

[0044] In terms of the more excellent effects of the present invention, in formula (1), it is preferable that L １ [[ID=3ģ]] is an (n + 1)-valent aromatic ring group and L ２ is a single bond. That is, the anion represented by formula (1) is preferably the anion represented by formula (11).

[0045]

[0046] In formula (11), R ａ１ , Ar １ , and n are respectively synonymous with R ａ１ , Ar １ , and n in formula (1). Ar ２ represents an optionally substituted (n + 1)-valent aromatic ring group. The preferred embodiments of the optionally substituted (n + 1)-valent aromatic ring group represented by Ar ２ are as described for L １ .

[0047] The anion represented by formula (1) may also preferably not contain a cation atom.

[0048] For superior resolution, the molecular weight of the anion represented by formula (1) is preferably 300 or more, and more preferably 400 or more. There is no particular upper limit, but it is often 2000 or less, preferably 1500 or less, and more preferably 1200 or less.

[0049] Specific examples of anions represented by formula (1) are shown below, but the present invention is not limited thereto.

[0050]

[0051] (Cation) The cation in the first compound is not particularly limited, but an organic cation is preferred. As the organic cation, a sulfonium cation or an iodonium cation is preferred, and a sulfonium cation is more preferred. In other words, the first compound is preferably a sulfonium salt compound of an anion represented by formula (1) and a sulfonium cation. The valency of the cation may be monovalent or divalent or more, but monovalent is preferred.

[0052] The sulfonium cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)"). The iodonium cation is preferably a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0053]

[0054] In the formula (ZaI), R ２０１ , R ２０２ , and R ２０３ Each of these independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R２０３ Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH ２ -CH ２ -O-CH ２ -CH ２ - is an example. When the resist composition of the present invention is used as an EUV resist, R ２０１ ~R ２０５ Preferably, the cation contains a fluorine atom or an iodine atom as a substituent. Preferred embodiments of the cation represented by formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b).

[0055] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ It is an arylsulfonium cation in which at least one of the groups is an aryl group. ２０１ ~R ２０３ All of them may be aryl groups, or R ２０１ ~R ２０３ A portion of it may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ One of them is an aryl group, R ２０１ ~R ２０３ The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH ２ -CH ２ -O-CH ２ -CH ２Examples of arylsulfonium cations include triarylsulfonium cation, diarylalkylsulfonium cation, diarylcycloalkylsulfonium cation, aryldialkylsulfonium cation, and aryldicycloalkylsulfonium cation.

[0056] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being 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 containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. The alkyl 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, with methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group being more preferred.

[0057] The 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, an arylthio group, or an alkyloxycarbonylalkyleneoxy group. The above substituent may further have a substituent when possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferable that the above substituents form an acid-decomposable group by any combination. The acid-decomposable group is a group that decomposes by the action of an acid and has an increased polarity, and preferably has a structure in which a polar group is protected by a group that detaches by the action of an acid.

[0058] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is R in the formula (ZaI). ２０１ ~R ２０３ is a cation in which each independently represents an organic group having no aromatic ring. The number of carbon atoms of the organic group having no aromatic ring as R ２０１ ~R ２０３ is preferably 1 to 30, more preferably 1 to 20. As R ２０１ ~R ２０３ each independently, an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group is preferable, a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group is more preferable, and a linear or branched 2-oxoalkyl group is even more preferable.

[0059] R ２０１ ~R ２０３The alkyl group and cycloalkyl group represented by include, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R ２０１ ~R ２０３ The alkyl group and cycloalkyl group represented by may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxy group, a cyano group, or a nitro group.

[0060] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0061]

[0062] In the formula (ZaI-3b), R １ｃ ~R ５ｃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a 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.

[0063] 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 any two or more of R ｘ and Rｙ These elements may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3 to 10-membered rings, 4 to 8-membered rings are preferred, and 5 or 6-membered rings are more preferred.

[0064] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of groups formed by the bonding include alkylene groups such as butylene and pentylene groups. The methylene group in the alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0065] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The rings formed by the bonding of these elements to each other may have substituents.

[0066] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0067]

[0068] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. １３R represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. １４ R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. １４ The fields in which multiple instances exist may be independent or distinct from each other. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0069] In formula (ZaI-4b), R １３ , R １４ and R １５ The alkyl group represented by may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

[0070] Next, we will explain equation (ZaII). In equation (ZaII), R ２０４ and R ２０５ Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group.２０４ and R ２０５ The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. Alternatively, it may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0071] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ２０４ and R ２０５ Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0072] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0073]

[0074]

[0075] <Second Compound> The second compound is -SO ３ － Base and S ＋The compound contains a betaine structure containing atoms and an N atom to which two or more aromatic rings are bonded. The resist composition preferably contains the second compound in terms of superior LWR. The second compound only needs to contain the above-mentioned betaine structure, and may be, for example, a compound that contains the above-mentioned betaine structure and does not have any other anionic groups or cationic atoms, or it may be an onium salt (sulfonium salt compound) of a cation (sulfonium cation) containing the above-mentioned betaine structure and an anion, or it may be an onium salt of an anion (sulfonium cation) containing the above-mentioned betaine structure and an anion. When the second compound is an onium salt of an anion (sulfonium cation) containing the above-mentioned betaine structure, it is preferable that the cation (sulfonium cation) containing the betaine structure contains an N atom to which at least two aromatic rings are bonded. Furthermore, when the second compound is an onium salt of an anion (sulfonium cation) containing the above-mentioned betaine structure, it is preferable that the anion (sulfonium cation) containing the betaine structure contains an N atom to which at least two aromatic rings are bonded.

[0076] The second compound contains -SO ３ － The number of groups is one or more, preferably one or two, and more preferably one. The second compound contains S ＋ The number of atoms is one or more, preferably 1 to 4, and more preferably 1 or 2. The number of N atoms bonded to two or more aromatic rings in the second compound is one or more, preferably 1 to 4, and more preferably 1 to 3.

[0077] The multiple aromatic rings bonded to the N atom may be identical or different from each other. The aromatic rings may be either aromatic hydrocarbon rings or aromatic heterorings, with aromatic hydrocarbon rings being preferred. Examples of aromatic hydrocarbon rings include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. The aromatic heterorings preferably contain at least one heteroatom selected from nitrogen, oxygen, and sulfur atoms as ring members. Examples of aromatic heterorings include aromatic heterorings having 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. The number of aromatic rings bonded to the N atom is 2 or more, and 3 is also preferred.

[0078] The second compound is preferably a compound represented by formula (2), a compound represented by formula (3), or a compound represented by formula (4), with the compound represented by formula (2) or the compound represented by formula (3) being more preferred.

[0079]

[0080] In equations (2) and (3), R ａ１１ and R ａ１４ Each of these independently represents a hydrogen atom or a substituent. ａ１２ , R ａ１３ , R ａ１５ , and R ａ１６ Each of these independently represents a substituent. ａ１１ and R ａ１２ They may be bonded to each other to form a ring which may have substituents, R ａ１４ and R ａ１５ They may be bonded to each other to form a ring which may have substituents. １１ and Ar １２ Each of these independently represents a divalent aromatic ring group which may have substituents. １１ L represents a divalent linking group. １２ and L １４ Each of these independently represents a single bond or a divalent linking group.１３ This represents a linking group with m+1 valency. m represents an integer greater than or equal to 2. － R represents an anion. However, in the above formula (2), R ａ１１ L represents a monovalent aromatic ring group which may have substituents, or １１ R represents a divalent aromatic ring group which may have substituents. In formula (3) above, R ａ１３ L represents a monovalent aromatic ring group which may have substituents, or １３ R represents an m+1 valent aromatic ring group which may have substituents. In formula (4), R ａ１７ R represents a hydrogen atom or substituent. ａ１８ and R ａ１９ Each of these independently represents a substituent. Ar １３ R represents a monovalent aromatic ring group which may have substituents. ａ１７ and Ar １３ These may be linked to each other via single bonds or divalent linking groups to form a ring which may have substituents. １５ This represents a p+2 valent linking group. １６ and L １７ Each of these independently represents a single bond or a divalent linking group. p represents an integer of 1 or more. However, in formula (4) above, R ａ１７ L represents a monovalent aromatic ring group which may have substituents, or １５ However, it represents a p+2 valent aromatic ring group which may have substituents.

[0081] In equations (2) and (3), R ａ１１ and R ａ１４Each of these independently represents a hydrogen atom or a substituent. Examples of the substituents include a substituted monovalent aromatic ring group, a substituted alkyl group, a substituted alkylcarbonyl group, a substituted arylcarbonyl group, a substituted heteroarylcarbonyl group, a substituted alkoxycarbonyl group, a substituted aryloxycarbonyl group, and a substituted heteroaryloxycarbonyl group. A substituted monovalent aromatic ring group is preferred in terms of superior LWR and resolution. ａ１１ and R ａ１４ Examples and preferred embodiments of the monovalent aromatic ring group represented by formula (1) are as follows: １ This is the same as the monovalent aromatic ring group represented by . The alkyl group, as well as the alkyl group in the alkylcarbonyl group and alkoxycarbonyl group, may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The number of carbon atoms in the alkylcarbonyl group and alkoxycarbonyl group is preferably 2 to 16, and more preferably 2 to 11.

