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

Abstract

The present invention addresses the problem of providing an actinic light-sensitive or radiation-sensitive resin composition that exhibits an excellent sensitivity to photoexposure. The present invention also addresses the problem of providing a resist film, a pattern formation method, and a method for producing electronic devices, that each involve the actinic light-sensitive or radiation-sensitive resin composition. The actinic light-sensitive or radiation-sensitive resin composition contains a resin that undergoes an increase in polarity through decomposition by the action of acid, and the resin composition satisfies at least one of the following: the resin composition contains a compound given by formula (1); and the resin that undergoes an increase in polarity through decomposition by the action of acid has a residue formed by removing one hydrogen atom from the compound given by formula (1).

Description

[Technical Field]

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

[0002] Examples of the pattern formation method include the following methods. An actinic ray-sensitive or radiation-sensitive resin film (hereinafter also referred to as "resist film") formed using an actinic ray-sensitive or radiation-sensitive resin composition is exposed to light, causing a change in the solubility of the resist film in a developer in areas that reflect the exposure pattern. Thereafter, development is carried out using a developer (for example, an alkaline aqueous or organic solvent-based developer) to remove exposed or unexposed areas of the resist film, thereby obtaining a desired pattern.

[0003] For example, Patent Document 1 discloses a photoresist composition comprising a photoresist polymer containing a repeating unit represented by the following chemical formula; a photoacid generator that generates an acid; and an organic solvent, wherein the content of the photoacid generator is 0.1 to 20 parts by weight and the content of the organic solvent is 300 to 5000 parts by weight per 100 parts by weight of the photoresist polymer (claims 3 and 6).

[0004] [ka] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-111120 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have studied the photoresist composition (actinic ray-sensitive or radiation-sensitive resin composition) described in Patent Document 1 and have found that there is room for improvement in the sensitivity of the photoresist composition to exposure.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent sensitivity to exposure to light. Another object of the present invention is to provide a resist film, a pattern forming method, and a method for producing an electronic device, which are related to the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

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

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes under the action of an acid to increase its polarity, Further, the compound may contain a compound represented by the formula (1) described below, and an actinic ray-sensitive or radiation-sensitive resin composition that satisfies at least one of the following: the resin that decomposes under the action of an acid to increase its polarity has a residue formed by removing one hydrogen atom from the compound represented by formula (1). [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the residue includes at least one selected from the group consisting of a group represented by formula (2a) shown below and a group represented by formula (2b) shown below. [3] Above R 4 represents an aromatic ring group. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a nitrogen-containing basic compound. [5] the resin that is decomposed by the action of an acid to increase its polarity contains a repeating unit b having a group that is decomposed by the action of an acid to increase its polarity, The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the content of the repeating unit b is 15 mol % or more based on all repeating units. [6] the resin that is decomposed by the action of an acid to increase its polarity contains a repeating unit b having a group that is decomposed by the action of an acid to increase its polarity, The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the repeating unit b includes at least one selected from the group consisting of repeating units represented by formulas (M1) to (M5) described below. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to [6], wherein the repeating unit b comprises at least one selected from the group consisting of a repeating unit represented by formula (M4) above and a repeating unit represented by formula (M5) above. [8] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]. [9] forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]; exposing the resist film to light; and developing the exposed resist film using a developer.

[10] A method for manufacturing an electronic device, comprising the pattern forming method according to [9]. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent sensitivity to exposure to light. The present invention also provides a resist film, a pattern forming method, and a method for producing an electronic device, which are related to the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0012] The following notations used in this specification have the following meanings. Regarding the notation of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted includes both a group having a substituent and a group having a substituent, unless it is contrary to the spirit of the present invention. For example, an "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group). "Organic group" refers to a group containing at least one carbon atom. Substituents are monovalent substituents unless otherwise specified. "Actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). "Light" means actinic rays or radiation. Unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams. The symbol "~" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. The bonding direction of the divalent groups shown in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-OZ" or "XO-CO-Z".

[0013] (Meth)acrylate refers to acrylate and methacrylate. (Meth)acrylic refers to acrylic and methacrylic.

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

[0015] The composition ratio of the resin (molar ratio or mass ratio, etc.) is 13 It is measured by C-NMR (nuclear magnetic resonance).

[0016] The acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and is specifically a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0017] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0018] On the other hand, pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + One method is to calculate the dissociation free energy. +The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian 16.

[0019] As described above, pKa refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and known literature values. However, if pKa cannot be calculated using this method, a value obtained using Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as mentioned above, pKa means "pKa in aqueous solution," and if pKa in aqueous solution cannot be calculated, it is referred to as "pKa in dimethyl sulfoxide (DMSO) solution."

[0020] "Solid content" refers to the components that form the resist film, and does not include solvents. In addition, any component that forms the resist film is considered to be a solid content even if it is in liquid form.

[0021] 1 inch means 25.4 mm.

[0022] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") is a resist composition that contains a resin that decomposes under the action of an acid to increase its polarity, and further satisfies at least one of the following: it contains a compound represented by formula (1) (hereinafter also referred to as "compound (1)"), and the resin that decomposes under the action of an acid to increase its polarity has a residue (hereinafter also referred to as "specific group") formed by removing one hydrogen atom from the compound represented by formula (1). Hereinafter, the resin having a specific group and decomposing under the action of an acid to increase its polarity will also be referred to simply as "resin A."

[0023] The mechanism by which the sensitivity to light exposure is improved by adopting such a configuration is not entirely clear, but the present inventors speculate as follows. First, in a resist film formed using a typical chemically amplified resist composition, the acid generated from a photoacid generator upon exposure acts on a resin that decomposes under the action of acid to increase its polarity, causing decomposition of groups in the resin that decompose under the action of acid to increase their polarity (hereinafter also referred to as "acid-decomposable groups"), thereby causing a change in polarity in the exposed area. In this case, the inventors have found that the sensitivity of the resist composition to exposure varies depending on the ease with which the photoacid generator decomposes upon exposure to light. On the other hand, the resist composition of the present invention contains compound (1) or resin A. The specific group in compound (1) or resin A is easily decomposed upon exposure and therefore easily generates acid. As a result, it is presumed that the resist composition has excellent sensitivity to exposure. Hereinafter, superior sensitivity to exposure is also referred to as superior effect of the present invention.

[0024] The resist composition of the present invention will be described in detail below. The resist composition may be either a positive resist composition or a negative resist composition, and may also be either a resist composition for alkali development or a resist composition for organic solvent development. The resist composition may be a non-chemically amplified resist composition, or may also utilize the mechanism of a chemically amplified resist composition in combination with the resist composition. The various components of the resist composition will now be described in detail.

[0025] [Compound (1)] Compound (1) is a compound represented by formula (1). Compound (1) can also function as a photoacid generator, which will be described later.

[0026] [ka]

[0027] In formula (1), R 1 and R 4 R each independently represents a substituent. 2 and R 3 Each of L independently represents a hydrogen atom or a substituent. 1 represents a single bond or a divalent linking group, and n represents an integer of 1 or greater.

[0028] R 1 and R 4 each independently represents a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a thiol group, an amino group, a sulfonic acid group, an organic group, and a group formed by combining these groups. An organic group is preferred, and an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkenyl group, a cyano group, a cycloalkyl group, and an aromatic ring group are more preferred.

[0029] The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Examples of the alkyl group moiety in the alkoxy group and the alkoxycarbonyl group include the same groups as the alkyl group described above.

[0030] The alkenyl group may be either linear or branched. The alkenyl group preferably has 1 to 5 carbon atoms. The alkenyl group may, for example, be a vinyl group.