[0082] Examples of substituents that each of the groups exemplified above may have include the substituent T mentioned above, and a preferred embodiment is Ar １ It is the same substituent that may be present on a monovalent aromatic ring group represented by . Also, R ａ１１ and R ａ１４ The substituent represented by may also preferably have a sulfonium cation moiety. For example, R ａ１１ and R ａ１４ The substituent represented by -R ａ１１１ -S ＋ (R ａ１１２ ) (Caution ａ１１３ ) Y － It may also be a group represented by R. ａ１１１ R represents a divalent linking group. ａ１１１ As a divalent linking group represented by the above formula (1), L ２ The group shown as an example of a divalent linking group represented by R is an example. ａ１１１Among these, a divalent aromatic ring group, which may have substituents, is preferred. ａ１１２ and R ａ１１３ Each of these independently represents a substituent. ａ１１２ and R ａ１１３ The definition and preferred embodiment of the group represented by R ａ１２ and R ａ１３ It is the same as the base represented by Y. － Y represents an anion. － The definition and preferred embodiment of the anion represented by formula (3) is X － It is the same as the anion represented by .

[0083] In equations (2) and (3), R ａ１２ , R ａ１３ , R ａ１５ , and R ａ１６ Each of these independently represents a substituent. For example, in the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ Examples of organic groups represented by are given, and the preferred embodiment is the same. ａ１２ , R ａ１３ , R ａ１５ , and R ａ１６ Among these, optionally substituted aromatic ring groups or optionally substituted alkyl groups are preferred, and optionally substituted aryl groups are more preferred.

[0084] In formula (2), R ａ１１ and R ａ１２ They may be bonded to each other to form a ring which may have substituents, in formula (3), R ａ１４ and R ａ１５ They may be bonded to each other to form a ring which may have substituents. In formula (2), R ａ１１ and R ａ１２ An example of a configuration in which the elements are bonded to each other to form a ring which may have substituents is the configuration represented by formula (201). Also, in formula (3), R ａ１４ and R ａ１５ An example of a configuration in which the elements are bonded to each other to form a ring which may have substituents is the configuration represented by formula (301).

[0085]

[0086] In formula (201), R ａ１３ Ar １１ , L １１ , and L １２ These are R in equation (2), respectively. ａ１３ Ar １１ , L １１ , and L １２ This is synonymous with L. １１１ This represents a divalent linking group, and a divalent aromatic ring group, which may have substituents, is preferred in that it provides superior effects for the present invention. １１１ A preferred embodiment of the divalent aromatic ring group which may have substituents represented by Ar, is described later. １１ It is the same as a divalent aromatic ring group which may have substituents represented by . However, in formula (201), L １１１ L represents a divalent aromatic ring group which may have substituents, or １１ This represents a divalent aromatic ring group which may have substituents.

[0087] In formula (301), R ａ１６ Ar １２ , L １３ , L １４ , and m are R in equation (3), respectively. ａ１６ Ar １２ , L １３ , L １４ , and is synonymous with m. L １１２ This represents a divalent linking group, and a divalent aromatic ring group, which may have substituents, is preferred in that it provides superior effects for the present invention. １１２ A preferred embodiment of the divalent aromatic ring group which may have substituents represented by Ar, is described later. １２ It is the same as a divalent aromatic ring group which may have substituents represented by . However, in formula (301), L １１２ L represents a divalent aromatic ring group which may have substituents, or １３ This represents an m+1 valent aromatic ring group which may have substituents.

[0088] In equations (2) and (3), Ar １１ and Ar １２Each independently represents a divalent aromatic ring group which may have a substituent. The above aromatic ring group may be either a monocyclic or polycyclic group, with a monocyclic group being preferred. The above aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. Examples of the above aromatic hydrocarbon group include groups containing an aromatic hydrocarbon ring having 6 to 18 carbon atoms such as benzene, naphthalene, anthracene, and naphthacene. The above aromatic heterocyclic group preferably contains at least one heteroatom selected from nitrogen, oxygen, and sulfur atoms as ring members. Examples of the aromatic heterocyclic group include groups containing an aromatic heterocyclic ring having 4 to 20 ring member atoms such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. The above Ar １１ and Ar １２ Examples of the substituent which the monovalent aromatic ring group represented by may have include the groups exemplified as the substituent which the monovalent aromatic ring group represented by Ar １ in the above formula (1) may have, and the preferred embodiments are also the same.

[0089] In formula (2), L １１ represents a divalent linking group. Examples of the divalent linking group represented by L １１ include the groups exemplified as the (n + 1)-valent linking group represented by L １ where n = 1, and the preferred embodiments are also the same. Among them, L １１ is preferably a divalent aromatic ring group which may have a substituent.

[0090] In formula (2) and formula (3), L １２ and L １４ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group represented by L １２ and L １４ include the groups exemplified as the divalent linking group represented by L ２ in the above formula (1), and the preferred embodiments are also the same. Among them, L １２ and L １４ are preferably a single bond.

[0091] In formula (3), L １３ This represents an m+1 valent linking group. １３ As an m+1 valent linking group represented by L, １ Among the groups listed as n+1 valent linking groups represented by , the group where n=m can be cited, and the preferred embodiment is the same. In particular, L １３ As such, an m+1 valent aromatic ring group, which may have substituents, is preferred.

[0092] In formula (3), m represents an integer of 2 or more, and is preferably 2 or 3, with 2 being more preferred, in terms of superior LWR and resolution.

[0093] In formula (3), X － X represents an anion. － Anions represented by will be discussed later.

[0094] There are multiple R ａ１４ , R ａ１５ , R ａ１６ , and Ar １２ These can be the same or different from each other. Also, if m is an integer greater than or equal to 3, there can be multiple X － They may be the same or different from one another.

[0095] In formula (2), R ａ１１ L represents a monovalent aromatic ring group which may have substituents, or １１ This represents a divalent aromatic ring group. In terms of superior LWR and resolution, R ａ１１ L represents a monovalent aromatic ring group which may have substituents, and １１ However, it is preferable to represent a divalent aromatic ring group which may have substituents. In formula (3), R ａ１４ L represents a monovalent aromatic ring group which may have substituents, or １３ This represents an m+1 valent aromatic ring group. In terms of superior LWR and resolution, R ａ１４ L represents a monovalent aromatic ring group which may have substituents, and １３ However, it is preferable to represent an m+1 valent aromatic ring group which may have substituents.

[0096] In formula (4), R ａ１７R represents a hydrogen atom or substituent. ａ１７ The substituent represented by is R in formula (1) above. ａ１ Examples of substituents represented by include the groups shown, and the preferred embodiment is the same. ａ１７ Among these, monovalent aromatic ring groups, which may have substituents, are preferred because they offer superior LWR and resolution.

[0097] In formula (4), R ａ１８ and R ａ１９ Each of these independently represents a substituent. ａ１８ and R ａ１９ The substituents represented by are R in formulas (2) and (3). ａ１２ , R ａ１３ , R ａ１５ , and R ａ１６ Examples of substituents represented by the given symbol include the group shown, and the preferred embodiment is the same.

[0098] In formula (4), Ar １３ Ar represents a monovalent aromatic ring group which may have substituents. １３ A monovalent aromatic ring group which may have substituents represented by the above formula (1) is Ar １ Examples of monovalent aromatic ring groups that may have substituents represented by the given symbol include the groups shown, and the preferred embodiments are the same.

[0099] In formula (4), R ａ１７ and Ar １３ These may be bonded to each other via single bonds or divalent linking groups to form a ring which may have substituents. Examples of the divalent linking groups are -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have substituents.

[0100] In formula (4), L １５ This represents a p+2 valent linking group. １５ As a p+2 valent linking group represented by , L １Among the groups listed as n+1 valent linking groups represented by , the group where n=p+1 is an example, and the preferred embodiment is the same. L １５ Among these, a p+2 valent aromatic ring group, which may have substituents, is preferred.

[0101] In formula (4), L １６ and L １７ Each of these independently represents a single bond or a divalent linking group. １６ and L １７ As a divalent linking group represented by the above formula (1), L ２ The divalent linking group represented by is exemplified by the group shown, and the preferred embodiment is the same. １６ Among these, single bonds are preferred. １７ Among these, a single bond or a divalent aromatic ring group which may have substituents is preferred.

[0102] In formula (4), p represents an integer of 1 or more. p is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0103] In formula (4), R ａ１７ L represents a monovalent aromatic ring group which may have substituents, or １５ However, it represents a p+2 valent aromatic ring group which may have substituents. ａ１７ R represents an aromatic ring group which may have substituents, and the above R ａ１７ and Ar １３ In some embodiments, R forms a ring which may have substituents via a single bond or a divalent linking group. ａ１７ This is included in embodiments that represent a monovalent aromatic ring group which may have substituents. In terms of superior LWR and resolution, ａ１７ L represents a monovalent aromatic ring group which may have substituents, and １５ However, it is preferable to represent a p+2 valent aromatic ring group which may have substituents.

[0104] In terms of the superior effects of the present invention, in formula (2), L １１ L is a divalent aromatic ring group which may have substituents. １２It is also preferable that the bond is a single bond. That is, the compound represented by formula (2) is also preferable to be the compound represented by formula (21). Furthermore, in terms of the superior effects of the present invention, in formula (3), L １３ L is an m+1 valent aromatic ring group which may have substituents. １４ It is also preferable that the bond is a single bond. That is, the compound represented by formula (3) is also preferable to be the compound represented by formula (31). Furthermore, in terms of the superior effects of the present invention, in formula (4), L １５ L is a p+2 valent aromatic ring group which may have substituents. １６ It is also preferable that the bond is a single bond. That is, the compound represented by formula (4) is also preferable to be the compound represented by formula (41).

[0105]

[0106] In formula (21), R ａ１１ , R ａ１２ , R ａ１３ , and Ar １１ These are R in equation (2), respectively. ａ１１ , R ａ１２ , R ａ１３ , and Ar １１ This is synonymous with Ar. ２１ Ar represents a divalent aromatic ring group which may have substituents. ２１ The definition and preferred embodiment of a divalent aromatic ring group which may have substituents represented by L １１ As stated above.

[0107] In formula (31), R ａ１４ , R ａ１５ , R ａ１６ Ar １２ , m, and X － These are R in equation (3), respectively. ａ１４ , R ａ１５ , R ａ１６ Ar １２ , m, and X － This is synonymous with Ar. ２２ Ar represents an m+1 valent aromatic ring group which may have substituents. ２２ The definition and preferred embodiment of an m+1 valent aromatic ring group which may have substituents represented by L１３ As stated above.

[0108] In formula (41), R ａ１７ , R ａ１８ , R ａ１９ Ar １３ , L １７ , and p are R in equation (4), respectively. ａ１７ , R ａ１８ , R ａ１９ Ar １３ , L １７ , and is synonymous with p. Ar ２３ Ar represents a p+2 valent aromatic ring group which may have substituents. ２３ The definition and preferred embodiment of a p+2 valent aromatic ring group which may have substituents represented by L １５ As stated above.

[0109] (Anion) X as described above － The anion represented by will be described in detail. Organic anions are preferred as the above anions. Anions with a remarkably low ability to undergo nucleophilic reactions are preferred, and non-nucleophilic anions are more preferred.

[0110] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0111] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group may be, for example, a fluoroalkyl group (which may have substituents other than fluorine atoms; it may also be a perfluoroalkyl group).

[0112] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0113] The alkyl groups, cycloalkyl groups, and aryl groups listed above may have substituents. Examples of substituents include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms). When the resist composition of the present invention is used as an EUV resist, it is also preferable, and more preferable, to include a fluorine atom or an iodine atom as a substituent. There is no limit to the number of fluorine or iodine atoms, but from the viewpoint of EUV light absorption efficiency, the more the better.

[0114] In aralkyl carboxylate anions, aralkyl groups having 7 to 14 carbon atoms are preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl groups.

[0115] An example of a sulfonylimid anion is the saccharin anion.

[0116] In bis(alkylsulfonyl)imido anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in bis(alkylsulfonyl)imido anions may be bonded to each other to form a ring structure.

[0117] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF). ６ － ), fluorinated boron (for example, BF ４ － ), and fluorinated antimony (e.g., SbF ６ － ) are some examples.

[0118] As the above organic anion, the organic anion represented by the following formula (DA) is also preferred.

[0119]

[0120] In formula (DA), A ３１ － R represents an anionic group. ａ１ L represents a hydrogen atom or a monovalent organic group. ａ１ This represents a single bond or a divalent linking group.

[0121] A ３１ － This represents an anionic group. ３１ － The anionic group represented by is not particularly limited, but a group selected from the group consisting of groups represented by formulas (B-1) to (B-14) is preferred.

[0122]

[0123] *-O － Formula (B-14)

[0124] In equations (B-1) to (B-14), * indicates the bonding position. In equations (B-1) to (B-5) and equation (B-12), R Ｘ１ Each of these independently represents a monovalent organic group. In formulas (B-7) and (B-11), R Ｘ２ Each of these independently represents a hydrogen atom, or a substituent other than a fluorine atom and a perfluoroalkyl group. The two R in formula (B-7) Ｘ２ They may be the same or different. In formula (B-8), R ＸＦ１ R represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, two R ＸＦ１ Of these, at least one represents a fluorine atom or a perfluoroalkyl group. The two R in formula (B-8) ＸＦ１ They may be the same or different. In formula (B-9), R Ｘ３ R represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer from 0 to 4. If n1 represents an integer from 2 to 4, multiple R Ｘ３ They may be the same or different. In formula (B-10), R ＸＦ２ * represents a fluorine atom or a perfluoroalkyl group. The bond position represented by * in formula (B-14) and the bond partner are preferably a phenylene group which may have substituents. Examples of substituents which the phenylene group may have include halogen atoms.

[0125] In equations (B-1) to (B-5), and equation (B-12), R Ｘ１ Each of these independently represents a monovalent organic group. Ｘ１ Preferred members include alkyl groups (which may be linear or branched; preferably with 1 to 15 carbon atoms), cycloalkyl groups (which may be monocyclic or polycyclic; preferably with 3 to 20 carbon atoms), or aryl groups (which may be monocyclic or polycyclic; preferably with 6 to 20 carbon atoms). Also, R Ｘ１ The above group represented by may have substituents. Note that in formula (B-5), R Ｘ１ The atoms directly bonded to N- are the carbon atoms in -CO- and -SO ２ It is also preferable that it is not any of the sulfur atoms in -

[0126] R Ｘ１ The cycloalkyl group in R may be monocyclic or polycyclic. Ｘ１ Examples of cycloalkyl groups in this context include norbornyl and adamantyl groups. Ｘ１ The substituents that the cycloalkyl group in R may have are not particularly limited, but alkyl groups (which may be linear or branched; preferably having 1 to 5 carbon atoms) are preferred. Ｘ１ One or more of the carbon atoms that are ring member atoms of the cycloalkyl group may be replaced by carbonyl carbon atoms.

[0127] R Ｘ１ The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Ｘ１ The substituents that the alkyl group in R may have are not particularly limited, but for example, cycloalkyl groups, fluorine atoms, or cyano groups are preferred. An example of a cycloalkyl group as the substituent is R Ｘ１ The cycloalkyl groups described above are similarly listed when R is a cycloalkyl group. Ｘ１ If the alkyl group in has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group. Also, R Ｘ１ The alkyl group in this case is one or more -CH ２ The negative sign may be substituted with a carbonyl group.

[0128] R Ｘ１ In this case, a benzene ring group is preferred as the aryl group. Ｘ１ The substituents that the aryl group in R may have are not particularly limited, but alkyl groups, fluorine atoms, or cyano groups are preferred. An example of an alkyl group as the substituent is R Ｘ１ The alkyl groups described above are similarly listed when the alkyl group is an alkyl group.

[0129] In equations (B-7) and (B-11), R Ｘ２Each of these independently represents a hydrogen atom, or a substituent other than a fluorine atom and a perfluoroalkyl group (e.g., an alkyl group that does not contain a fluorine atom and a cycloalkyl group that does not contain a fluorine atom). The two R in formula (B-7) Ｘ２ They may be the same or different.

[0130] In formula (B-8), R ＸＦ１ R represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, multiple Rs are not allowed. ＸＦ１ Of these, at least one represents a fluorine atom or a perfluoroalkyl group. The two R in formula (B-8) ＸＦ１ They may be the same or different. ＸＦ１ The number of carbon atoms in the perfluoroalkyl group represented by is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0131] In formula (B-9), R Ｘ３ R represents a hydrogen atom, a halogen atom, or a monovalent organic group. Ｘ３ Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. Ｘ３ A monovalent organic group as R Ｘ１ It is similar to the monovalent organic group described as follows. n1 represents an integer from 0 to 4. n1 is preferably an integer from 0 to 2, and preferably 0 or 1. When n1 represents an integer from 2 to 4, multiple R Ｘ３ They may be the same or different.

[0132] In formula (B-10), R ＸＦ２ R represents a fluorine atom or a perfluoroalkyl group. ＸＦ２ The number of carbon atoms in the perfluoroalkyl group represented by is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0133] In formula (DA), R ａ１ The monovalent organic group represented by is not particularly limited, but generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms. ａ１ The group is preferably an alkyl group, a cycloalkyl group, or an aryl group.

[0134] The alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, and even more preferably having 1 to 10 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably having 3 to 15 carbon atoms, and even more preferably having 3 to 10 carbon atoms. The aryl group may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, more preferably having 6 to 15 carbon atoms, and even more preferably having 6 to 10 carbon atoms.

[0135] The cycloalkyl group may contain heteroatoms as ring member atoms. The heteroatoms are not particularly limited, but examples include nitrogen and oxygen atoms. Furthermore, the cycloalkyl group may contain carbonyl bonds (>C=O) as ring member atoms. The alkyl group, cycloalkyl group, and aryl group may further have substituents.

[0136] L ａ１ The divalent linking group represented by is not particularly limited, but can include alkylene groups, cycloalkylene groups, aromatic ring groups, -O-, -CO-, -SO-, and -SO ２- represents a group formed by combining two or more of these. The alkylene group may be linear or branched, and is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, and is preferably a cycloalkylene group having 3 to 20 carbon atoms, and more preferably a cycloalkylene group having 3 to 10 carbon atoms. The aromatic ring group is a divalent aromatic ring group, and is preferably an aromatic ring group having 6 to 20 carbon atoms, and more preferably an aromatic ring group having 6 to 15 carbon atoms. The aromatic ring constituting the aromatic ring group is not particularly limited, but for example, an aromatic ring having 6 to 20 carbon atoms can be mentioned, specifically, a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. As the aromatic ring constituting the aromatic ring group, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The alkylene group, cycloalkylene group, and aromatic ring group may have further substituents, and halogen atoms are preferred as substituents. ３１ － and R ａ１ These elements may join together to form a ring.