[0031] The cycloalkyl group preferably has 3 to 15 ring atoms. The cycloalkyl is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group, and more preferably a polycyclic cycloalkyl group. The cycloalkyl group may have one or more (e.g., 1 to 3) methylene groups constituting the ring replaced with a heteroatom (e.g., -O-, -S-, etc.), -SO2-, -SO3-, an alkoxycarbonyl group, a carbonyl group, or a vinylidene group. Furthermore, the cycloalkyl group may have one or more (e.g., 1 to 2) ethylene groups constituting the cycloalkane ring replaced with a vinylene group.

[0032] The aromatic ring group may be either monocyclic or polycyclic. The aromatic ring group preferably has 5 to 15 ring atoms. The ring member atoms of the aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (for example, oxygen atoms, sulfur atoms, and / or nitrogen atoms). Examples of the aromatic ring group include aryl groups such as a benzene ring group, a naphthalene ring group, and an anthracene ring group, and thiazole ring groups such as a benzothiazole ring group.

[0033] The alkyl group, the alkoxy group, the alkoxycarbonyl group, the alkenyl group, the cycloalkyl group and the aromatic ring group may further have a substituent. Examples of the substituent include a halogen atom (e.g., a fluorine atom), a hydroxyl group, a nitro group, a cyano group, a cycloalkyl group, and an aromatic ring group. Specifically, the alkyl group may have a fluorine atom as a substituent to form a perfluoroalkyl group. Examples of the cycloalkyl group and aromatic ring group as a substituent include R 1 and R 4 The substituent represented by the following formula (I) can take the form of the cycloalkyl group and the aromatic ring group described above.

[0034] As described above, the alkyl group, the alkoxy group, the alkoxycarbonyl group, the alkenyl group, the cycloalkyl group, and the aromatic ring group may further have a substituent, and the substituent may further have a substituent (hereinafter also referred to as "substituent X"). For example, the cycloalkyl group and the aromatic ring group may further have a substituent. Examples of the substituent X include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group. Examples of the alkyl group, alkoxy group, alkoxycarbonyl group, and alkenyl group as the substituent X include R 1 and R 4 The alkyl group, alkoxy group, alkoxycarbonyl group, and alkenyl group described above as possible forms of the substituent represented by the formula (I) may further have the above-mentioned substituent.

[0035] R 1 As the group, an alkyl group, a cycloalkyl group or an aromatic ring group is preferable, and an alkyl group, a cycloalkyl group or an aryl group is more preferable. R 4 As the group, an alkyl group, an alkoxy group or an aromatic ring group is preferable, and from the viewpoint of superior sensitivity, an aromatic ring group is more preferable, and an aryl group is even more preferable.

[0036] R 2 and R 3 each independently represents a hydrogen atom or a substituent. The above-mentioned substituents include the above-mentioned R 1 and R 4 Examples of the substituents include those in the formula: R 2 and R 3 is preferably a hydrogen atom, an alkyl group or an aryl group.

[0037] R 2 ~R 4 At least two of may be bonded to each other to form a ring. R 2 or R 3 and R 4 and preferably bond to each other to form a ring. The ring formed by bonding to each other may be either a monocyclic ring or a polycyclic ring. The number of ring atoms in the ring is preferably 4 to 15.

[0038] L 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups combining these. N is a substituent (e.g., the above R 1 ~R 4 The hydrocarbon group may further have a substituent, and preferably has a halogen atom as the substituent. The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 4 carbon atoms. The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 15 carbon atoms. One or more (e.g., one or two) -CH2- groups constituting the ring structure of the cycloalkylene group may be replaced by a heteroatom (e.g., -O- and -S-), -SO2-, -SO3-, an alkoxycarbonyl group, or a carbonyl group. L 1 is preferably a single bond or an alkylene group, more preferably a single bond.