[0137] Examples of the above-mentioned anions include those contained in the photoacid generators disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345, the contents of which are incorporated herein by reference.

[0138] For superior resolution, the molecular weight of the second compound is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more. There is no particular upper limit to the molecular weight of the second compound, but it is often 2000 or less, preferably 1500 or less, and even more preferably 1200 or less. If the second compound is the compound represented by formula (3) described above, the molecular weight of the cation in the compound represented by formula (3) is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more. There is no particular upper limit to the molecular weight of the above cation, but it is often 2000 or less, preferably 1500 or less, and even more preferably 1200 or less. Note that the cation in the compound represented by formula (3) refers to X in formula (3). － This refers to the part excluding the anion represented by [the symbol].

[0139] Specific examples of the second compound are shown below, but the present invention is not limited thereto.

[0140]

[0141] The content of the photoacid generator is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, relative to the total solid content of the resist composition. One type of photoacid generator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0142] [Resin] The resist composition contains a resin. The resin is preferably one whose polarity changes upon the action of an acid (hereinafter also referred to as "acid-degradable resin"). The acid-degradable resin is preferably one whose polarity increases upon the action of an acid, thereby increasing its solubility in an alkaline developer. It is also preferable that the acid-degradable resin's polarity increases upon the action of an acid, thereby decreasing its solubility in an organic solvent. The acid-degradable resin is preferably one that has a group that decomposes and changes polarity upon the action of an acid (hereinafter also referred to as "acid-degradable group"), and more preferably one that contains repeating units having an acid-degradable group.

[0143] <Repeating units having acid-degradable groups> (Acid-degradable groups) Acid-degradable groups may be either groups that decompose upon the action of an acid, increasing or decreasing in polarity, but it is preferable that they are groups that decompose upon the action of an acid, increasing in polarity, and typically they are groups that decompose upon the action of an acid to produce a polar group. It is preferable that acid-degradable groups have a structure in which the polar group is protected by a group that is left behind upon the action of an acid (leaving group). Examples of the above polar groups include acidic groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0144] Examples of groups that are eliminated by the action of an acid include the group represented by any of the following formulas: (Y1), (Y2), and (Y3). Formula (Y1): -C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(R ３６ ) (Caution ３７ ) ( OR ３８ ) Formula (Y3): -C(Rn)(H)(Ar)

[0145] In formula (Y1), Rx １ ~Rx ３ Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an alkynyl group, or an aryl group (monocyclic or polycyclic). １ ~Rx ３ If all of them are alkyl groups (linear or branched), then Rx １ ~Rx３ Preferably, at least two of them are methyl groups. Among them, Rx １ ~Rx ３ Each preferably independently represents a linear or branched alkyl group, and Rx １ ~Rx ３ It is more preferable that each of these independently represents a linear alkyl group. １ ~Rx ３ These two may combine to form a monocycle or polycycle. Rx １ ~Rx ３ Preferred alkyl groups include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The alkynyl group is preferably an ethynyl group or a propargyl group. Rx １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group.

[0146] Rx １ ~Rx ３ A cycloalkyl group is preferred as the ring formed by the bonding of these two. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with a monocyclic cycloalkyl group having 5 to 6 carbon atoms being more preferred. １~Rx ３ The cycloalkyl group formed by the bonding of these two groups 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. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group.

[0147] When the resist composition of the present invention is used as an EUV resist, Rx １ ~Rx ３ Alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and Rx are represented by １ ~Rx ３ The ring formed by the bonding of these two elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0148] In formula (Y2), R ３６ ~R ３８ Each of these independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and alkynyl groups. ３６ It is also preferable that it be a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl group may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. ３８ R may bond with other substituents on the repeating main chain to form a ring. ３８The group formed by the bonding of the repeating unit main chain with another substituent is preferably an alkylene group such as a methylene group. When the resist composition of the present invention is used as an EUV resist, R ３６ ~R ３８ A monovalent organic group represented by, and R ３７ and R ３８ The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0149] In formula (Y3), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. When the resist composition of the present invention is used as an EUV resist, it is also preferable that the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0150] From the standpoint of excellent acid decomposition properties of repeating units, in a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0151] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0152] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (B1) is preferred.

[0153]

[0154] In formula (B1), R ｂ１ and R ｂ２ Each of these independently represents a hydrogen atom or an alkyl group which may have a substituent. ｂ１Ar represents a single bond or a -COO- bond. ｂ１ This represents an s+t+1 valent aromatic ring group. ｂ１ is, -OR ｂ or -COOR ｂ Represents R ｂ R represents a leaving group. ｂ３ is, -OR ｂ and -COOR ｂ Represents a substituent different from the given one. s represents an integer greater than or equal to 1. t represents an integer greater than or equal to 0. R ｂ１ and Ar ｂ１ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ and R ｂ３ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ３ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ These elements may be linked to each other via single bonds or divalent linking groups to form a ring.

[0155] In formula (B1), R ｂ１ and R ｂ２ Each of these independently represents a hydrogen atom or an alkyl group which may have substituents. ｂ１ and R ｂ２ Examples of alkyl groups that may have the above substituents represented by include a methyl group or -CH ２ -R １１ The group represented by R is an example. １１ R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred, and methyl groups being more preferred. ｂ１ A hydrogen atom is preferred as the component. ｂ２ Preferably, the group is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0156] In formula (B1), Ar ｂ１ represents an s+t+1 valent aromatic ring group. The above aromatic ring group may be monocyclic or polycyclic. The above aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with aromatic hydrocarbon groups being preferred. As the above aromatic hydrocarbon group, groups containing aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene, are preferred. As the heteroatoms of the above aromatic heterocyclic group, nitrogen atoms, oxygen atoms, or sulfur atoms are preferred. As the aromatic heterocyclic group, groups containing aromatic heterocyclic rings with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole, are preferred. The number of ring member atoms of the above aromatic ring group is preferably 6 to 18, and more preferably 6 to 10.

[0157] In formula (B1), Y ｂ１ is, -OR ｂ or -COOR ｂ Represents R ｂ R represents a leaving group. ｂ The definition and preferred embodiment of the leaving group represented by are as described above, and the group represented by formulas (Y1) to (Y3) is preferred. When s is an integer of 2 or more, there are multiple Y ｂ１ They may be the same or different from one another.

[0158] In formula (B1), R ｂ３ is, -OR ｂ and -COOR ｂ Represents a different substituent. ｂ３ It is also preferable that the group does not contain an acid-degradable group. ｂ３ Examples of groups represented by include halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, aryl groups, heteroaryl groups, ester groups, carboxyl groups, and groups formed by combining two or more of these. When t is an integer of 2 or more, there are multiple R groups. ｂ３ They may be identical or different to each other.

[0159] In formula (B1), s represents an integer of 1 or more, preferably an integer between 1 and 4, and more preferably 1 or 2. t represents an integer of 0 or more, preferably an integer between 0 and 4, and more preferably an integer between 0 and 2.

[0160] In formula (B1), R ｂ１ and Ar ｂ１ They may be linked to each other via single bonds or divalent linking groups to form a ring. When t represents an integer of 1 or more, R ｂ and R ｂ３ They may be linked to each other via single bonds or divalent linking groups to form a ring. When s represents an integer of 2 or more, R ｂ They may be linked to each other via single bonds or divalent linking groups to form a ring, and when t represents an integer of 2 or more, R ｂ３ These elements may be bonded to each other via single bonds or divalent linking groups to form a ring. Examples of the divalent linking groups include -O-, -S-, -CO-, and -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have substituents.

[0161] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0162]

[0163] L １ R represents a divalent linking group which may have a fluorine atom or an iodine atom. １ R represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. ２ This represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. However, L １ , R １ and R ２ At least one of them has a fluorine atom or an iodine atom.１ Divalent linking groups that may have a fluorine atom or an iodine atom, represented by -CO-, -O-, -S-, -SO-, -SO ２ - Hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linked groups formed by linking multiple thereof. Among these, L １ The alkylene group is preferably -CO-, an arylene group, or an -arylene group-an alkylene group having a fluorine or iodine atom, and more preferably -CO-, or an -arylene group-an alkylene group having a fluorine or iodine atom. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine and iodine atoms in the alkylene group having a fluorine or iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0164] R １ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0165] R ２ Examples of leaving groups that may have a fluorine atom or an iodine atom, represented by formula (Y1), formula (Y2), and formula (Y3) above, include leaving groups that have a fluorine atom or an iodine atom.

[0166] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0167]

[0168] In equation (AI), Xa １ Rx represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. １ ~Rx ３ The definition and preferred embodiment of Rx in formula (Y1) １ ~Rx ３ They are the same.

[0169] Xa １ Examples of alkyl groups that may have substituents, represented by , include a methyl group or -CH ２ -R １１ The group represented by R is an example. １１ R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. １ Preferably, the group is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0170] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ -, - (CH ２ ) ２ - or - (CH ２ ) ３ - is preferable.

[0171] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0172] The repeating unit represented by formula (AI) is an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (Xa １ A repeating unit in which represents a hydrogen atom or a methyl group, and T represents a single bond, is preferred.

[0173] The repeating unit having an acid-degradable group may have an acid-degradable group containing an unsaturated bond. The repeating unit represented by formula (B) is preferred as the repeating unit having an acid-degradable group containing an unsaturated bond.

[0174]

[0175] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. １ ~Ry ３ Each of these independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, Ry １ ~Ry ３ At least one of these represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ These two may combine to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.) structure.

[0176] In formula (B), the optionally substituted alkyl group represented by Xb is, for example, a methyl group or -CH ２ -R １１ The group represented by R is an example. １１Xa is as described above. For Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0177] In formula (B), the divalent linking group represented by L includes -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group. As for L, -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO- are preferred.

[0178] In formula (B), Ry １ ~Ry ３ The alkyl group represented is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group. １ ~Ry ３ The cycloalkyl group represented by is preferably 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. １ ~Ry ３ A vinyl group is preferred as the alkenyl group represented by Ry. １ ~Ry ３ As the alkynyl group represented by , an ethynyl group is preferred. １ ~Ry ３ The cycloalkenyl group represented by is preferably a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group that contains a double bond in part. １ ~Ry ３ The aryl group represented by is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group.

[0179] Ry １ ~Ry ３The cycloalkyl group formed by the bonding of these two groups is preferably 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. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ A cycloalkyl group or cycloalkenyl group formed by the bonding of these two elements may, for example, have one of the methylene groups constituting the ring be a heteroatom such as an oxygen atom, a carbonyl group, or -SO ２ -Base and -SO ３ - These groups may be replaced by groups containing heteroatoms such as - groups, vinylidene groups, or combinations thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane or cycloalkene ring may be replaced by vinylene groups. The repeating unit represented by formula (B) is, for example, Ry １ is a methyl group, ethyl group, vinyl group, allyl group, or aryl group, R ２ and Ry ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group or cycloalkenyl group.

[0180] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0181] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (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 ring group)).

[0182] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond include, for example, the repeating units described in

[0067] to

[0071] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0183] Specific examples of repeating units having acid-degradable groups are shown below, but are not limited to these. Repeating units having acid-degradable groups described in the examples later are also preferred. Furthermore, for repeating units having acid-degradable groups, one can refer to, for example, the descriptions in

[0029] to

[0071] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0184]

[0185] The repeating unit having an acid-degradable group preferably includes at least one repeating unit selected from the group consisting of the repeating unit represented by formula (B1) and the repeating unit represented by formula (AI) described above, and more preferably includes the repeating unit represented by formula (B1) described above.

[0186] The repeating units having acid-degradable groups may be used individually or in combination of two or more types. The content of the repeating units having acid-degradable groups is preferably 5 to 100 mol%, more preferably 10 to 80 mol%, and even more preferably 15 to 70 mol%, relative to the total repeating units in the acid-degradable resin.

[0187] <Repeating units having acidic groups> The resin preferably contains repeating units having acidic groups. The repeating units having acidic groups are preferably different from the repeating units having acid-degradable groups. The repeating units having acidic groups may also have fluorine atoms or iodine atoms. Preferred acidic groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups, with phenolic hydroxyl groups being more preferred. In other words, the resin preferably contains repeating units having phenolic hydroxyl groups. In the hexafluoroisopropanol group, one or more fluorine atoms (preferably 1 to 2) may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As for the acidic group, the -C(CF) formed in this way ３ ) (OH)-CF ２ - is also preferable. In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom, -C(CF ３ ) (OH)-CF ２ A ring containing - may be formed.

[0188] As the repeating unit having an acid group, the repeating unit represented by the following formula (Pa1) is preferred; that is, the resin preferably contains the repeating unit represented by the following formula (Pa1).

[0189]

[0190] In formula (Pa1), R ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ Ar represents a single bond or a divalent linking group. ａ１ Ar represents an aromatic ring group with (m+n+1) valency. ａ１ And, R ａ２ or L ａ１ This may be a single bond or a bond via a linking group. Ｘ represents a substituent other than a hydroxyl group. n represents an integer between 1 and 9 (inclusive). m represents an integer between 0 and 8 (inclusive).

[0191] In the above formula (Pa1), R ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituents represented are not particularly limited, but alkyl groups, cycloalkyl groups, halogen atoms, cyano groups, or alkoxycarbonyl groups are preferred. ａ１ and R ａ２ The alkyl group represented by may be linear or branched, and may have substituents. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. ａ１ and R ａ２ The number of carbon atoms in the cycloalkyl group represented by R is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have substituents. ａ１ and R ａ２ Examples of halogen atoms represented by include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or iodine atoms being preferred. ａ１ and R ａ２ The alkyl group contained in the alkoxycarbonyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. The alkoxycarbonyl group may have substituents.

[0192] In the above formula (Pa1), L ａ１ L represents a single bond or a divalent linking group. ａ１ Examples of divalent linking groups represented by include -COO- and -CONR ａ３ -, alkylene groups, or groups formed by combining two or more of these groups.ａ３ R represents a hydrogen atom or an alkyl group. Preferred alkylene groups include C1-C8 alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, and octylene. The alkylene group may have substituents. ａ３ Examples of alkyl groups when represents an alkyl group include alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or fewer carbon atoms being preferred.

[0193] In the above formula (Pa1), Ar ａ１ Ar represents an aromatic ring group with (m+n+1) valency. ａ１ The aromatic ring group represented by may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferred aromatic hydrocarbon groups include groups containing aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. Preferred aromatic heterocyclic groups include groups containing aromatic heterocyclic rings with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0194] Ar ａ１ And, R ａ２ or L ａ１ These may be bonded via single bonds or linking groups. Examples of linking groups include -O-, -S-, -CO-, and -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have substituents.

[0195] In the above formula (Pa1), R Ｘ R represents substituents other than hydroxyl groups.Ｘ Examples of substituents represented by include carboxyl groups, sulfonic acid groups, cyano groups, halogen atoms, hydrocarbon groups, amino groups, nitro groups, and groups formed by combining two or more of these. Ｘ Examples of hydrocarbon groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 5 to 15 carbon atoms), and alkenyl groups (preferably having 2 to 10 carbon atoms). Ｘ The hydrocarbon group represented by may have substituents. Also, R Ｘ The hydrocarbon group represented is -CH ２ If it contains -, -CH ２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - May be replaced by at least one selected from the group consisting of -. Ｘ The substituent represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom.

[0196] In the above formula (Pa1), n ​​represents an integer from 1 to 9, preferably an integer from 1 to 5, and more preferably an integer from 1 to 4. m represents an integer from 0 to 8, preferably an integer from 0 to 4, and more preferably an integer from 0 to 3.

[0197] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa2), that is, the resin preferably contains a repeating unit represented by the following formula (Pa2).

[0198]

[0199] In formula (Pa2), R ａ４ L represents a hydrogen atom or an alkyl group. ａ２ represents a single join or -COO-. r represents an integer between 0 and 3 (inclusive). Ｘ１ represents a halogen atom or hydrocarbon group. n1 represents an integer between 1 and 5. m1 represents an integer between 0 and 4.

[0200] In the above formula (Pa2), R ａ４ R represents a hydrogen atom or an alkyl group.ａ４ The alkyl group represented by may be linear or branched and may have substituents. 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 alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.

[0201] In the above formula (Pa2), L ａ２ represents a single bond or -COO-, with a single bond being preferred. r represents an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 0. In formula (Pa2), the aromatic ring is benzene when r is 0, naphthalene when r is 1, anthracene when r is 2, and naphthacene when r is 3. n1 represents an integer between 1 and 5, preferably between 1 and 4. m1 represents an integer between 0 and 4, preferably between 0 and 3.

[0202] In the above formula (Pa2), R Ｘ１ R represents a halogen atom or hydrocarbon group. Ｘ１ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine or iodine being more preferred. Ｘ１ Examples of hydrocarbon groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 5 to 15 carbon atoms), and alkenyl groups (preferably having 2 to 10 carbon atoms). Ｘ１ The hydrocarbon group represented by may have substituents. Also, R Ｘ１ The hydrocarbon group represented is -CH ２ If it contains -, -CH ２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - May be replaced by at least one selected from the group consisting of -. Ｘ１ The hydrocarbon group represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom.

[0203] Specific examples of repeating units having an acid group include, for example, the repeating units described in

[0079] to

[0110] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0204] The repeating units having acidic groups may be used alone or in combination of two or more types. The content of repeating units having acidic groups is preferably 5 to 90 mol%, more preferably 10 to 90 mol%, and even more preferably 20 to 80 mol%, relative to the total repeating units of the resin.

[0205] <Other Repeating Units> The resin may contain other repeating units other than those described above. The content of other repeating units is preferably 0 to 50 mol%, and more preferably 0 to 30 mol%, relative to the total repeating units of the resin.

[0206] (Repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom) The resin may have repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom (hereinafter also simply referred to as "repeating unit X"). It is preferable that repeating unit X is different from repeating units Y and P described later. As repeating unit X, the repeating unit represented by formula (C) is preferred.

[0207]

[0208] In formula (C), L ５ R represents a single bond or an ester group. ９ R represents an alkyl group which may have a hydrogen atom, or a fluorine atom or an iodine atom. １０ This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof.

[0209] The content of repeating unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in the resin. The content of repeating unit X is preferably less than 40 mol%, and more preferably 35 mol% or less, relative to the total repeating units in the resin.

[0210] The resin may have repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom. Examples of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom. The total content of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom among the repeating units of the resin is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of the resin. There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of the resin.