[0039] n represents an integer of 1 or more. n is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0040] Examples of compound (1) include the following compounds:

[0041] [ka]

[0042] When the resist composition contains compound (1), the content of compound (1) is preferably 0.5% by mass or more, and more preferably 1% by mass or more, based on the total solid content of the resist composition, and the upper limit of the content of compound (1) is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total solid content of the resist composition. The compound (1) may be used singly or in combination of two or more. When two or more compounds are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0043] [Resins that decompose under the action of acid and increase polarity] A resin that decomposes under the action of an acid to increase its polarity (hereinafter also referred to simply as "acid-decomposable resin") has an acid-decomposable group. The "acid-decomposable group" means a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a leaving group that is released under the action of an acid. The acid-decomposable group can decompose under the action of an acid to generate a polar group. The acid-decomposable group will be described later. In the pattern formation method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is suitably formed.

[0044] As described above, the acid-decomposable resin may be a resin having a specific group. Resin A is preferably a resin having a repeating unit (hereinafter simply referred to as "repeating unit a") having a specific group, which is a nonionic group that decomposes upon irradiation (exposure) with actinic rays or radiation. The specific group is decomposed by irradiation with actinic rays or radiation to generate a polar group. That is, Resin A has a repeating unit having a group that decomposes upon exposure to generate a polar group. For example, upon exposure, the polarity of Resin A increases, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents.

[0045] (Specific group) The specific group is a residue formed by removing one hydrogen atom from the compound (1). The specific group is R 1 or R 4 It is preferably a residue formed by removing one hydrogen atom from the formula (2a), more preferably containing at least one selected from the group represented by formula (2a) and the group represented by formula (2b), and further preferably the group represented by formula (2a). Another preferred embodiment of the specific group is R 4 is preferably a residue formed by removing one hydrogen atom from compound (1) in which is an aromatic ring group.

[0046] [ka]

[0047] In formula (2a), R 5 and R 6 R each independently represents a hydrogen atom or a substituent. 7 represents a substituent. 2 represents a divalent linking group. 3 represents a single bond or a divalent linking group. n represents an integer of 1 or more. * represents the bonding position.

[0048] R 5 , R 6 , R 7 , L 3 and n are the R in (1) above, respectively. 2 , R 3 , R 4 , L 1 and n have the same meanings and preferred embodiments.

[0049] L 2 represents a divalent linking group. L2 As the R in formula (1), 1 A group formed by removing one hydrogen atom from is preferred. R 1 The preferred embodiment of is as described above.

[0050] [ka]

[0051] In formula (2b), R 8 and R 9 R each independently represents a hydrogen atom or a substituent. 10 represents a substituent. 4 represents a single bond or a divalent linking group. 5 represents a divalent linking group. n represents an integer of 1 or more. * represents the bonding position.

[0052] R 8 , R 9 , R 10 , L 4 and n are the R in (1) above, respectively. 2 , R 3 , R 1 , L 1 and n have the same meanings and preferred embodiments.

[0053] L 5 represents a divalent linking group. L 5 As the R in formula (1), 4 A group formed by removing one hydrogen atom from is preferred. Above R 4 The preferred embodiment of is as described above.

[0054] <Repeating unit a> The repeating unit a is a repeating unit having a specific group. The specific group may be directly bonded to the main chain of the repeating unit a, or may constitute a part of the main chain of the repeating unit a. Specifically, when the main chain is an ethylene chain, a part of the ethylene chain may be constituted by the specific group.

[0055] [ka]

[0056] In formula (a), R 1A ~R 3A Each of L independently represents a hydrogen atom or a substituent. 1A represents a single bond or a divalent linking group. T represents a specific group.

[0057] R 1A ~R 3A each independently represents a hydrogen atom or a substituent. R 1A ~R 3A are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, and still more preferably a hydrogen atom or a methyl group.

[0058] L 1A represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups combining these. N is a substituent (e.g., the above R 1 ~R 4 The hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as the substituent.