[0211] Specific examples of repeating units having fluorine atoms or iodine atoms include, for example, the repeating units described in

[0116] to

[0117] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0212] (Repeating units having lactone groups, sultone groups, or carbonate groups) The resin may have repeating units (hereinafter also simply referred to as "repeating unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that repeating unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0213] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. More preferably, the 5-7 membered ring lactone structure is fused with another ring structure in the form of a bicyclo or spiro structure, or the 5-7 membered ring sultone structure is fused with another ring structure in the form of a bicyclo or spiro structure. For units containing a lactone group or sultone group, refer, for example, to the descriptions in International Publication No. 2022 / 024928

[0119] to

[0126] and

[0132] to

[0133] , which are incorporated herein by reference.

[0214] A cyclic carbonate ester group is preferred as the carbonate group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in

[0127] to

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

[0215] When the resin contains repeating units Y, the content of repeating units Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in the resin. The content of repeating units Y is preferably less than 40 mol%, and more preferably 35 mol% or less, relative to the total repeating units in the resin.

[0216] (Repeating units having photoacid generating groups) The resin may contain repeating units (hereinafter simply referred to as "repeating units P") that have groups that generate acid upon irradiation with active light or radiation (also called "photoacid generating groups"), but it is also preferable that the resin does not contain repeating units P. An example of repeating units P is the repeating unit represented by formula (4).

[0217]

[0218] In formula (4), R ４１ L represents a hydrogen atom or a methyl group. ４１ L represents a single bond or a divalent linking group. ４２ R represents a divalent linking group. ４０ This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain.

[0219] In formula (4), L ４１ represents a single bond or a divalent linking group, and a single bond or -COO- is preferred. ４２ The symbols represent divalent linking groups, including alkylene groups, cycloalkylene groups, arylene groups, -O-, -CO-, -S-, -SO-, and -SO ２ A linking group consisting of at least one selected from the group consisting of - and -NR- is preferred. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, cycloalkyl group, or aryl group). The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred. The cycloalkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is not particularly limited, but 3 to 20 is preferred, and 5 to 15 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. The alkylene group, cycloalkylene group and arylene group may have substituents, and the substituent T mentioned above is an example of a substituent.

[0220] In formula (4), R ４０ The group is preferably represented by the following formula (S4-1).

[0221]

[0222] In equation (S4-1), Q － represents an acid residue, M ＋ * represents a cation. * represents L ４１ This indicates the bonding position. An acid residue is a group formed when a proton dissociates from an acid. Q － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or sulfonamide group (N － -SO ２ R Ｎ１ It is represented by R Ｎ１represents an organic group, and examples include organic groups having 1 to 10 carbon atoms, with alkyl groups, fluoroalkyl groups, or aryl groups being preferred. A sulfonate anion group is more preferred. ＋ Examples of cations represented by this formula include the cation contained in the first compound described above.

[0223] Specific examples of repeating units P include, for example, the repeating units described in paragraphs

[0094] to

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

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

[0138] of International Publication No. 2022 / 024928, and these descriptions are incorporated herein by reference. Furthermore, examples of repeating units represented by formula (4) include, for example, the repeating units described in paragraphs

[0094] to

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

[0094] of International Publication No. 2018 / 193954, and these descriptions are incorporated herein by reference.

[0224] When the resin contains repeating units P, the content of repeating units P is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the total repeating units in the resin. Furthermore, the content of repeating units P is preferably less than 40 mol%, more preferably 30 mol% or less, and even more preferably 20 mol% or less, relative to the total repeating units in the resin.

[0225] (Repeating units represented by formula (V-1) or formula (V-2)) The resin may have repeating units represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating units represented by formula (V-1) and the following formula (V-2) are different from the repeating units described above.

[0226]

[0227] In equation (V-1) and equation (V-2) below, R ６ and R ７Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms are preferred. ３ n represents an integer between 0 and 6. ４ X represents an integer between 0 and 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954, which are incorporated herein by reference.

[0228] (Repeating units to reduce the mobility of the main chain) A higher glass transition temperature (Tg) is preferable for the resin in that it can suppress excessive diffusion of generated acid or pattern breakdown during development. The resin may have repeating units to reduce the mobility of the main chain in order to adjust the glass transition temperature. For repeating units to reduce the mobility of the main chain, refer to the contents of

[0144] to

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

[0229] (Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups include the repeating units described for repeating unit Y above. The preferred content is also as described for repeating unit Y.

[0230] The resin may have repeating units having a hydroxyl group or a cyano group. This improves substrate adhesion. The repeating units having a hydroxyl group or a cyano group are preferably repeating units having saturated hydrocarbon groups (substituted with a hydroxyl group or a cyano group) that have a hydroxyl group or a cyano group. Alternatively, they may be repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating units having a hydroxyl group or a cyano group are preferably not having acid-degradable groups. Examples of repeating units having a hydroxyl group or a cyano group include the repeating units described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921, and the above description is incorporated herein by reference.

[0231] The resin may have repeating units having alkali-soluble groups. The inclusion of repeating units having alkali-soluble groups in the resin increases resolution in contact hole applications. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. Examples of repeating units having alkali-soluble groups include the repeating units described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921, which are incorporated herein by reference.

[0232] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) The resin may have repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0233] (Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group) The resin may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0234]

[0235] In formula (III), R ５ represents a hydrocarbon group having at least one ring structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or -CH ２ -O-Ra ２ It represents the base. In the formula, Ra ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-098921, which are incorporated herein by reference.

[0236] (Other Repeating Units) The resin may have other repeating units other than those described above. For example, refer to the descriptions in

[0141] to

[0143] and

[0169] to

[0170] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0237] In addition to the repeating structural units described above, the resin may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0238] A preferred embodiment of the present invention is that the resin has at least one selected from the group consisting of lactone groups, carbonate groups, sultone groups, and saturated hydrocarbon groups having hydroxyl groups. Having at least one selected from the group consisting of lactone groups, carbonate groups, sultone groups, and saturated hydrocarbon groups having hydroxyl groups further improves etching resistance and LWR performance.

[0239] A preferred embodiment of the present invention is that the resin contains repeating units having iodine atoms. By including repeating units having iodine atoms in the acid-degradable resin, the absorption rate of EUV light and the like is increased, the effects of shot noise can be reduced, and the LWR performance is further improved.

[0240] The resin can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight (Mw) of the resin, expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The polydispersity (molecular weight distribution, Mw / Mn) of the resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5. A lower polydispersity results in better resolution and resist shape, smoother sidewalls of the resist pattern, and superior roughness.

[0241] The resin content is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 99.9% by mass, and even more preferably 50.0 to 90.0% by mass, relative to the total solid content of the resist composition. Only one type of resin may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the above preferred content range.

[0242] [Acid Diffusion Control Agent] The resist composition preferably further contains an acid diffusion control agent. The acid diffusion control agent can act as a quencher to trap excess acid generated from the photoacid generator described above by irradiation (exposure) with active light or radiation, and to suppress the reaction of the acid-degradable resin in the unexposed areas due to the excess acid. Note that the acid diffusion control agent is a different compound from the photoacid generator described above.

[0243] The type of acid diffusion control agent is not particularly limited, but examples include compounds selected from basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. It is also preferable that the acid diffusion control agent is a compound that generates an acid with a pKa of 0 or more upon irradiation with active light or radiation.

[0244] <Basic Compounds (CA)> As basic compounds (CA), compounds having a structure represented by any of the following formulas (A) to (E) are preferred. In formulas (B), (C), (D), and (E), * represents the bond position.

[0245]

[0246] In formula (A), R ２００ ~R ２０２ Each of these 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). ２００ ~R ２０２ At least two of them may be joined to form a ring. In formula (E), R ２０３ ~R ２０６ Each of these independently represents an alkyl group having 1 to 20 carbon atoms.

[0247] R in equations (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ , and R ２０６ The alkyl group or cycloalkyl group represented by may have substituents. Preferred substituent alkyl groups are C1-C20 aminoalkyl groups, C1-C20 hydroxyalkyl groups, or C1-C20 cyanoalkyl groups. R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ , and R ２０６The alkyl group or cycloalkyl group represented by is preferably unsubstituted.

[0248] Examples of basic compounds (CA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (CA) may also 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 also be an alkylamine derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond.

[0249] The difference between the pKa of the conjugate acid of the basic compound (CA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (CA)) is preferably 1.00 or higher, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. Furthermore, the pKa of the conjugate acid of the basic compound (CA) is preferably, for example, 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0250] Specific examples of basic compounds (CA) include, for example, the compounds described in paragraphs

[0132] to

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

[0251] <Compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation> Specifically, examples of compounds (CC) include onium salts (CD) of acids that are relatively weak acids with respect to the acid generated from the above-mentioned photoacid generator, and basic compounds (CE) whose basicity is reduced or lost by irradiation with active light or radiation.

[0252] Compound (CD) may be a compound that generates acid upon exposure. Preferably, compound (CD) is a compound that generates an acid with a pKa of 1.00 or more greater than the acid generated from the photoacid generator. The difference between the pKa of the acid generated from compound (CD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from compound (N) or the photoacid generator from the pKa of the acid generated from compound (CD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. Furthermore, the pKa of the acid generated from compound (CD) is preferably, for example, 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0253] The compound (CD) is preferably an onium salt consisting of an anion and a cation. Examples of the compound (CD) include "M ＋ X － Examples include compounds represented by " (onium salts). ＋ represents a cation, preferably an organic cation. ＋ Examples include the same cations described in the above-mentioned photoacid generator (for example, the cation in the first compound). － X represents an anion, preferably an organic anion. － Examples include the anions described above in relation to the photoacid generator.

[0254] In particular, when the above compound (CC) is an onium salt (CD) that is relatively weak acid with respect to the acid generated from the above photoacid generator, it is preferable that the above onium salt (CD) is a compound containing an anion part represented by any of the following formulas (BB-1) to (BB-7).

[0255]

[0256] Specific examples of onium salts (CD) include, for example, the compounds described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337, which are incorporated herein by reference. Specific examples of basic compounds (CE) include the compounds described in paragraphs

[0137] to

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

[0164] of International Publication No. 2020 / 066824, which are incorporated herein by reference.

[0257] In addition to the compounds described above, other known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can also be suitably used as acid diffusion control agents, and such descriptions are incorporated herein by reference.

[0258] The molecular weight of the acid diffusion control agent is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0259] In terms of superior effects of the present invention, the acid diffusion control agent is preferably an onium salt. Examples of onium salts include the onium salt (CD) described above.

[0260] When the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.1 to 40.0% by mass, more preferably 1.0 to 30.0% by mass, and even more preferably 2.0 to 25.0% by mass, based on the total solid content of the resist composition. Only one type of acid diffusion control agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0261] [Hydrophobic Resin] The resist composition may also contain a hydrophobic resin as a resin different from the acid-degradable resin described above. The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances.

[0262] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 atoms in the side chain portion of the resin. ３ It is preferable that the substructure has one or more of these substructures, and more preferably two or more. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

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

[0263] 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 even 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 their total content is within the range of the above preferred content.

[0264] [Surfactants] The resist composition of the present invention may contain surfactants. The inclusion of surfactants allows for superior adhesion and the formation of patterns with fewer development defects. Fluorine-based and / or silicone-based surfactants are preferred. Examples of fluorine-based and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

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

[0265] If the resist composition contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.01 to 1.0% by mass, relative to the total solid content of the resist composition. One type of surfactant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content is within the above preferred content range.

[0266] [Solvent] The resist composition preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2). Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0267] [Other Additives] The resist composition may further contain, as other additives, at least one selected from the group consisting of dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer (for example, phenol compounds with a molecular weight of 1000 or less, or alicyclic or aliphatic compounds containing a carboxyl group). The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developers.

[0268] 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, relative to the total solid content of the resist composition. Only one type of other additive may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0269] Furthermore, the resist composition may contain water as an impurity. When water is present as an impurity, a lower water content is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total resist composition. Furthermore, the resist composition may contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are present as impurities, a lower residual monomer content is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total solid content of the resist composition.

[0270] [Pattern Forming Method and Resist Film] The pattern forming method of the present invention is not particularly limited as long as it is a method of forming a pattern using the resist composition of the present invention, but a preferred pattern forming method comprises the steps of (1) forming a resist film on a substrate with the resist composition of the present invention, (2) exposing the resist film, and (3) developing the exposed resist film using a developer. Each of the above steps will be described in detail below.

[0271] [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 used in Step (1) are as described above.

[0272] One method for forming a resist film on a substrate using a resist composition is to coat the resist composition onto 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, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the filter pore size is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but if it is a polymer, it is preferably made of 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 perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimide, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof. In addition to resins, materials such as diatomaceous earth and glass may also be used.

[0273] The resist composition may be filtered using one filter or a combination of two or more filters. If two or more filters are used, they may be the same filter or different filters. The resist composition may also be circulated and filtered repeatedly using the same filter.

[0274] The resist composition can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The preferred rotation speed when spin coating using a spinner is 1000 to 3000 rpm (rotations per minute). After applying the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films, etc.) may be formed in the layer below the resist film.

[0275] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in at least one of a normal exposure machine and a developer machine, and may also be carried out using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0276] The present invention also includes a resist film obtained in step (1). The thickness of the resist film is not particularly limited, but 10 to 120 nm is preferred in that it is possible to form finer patterns with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0277] A topcoat may be formed on the upper layer of the resist film using a topcoat composition. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be contained in the resist composition.

[0278] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). Methods of exposure include irradiating the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams. The resist composition of the present invention is particularly suitable for pattern formation by EUV exposure or electron beam (EB) exposure. In other words, step (2) above is preferably a step of exposing the resist film using extreme ultraviolet light or an electron beam.

[0279] It is preferable to bake (heat) the image after exposure but before developing. This process is also called post-exposure baking (PEB). Baking promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. The baking temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The baking time 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 using means provided in at least one of a normal exposure machine and a developer, and may also be done using a hot plate or the like.

[0280] [Step (3)] Step (3) is a step in which the resist film exposed in step (2) is developed using a developer. By performing step (3), a resist pattern (also simply called a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (hereinafter also called an organic developer). Examples of development methods include immersing the substrate in a tank filled with developer for a certain period of time (dip method), puddling the developer on the substrate surface using surface tension and letting it stand for a certain period of time to develop (paddle method), spraying the developer onto the substrate surface (spray method), and continuously dispensing the developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). The development time is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C. In step (3), a step of stopping development while substituting with another solvent may be performed.

[0281] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0282] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0283] The above organic solvents may be mixed in multiple quantities, or mixed with solvents other than the above organic solvents or with water. The water content of the organic developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the organic developer.

[0284] The organic developer 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 developer may be just one type or two or more types. 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, even more preferably at least one selected from the group consisting of nonanes, decanes, undecanes, and dodecanes, particularly preferably at least one selected from the group consisting of undecanes and dodecanes, and most preferably undecanes. The hydrocarbon having 9 to 12 carbon atoms may also contain structural isomers.

[0285] The butyl acetate content in the organic developer is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, and even more preferably 75 to 90% by mass, based on 100% by mass of the entire organic developer. The hydrocarbon content in the organic developer (total amount if multiple types of hydrocarbons with 9 to 12 carbon atoms are included) is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on 100% by mass of the entire organic developer.

[0286] The mass ratio of butyl acetate to hydrocarbons having 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having 9 to 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, even more preferably 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0287] Organic developers may contain other components in addition to butyl acetate and hydrocarbons having 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having 9 to 12 carbon atoms, surfactants, antioxidants, and basic compounds.

[0288] [Other steps] The pattern forming method of the present invention may include other steps other than those described above.

[0289] <Rinsing Step> After step (3), rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general solvent can be used. The rinsing solution preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0290] The rinsing method is not particularly limited and includes, for example, a method in which rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (rotary coating method), a method in which the substrate is immersed in a tank filled with rinsing liquid for a certain period of time (dip method), and a method in which rinsing liquid is sprayed onto the surface of the substrate (spray method).

[0291] Furthermore, the pattern formation method of the present invention may include a heating step (PB; Post Bake) after step (3). This step removes any developer and rinse solution remaining between and inside the patterns. This step also has the effect of mellowing 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).

[0292] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step (3) may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate. The method of processing the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step (3) as a mask. Dry etching is not particularly limited, but oxygen plasma etching is preferred.

[0293] In the pattern forming method of the present invention, the developer, resist composition, and other various materials (e.g., solvent, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) used are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 ppt or more. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0294] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as constituent materials for various materials, performing filter filtration on the constituent materials of various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®. Details of filtration using filters are described in paragraph

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

[0295] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the manufacturing equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0296] [Method for Manufacturing Electronic Devices] This specification relates to a method for manufacturing electronic devices, including the pattern forming method of the present invention described above, and to electronic devices manufactured by this manufacturing method. Preferred embodiments of the electronic devices of this specification include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0297] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0298] [Components of the Resist Composition] The components used in the preparation of the resist compositions used in the examples and comparative examples are shown below.

[0299] <Photoacid Generator> As the photoacid generator, either the first compound consisting of anion and cation as shown in the table below, or the second compound as shown in the table below, is used. The anion contained in the first compound and the structure of the second compound are shown below. PA-1 to PA-7 and PA-10 correspond to the anion represented by formula (1), and PA-8 and PA-9 correspond to the second compound.

[0300]

[0301] Table 1 below shows the molecular weights of PA-1 to PA-7 and PA-10 (anions), the molecular weight of PA-8, and the molecular weight of the cation in PA-9.

[0302]

[0303] The structures of the anions contained in the comparative compounds are shown below.

[0304]

[0305] The structures of the cations contained in the first compound and the comparative compound are shown below.

[0306]

[0307] A photoacid generator consisting of PA-1 and PC-1 can be synthesized according to the following scheme. Other photoacid generators can also be synthesized in accordance with the above method.

[0308]

[0309] <Resin> The composition of the resin is shown below. The resin can be synthesized by known methods using monomers that provide each repeating unit. In Table 2, the "Content (mol%)" column shows the content (mol%) of each repeating unit relative to the total repeating units. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent values). The composition ratio (molar ratio) of the resin is as follows: １３ Measurement is performed using C-NMR (Nuclear Magnetic Resonance).

[0310]

[0311] The structure of each repeating unit is shown below.

[0312]

[0313] <Acid diffusion control agent>

[0314]

[0315] <Hydrophobic Resin> The following polymer AP-1 is used. Note that x:y = 70:30 (molar ratio) and Mw = 10000.

[0316]

[0317] <Surfactant> W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)

[0318] <Solvents> S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane) S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) S-3: Ethyl lactate S-4: γ-butyrolactone

[0319] <Preparation of Resist Compositions> The composition of each resist composition is shown below. Each component is mixed so that the composition (solid content ratio) of each resist composition is as shown in the table below, and the solid content concentration is as shown in the table below. Then, the resulting mixture is passed through a polyethylene filter with a pore size of 0.02 μm and filtered to prepare the resist compositions of each example and comparative example.