[0059] The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 4 carbon atoms. The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 15 carbon atoms. One or more (e.g., one or two) -CH2- groups constituting the ring structure of the cycloalkylene group may be replaced by a heteroatom (e.g., -O- and -S-), -SO2-, -SO3-, an alkoxycarbonyl group, or a carbonyl group.

[0060] T represents a specific group. The specific group is as described above.

[0061] Resin A more preferably has at least one repeating unit selected from the group consisting of repeating units represented by formulas (aa) to (ac).

[0062] [ka]

[0063] In formula (aa), R 1a ~R 3a Each of L independently represents a hydrogen atom or a substituent. 1a represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a group consisting of a combination thereof. Ar represents an aromatic ring group. Z represents a group represented by formula (Za) or a group represented by formula (Zb).

[0064] R 1a ~R 3a each independently represents a hydrogen atom or a substituent. R 1a ~R 3a are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, and still more preferably a hydrogen atom or a methyl group.

[0065] L 1a represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a group formed by combining these groups. The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 4 carbon atoms. The aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms in the aromatic ring group is preferably 5 to 15. The aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (for example, oxygen atoms, sulfur atoms, and / or nitrogen atoms) as ring atoms. The aromatic ring group is preferably a benzene ring group. Examples of the combined group include -COO-alkylene group and -COO-aromatic ring group-. The alkylene group and the aromatic ring group may further have a substituent. The substituents include R in formula (1). 1 and R 4 Examples of substituents that can be taken include: L 1a is preferably a single bond or an alkylene group, more preferably a single bond.

[0066] Ar represents an aromatic ring group. The aromatic ring group may be either monocyclic or polycyclic. The aromatic ring group preferably has 5 to 15 ring atoms. The aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (for example, oxygen atoms, sulfur atoms, and / or nitrogen atoms) as ring member atoms. The aromatic ring group may further have a substituent. The substituents include R in formula (1). 1 and R 4 Examples of substituents that can be taken include: Further, examples of the substituent include a group represented by formula (Za) or a group represented by formula (Zb). As the aromatic ring group, an arylene group such as a phenylene group or a naphthylene group is preferred, and a phenylene group is more preferred.

[0067] Z represents a group represented by formula (Za) or a group represented by formula (Zb). Z is preferably a group represented by formula (Za).

[0068] [ka]

[0069] In formula (Za), R 1za and R 2za R each independently represents a hydrogen atom or a substituent. 3za represents a substituent. za represents a single bond or a divalent linking group. za represents an integer of 1 or greater. * represents a bonding position.

[0070] R 1za , R 2za , R 3za , L za and n za are the R in (1) above, respectively. 2 , R 3 , R 4 , L 1 and n have the same meanings and preferred embodiments.

[0071] [ka]

[0072] In formula (Zb), R 1zb and R 2zb R each independently represents a hydrogen atom or a substituent. 3zb represents a substituent. zb represents a single bond or a divalent linking group. zb represents an integer of 1 or greater. * represents a bonding position.

[0073] R 1zb , R 2zb , R 3zb , L zb and n zb are the R in (1) above, respectively. 2 , R 3 , R 1 , L 1 and n have the same meanings and preferred embodiments.

[0074] In formula (ab), R 1b~R 3b Each of L independently represents a hydrogen atom or a substituent. 1b represents a single bond, an alkylene group, -COO-, or a group combining these. 2b represents a single bond or an alkylene group. Z represents a group represented by formula (Za) or a group represented by formula (Zb).

[0075] R 1b ~R 3b each independently represents a hydrogen atom or a substituent. R 1b ~R 3b are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, and still more preferably a hydrogen atom or a methyl group.

[0076] L 1b represents a single bond, an alkylene group, -COO- or a group formed by combining these. The alkylene group may be either linear or branched. The alkylene group preferably has 1 to 4 carbon atoms. An example of the combined group is a -COO-alkylene group. The alkylene group may further have a substituent. The substituents include R in formula (1). 1 and R 4 Examples of substituents that can be taken include: L 1b is preferably a single bond or an alkylene group, more preferably a single bond.