[0320] In the table below, the "mass%" column for each component (resin, photoacid generator, acid diffusion control agent, hydrophobic resin) indicates the content (mass%) relative to the solid content of the resist composition. In the table below, the "mass ratio" column for the "solvent" indicates the mixing ratio (mass ratio) of each solvent. As shown in the table below, when using the first compound or an onium salt consisting of an anion and a cation as the photoacid generator, the onium salt consisting of an anion and a cation shown in the table below was used. For example, resist composition R-1 contains an onium salt consisting of anion PA-1 and cation PC-1 as the photoacid generator. As shown in the table below, when using the second compound as the photoacid generator, the compound listed in the table below was used. For example, resist composition R-14 contains PA-8 as the photoacid generator.

[0321]

[0322] [Evaluation] [Pattern Formation (EB Exposure)] Each resist composition is coated onto a 6-inch Si wafer that has been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by changing the Si wafer to a chromium substrate. The wafer coated with the resist film obtained above is then patterned using an electron beam lithography system (Hitachi Ltd. HL750, acceleration voltage 50 keV). At this time, the pattern is drawn so that a 1:1 line and space pattern is formed. After electron beam lithography, the wafer is heated on a hot plate at 110°C for 60 seconds (this heating is also called "post-exposure heating"), then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 110°C for 60 seconds to obtain a resist pattern with a line width of 50 nm and a 1:1 line-and-space pattern.

[0323] [Pattern Formation (EUV Exposure)] The resist composition is applied to a 6-inch Si wafer that has been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by changing the Si wafer to a chromium substrate. The wafer on which the resist film obtained above has been formed is then subjected to pattern exposure using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) with an exposure mask (line / space = 1 / 1). After exposure, the wafer is heated on a hot plate at 110°C for 60 seconds (this heating is also called "post-exposure heating"), then developed by immersion in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and rinsed with water for 30 seconds. After that, the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a line width of 50 nm and a 1:1 line-and-space pattern.

[0324] [LWR Performance] The exposure amount (electron beam irradiation amount) when resolving a 1:1 line-and-space pattern with a line width of 50 nm using a length-measuring scanning electron microscope (Hitachi S-9380II) is defined as the sensitivity (Eop). A line-and-space pattern with a line width of 50 nm (1:1) resolved with the exposure amount that shows the above sensitivity (Eop) is observed from above using a length-measuring scanning electron microscope (Hitachi S-9380II). The line width of the pattern is observed at arbitrary points (160 points), and its standard deviation (σ) is determined. The measurement variability of the line width is set to 3σ, and the value of 3σ is defined as LWR (nm). The smaller the LWR value, the better the LWR performance.

[0325] [Resolution] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi S-9380II). The exposure amount (electron beam irradiation amount) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm is defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure amount that shows the above sensitivity (Eop) is defined as the resolution (nm). The smaller this value, the higher the resolution.

[0326] [PED Stability] When a 1:1 line-and-space pattern with a line width of 50 nm and a space width of 50 nm is exposed to an exposure dose that results in a line width of 50 nm, the line width is measured and defined as L0 when the resist composition is applied and immediately exposed, heated, developed, etc. in the manner described above to form the pattern. Separately, after 2 hours have elapsed since exposure, the line width is measured and defined as L3 when the same heating, developing, etc. is performed to form the pattern. From the obtained values, the line width change rate is calculated using the following formula: Line width change rate (%) = 100 × (L0 - L3) nm / 50 nm The line width change rate is used as an indicator of PED stability and is evaluated according to the evaluation criteria below. The smaller the line width change rate, the better the PED stability and the better the performance. In practical terms, a rating of B or higher is preferable, and A is more preferable.

[0327] A: Line width change rate less than 1% B: Line width change rate 1% or more, less than 3% C: Line width change rate 3% or more, less than 5% D: Line width change rate 5% or more

[0328] [Results] The resist compositions used in each example and comparative example, the pattern formation method (exposure light and resulting pattern), and the evaluation results obtained are shown in Tables 4 and 5. In the tables below, "EB-Positive" in the pattern formation method column indicates that a positive-type pattern is formed by pattern exposure using EB exposure. Also, "EUV-Positive" in the pattern formation method column indicates that a positive-type pattern is formed by pattern exposure using EUV exposure.

[0329]

[0330]

[0331] As shown in the table above, the resist composition of the present invention exhibits excellent PED stability. Furthermore, the resist composition of the present invention exhibits excellent resolution and LWR. Comparisons between Examples 1-14 to 16 and Examples 1-11 to 1-13, and between Examples 1-24 to 1-25 and Examples 1-21 to 1-23 show that when the photoacid generator is the second compound, the LWR is even better. Comparisons between Examples 1-1, 1-5, and 1-19 and other examples show that when the molecular weight of the anion represented by formula (1) and the molecular weight of the second compound are 400 or more, the resolution is even better. Comparisons between Example 1-17 and other examples show that in formula (1), L １ is an n+1 valent aromatic ring group, L ２ When it is a single bond, it is shown that the PED stability is better. A comparison of Examples 1-1 to 1-5 shows that when n in formula (1) is an integer of 2 or more, the LWR is better. A comparison of Examples 1-11 to 1-16 shows that when the photoacid generator is the first compound, the resolution is better.

Claims

A photosensitive or radiation-sensitive resin composition comprising a resin and at least one photoacid generator selected from the group consisting of a first compound and a second compound, The first compound is an onium salt containing an anion represented by formula (1), The second compound is -SO ３ － Base and S ＋ A photosensitive or radiation-sensitive resin composition comprising a betaine structure containing atoms and containing an N atom to which two or more aromatic rings are bonded. In formula (1), Ar １ This represents a monovalent aromatic ring group which may have substituents. R ａ１ represents a hydrogen atom or substituent. L １ This represents an n+1 valent linking group. L ２ This represents a single bond or a divalent linking group. 　 n represents an integer greater than or equal to 1. Ar １ and R ａ１ 、Ar １ and L １ 、and, R ａ１ and L １ may each be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. However, R ａ１ L represents a monovalent aromatic ring group which may have substituents, or １ This represents an n+1 valent aromatic ring group which may have substituents. 　 n is 1, L １ The phenylene group is L ２ It is a single bond, and L １ -SO bonded to the phenylene group represented by -SO ３ － Furthermore, if the N atom is at positions 1 and 4, the phenylene group has further substituents. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin comprises repeating units having groups that decompose upon the action of an acid and increase in polarity. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin comprises repeating units having phenolic hydroxyl groups. 　 The photoacid generator is a sulfonium salt compound, wherein the photoacid-generating agent is a photosensitive or radiation-sensitive resin composition according to claim 1. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the second compound is a compound represented by formula (2) or a compound represented by formula (3). In equations (2) and (3), R ａ１１ and R ａ１４ Each of these independently represents a hydrogen atom or a substituent. R ａ１２ , R ａ１３ , R ａ１５ , and R ａ１６ Each of these independently represents a substituent. R ａ１１ and R ａ１２ They may be bonded to each other to form a ring which may have substituents, R ａ１４ and R ａ１５ These elements may be bonded to each other to form a ring which may have substituents. Ar １１ and Ar １２ Each of these independently represents a divalent aromatic ring group which may have substituents. L １１ This represents a divalent linking group. L １２ and L １４ Each of these independently represents a single bond or a divalent linking group. L １３ This represents an m+1 valent linking group. 　 m represents an integer greater than or equal to 2. X － This represents an anion. However, in formula (2) above, R ａ１１ L represents a monovalent aromatic ring group which may have substituents, or １１ R represents a divalent aromatic ring group which may have substituents. In formula (3), R ａ１４ L represents a monovalent aromatic ring group which may have substituents, or １３ This represents an m+1 valent aromatic ring group which may have substituents. 　 The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having a group that decomposes and increases in polarity due to the action of the acid includes a repeating unit represented by formula (B1). In formula (B1), R ｂ１ and R ｂ２ Each of these independently represents a hydrogen atom or an alkyl group which may have a substituent. L ｂ１ This represents a single bond or a -COO- bond. Ar ｂ１ This represents an s+t+1 valent aromatic ring group. Y ｂ１ is, -OR ｂ or -COOR ｂ Represents R ｂ This represents a leaving group. R ｂ３ is, -OR ｂ and -COOR ｂ This represents a substituent different from the given one. s represents an integer greater than or equal to 1. t represents a non-negative integer. R ｂ１ and Ar ｂ１ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ and R ｂ３ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ３ They may be bonded to each other via single bonds or divalent linking groups to form a ring, R ｂ These elements may be linked to each other via single bonds or divalent linking groups to form a ring. 　 In the above formula (1), L １ is an n+1 valent aromatic ring group, L ２ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the bond is a single bond. 　 Furthermore, the photosensitive or radiation-sensitive resin composition according to claim 1, comprising an acid diffusion control agent. 　 The photosensitive or radiation-sensitive resin composition according to claim 8, wherein the acid diffusion control agent is an onium salt. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the molecular weight of the anion represented by formula (1) and the molecular weight of the second compound are 400 or more. A resist film formed using the photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10. 　 A pattern forming method comprising the steps of: forming a resist film on a substrate with a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10; exposing the resist film; and developing the exposed resist film using a developer. 　 A method for manufacturing an electronic device, comprising the pattern formation method described in claim 12.

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