[0077] L 2b represents a single bond or an alkylene group. The alkylene group includes L in formula (a). 1A Examples of the substituent include an alkylene group which can be represented by the following formula: Furthermore, examples of the substituent include a group represented by formula (Za) or a group represented by formula (Zb). L 2b As the alkylene group, an alkylene group is preferred.

[0078] Z represents a group represented by formula (Za) or a group represented by formula (Zb). The group represented by formula (Za) and the group represented by formula (Zb) are as described above.

[0079] In formula (ac), R 1c ~R 3c Each of L independently represents a hydrogen atom or a substituent. 1c represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a group formed by combining these groups. 2c represents a cycloalkylene group. 3c represents a single bond or a divalent linking group. Z represents a group represented by formula (Za) or a group represented by formula (Zb).

[0080] R 1c ~R 3c each independently represents a hydrogen atom or a substituent. R 1c ~R 3c are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, and still more preferably a hydrogen atom or a methyl group.

[0081] L 1c represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a group formed by combining these groups. L 1c As for L in formula (aa), 1a Examples include: L 1c is preferably a single bond, an alkylene group, -COO- or a group combining these, and more preferably -COO-.

[0082] L 2c represents a cycloalkylene group. The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 15 carbon atoms. One or more (e.g., one or two) -CH2- groups constituting the ring structure of the cycloalkylene group may be replaced by a heteroatom (e.g., -O- and -S-), -SO2-, -SO3-, an alkoxycarbonyl group, or a carbonyl group. The cycloalkylene group may further have a substituent. The substituents include R in formula (1). 1 and R 4 Examples of substituents that can be taken include: Further, examples of the substituent include a group represented by formula (Za) or a group represented by formula (Zb).

[0083] L 3c represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups combining these. N is a substituent (e.g., the above R 1 ~R 4 The hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as the substituent. Further, examples of the substituent include a group represented by formula (Za) or a group represented by formula (Zb). L 3c As the alkylene group, an alkylene group which may have a fluorine atom or an alkoxycarbonyl group which may have a fluorine atom is preferred.

[0084] Z represents a group represented by formula (Za) or a group represented by formula (Zb). The group represented by formula (Za) and the group represented by formula (Zb) are as described above.

[0085] Examples of the repeating unit a include the following repeating units:

[0086] [ka]

[0087] The content of the repeating unit a is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units of the acid-decomposable resin, and the upper limit is preferably less than 100 mol%, more preferably 90 mol% or less, and even more preferably 70 mol% or less, based on all repeating units. The repeating unit a may be used alone or in combination of two or more. When two or more repeating units a are used, the total content thereof is preferably within the above content range. When two or more types of resins A are present, it is preferable to include one or more resins A in which the content of repeating units a is 40 mol % or more relative to all repeating units. In this case, the resin A in which the content of repeating units a is 40 mol % or more relative to all repeating units is preferably included in an amount of 30 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 80 to 100 mass %, relative to the total content of resins A.

[0088] <Repeating Unit Having an Acid-Decomposable Group> The acid-decomposable resin may have a repeating unit having an acid-decomposable group (hereinafter, also simply referred to as "repeating unit b"). The acid-decomposable group does not include the above-mentioned specific group. In addition, the acid-decomposable group does not have the specific group as a part thereof. In other words, the repeating unit b does not include the repeating unit a.

[0089] The polar group is preferably an alkali-soluble group. Examples of the alkali-soluble group include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group. As described above, the acid-decomposable group preferably has a structure in which a polar group is protected with a leaving group that is released by the action of an acid. Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0090] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched, preferably having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), an alkenyl group (linear or branched, preferably having 2 to 6 carbon atoms), an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms), or a heteroaryl group (monocyclic or polycyclic, preferably having 5 to 15 ring atoms). Two of Rx1 to Rx3 may be bonded to each other to form a ring. The ring may be either a monocyclic or polycyclic ring. Examples of the monocyclic or polycyclic ring include a cycloalkane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. In the cycloalkane ring, for example, one or more (e.g., 1 to 3) methylene groups constituting the ring may be replaced with a heteroatom (e.g., -O- or S-), -SO2-, -SO3-, -COO-, a carbonyl group, or a vinylidene group. In addition, in these cycloalkane rings, one or more (e.g., 1 to 2) ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In formula (Y1), when two of Rx1 to Rx3 are bonded to each other to form a cycloalkane ring, and the cycloalkane ring forms a vinylene group with the α carbon and γ carbon relative to the C (carbon) atom in formula (Y1), the remaining one of Rx1 to Rx3 may be a hydrogen atom.

[0091] In formula (Y3), R 36 ~R 38 each independently represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group (linear or branched, preferably having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms), an aralkyl group (preferably having 7 to 18 carbon atoms), or an alkenyl group (linear or branched, preferably having 2 to 6 carbon atoms). R 37 and R 38 may be bonded to each other to form a ring. Examples of the ring formed above include the same monocyclic or polycyclic rings that can be formed by bonding two of Rx1 to Rx3.

[0092] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group (linear or branched, preferably having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), or an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms). Rn and Ar may be bonded to each other to form a non-aromatic ring. Rn is preferably an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms).

[0093] The repeating unit b preferably contains at least one selected from the group consisting of repeating units represented by formulae (M1) to (M5), and more preferably contains at least one selected from the group consisting of repeating units represented by formulae (M4) and (M5) in terms of better LWR.

[0094] [ka]

[0095] In formula (M1), R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 10 represents a single bond or a divalent linking group. 10 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0096] R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The alkyl group may be either linear or branched, and preferably has 1 to 6 carbon atoms. The cycloalkyl group may be either monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The number of carbon atoms in the alkoxycarbonyl group is preferably 1 to 10. Examples of the alkyl group moiety in the alkoxycarbonyl group include the same groups as the alkyl groups described above. R5 is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and even more preferably a methyl group. R6 and R7 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0097] L 10 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups combining these. N is a substituent (e.g., the above R 1 ~R 4 The hydrocarbon group may further have a substituent, and preferably has a halogen atom as the substituent. L 10 is preferably a single bond or an alkylene group.

[0098] R8~R 10 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The cycloalkyl group may be either monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The aralkyl group preferably has 7 to 18 carbon atoms. The alkenyl group may be either linear or branched, and preferably has 2 to 6 carbon atoms. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group may further have a substituent, and preferably have a halogen atom (preferably a fluorine atom) as the substituent. R8~R 10 As the group, an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. R8~R 10 At least two of these may be bonded to each other to form a ring.

[0099] In formula (M2), R 11 ~R 14 each independently represents a hydrogen atom or an organic group. 11 and R 12 At least one of the groups represents an organic group. X1 represents -CO-, -SO-, or SO2-. Y1 represents -O-, -S-, -SO-, -SO2-, or -NR 34 - represents R 34 represents a hydrogen atom or an organic group. 11 represents a single bond or a divalent linking group. 15 ~R 17 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0100] R 11 ~R 14 each independently represents a hydrogen atom or an organic group. 11 and R 12 At least one of the groups represents an organic group. Examples of the organic group include R 1 and R 4 Examples of the organic group include organic groups represented by the following formula: Among these, the organic group is preferably an alkyl group (linear or branched, preferably having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms), an aralkyl group (preferably having 7 to 18 carbon atoms), or an alkenyl group (linear or branched, preferably having 2 to 6 carbon atoms). R11 and R 12 As the alkyl group, an alkyl group having a fluorine atom is preferable, and an alkyl group having a fluorine atom is more preferable. R 13 and R 14 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0101] X1 represents -CO-, -SO- or -SO2-, and is preferably -CO-. Y1 is -O-, -S-, -SO-, -SO2- or -NR 34 Y1 is preferably -O- or -S-, and more preferably -O-. R 34 represents a hydrogen atom or an organic group. 34 is preferably an organic group.

[0102] L 11 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups combining these. N is a substituent (e.g., the above R 1 ~R 4 The hydrocarbon group may further have a substituent, and preferably has a halogen atom as the substituent. L 11 As the alkyl group, a hydrocarbon group is preferred, and an alkylene group is more preferred.

[0103] R 15 ~R 17 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. The alkyl group may be either linear or branched, and preferably has 1 to 6 carbon atoms. The cycloalkyl group may be either monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The aralkyl group preferably has 7 to 18 carbon atoms. The alkenyl group may be either linear or branched, and preferably has 2 to 6 carbon atoms. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group may further have a substituent, and preferably have a halogen atom (preferably a fluorine atom) as the substituent. R 15 ~R 17 is preferably an alkyl group or an aryl group. R 15 ~R 17 At least two of these may be bonded to each other to form a ring.

[0104] In formula (M3), R 18 and R 19 R each independently represents a hydrogen atom or an organic group. 20 and R 21 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0105] Examples of the organic group include R 1 and R 4 Examples of the organic group include an organic group (for example, an alkyl group) exemplified by the substituent represented by the following formula: R 18 and R 19 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. R 20 and R 21 Examples of the R in formula (M2) include 15 ~R 17 and a hydrogen atom or an alkyl group is preferred. R 18 ~R21 At least two of R may be bonded to each other to form a ring. 18 and R 19 and, and R 20 and R 21 and preferably bond to each other to form a ring.

[0106] In formula (M4), R 22 ~R 24 L each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 12 represents a single bond or a divalent linking group. Ar1 represents an aromatic ring group. R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0107] R 22 ~R 24 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The cycloalkyl group may be either monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The number of carbon atoms in the alkoxycarbonyl group is preferably 1 to 10. Examples of the alkyl group moiety in the alkoxycarbonyl group include the same groups as the alkyl groups described above. R 22 ~R 24 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0108] L 12 represents a single bond or a divalent linking group. L 12 As for L in formula (M2),11 A single bond is preferred.

[0109] Ar1 represents an aromatic ring group. The aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms in the aromatic ring group is preferably 5 to 15. The aromatic ring group may have one or more (e.g., 1 to 5) heteroatoms (e.g., oxygen atoms, sulfur atoms, and / or nitrogen atoms) as ring atoms. The aromatic ring group is preferably a benzene ring group.

[0110] R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 25 ~R 27 Examples of the R in formula (M2) include 15 ~R 17 Examples include: R 25 ~R 27 is preferably a hydrogen atom or an alkyl group. R 25 ~R 27 At least two of R may be bonded to each other to form a ring. 26 and R 27 and preferably bond to each other to form a ring. 24 or R 25 may be bonded to form a ring.

[0111] In formula (M5), R 28 ~R 30 L each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 13 represents a single bond or a divalent linking group. 31 and R 32 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 33represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0112] R 28 ~R 30 is R in formula (M4). 22 ~R 24 The same definition and preferred embodiments are also the same. L 13 is L in formula (M4) 12 The same definition and preferred embodiments are also the same. R 33 is R in formula (M2) 15 ~R 17 The same definition and preferred embodiments are also the same. R 31 ~R 33 At least two of R may be bonded to each other to form a ring. 32 and R 33 and preferably bond to each other to form a ring.

[0113] The content of the repeating unit b is preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units of the acid-decomposable resin, from the viewpoint of better resolution and LWR. The upper limit of the content is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units. The repeating unit b may be used alone or in combination of two or more types. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0114] <Repeating Unit Having a Lactone Group> The acid-decomposable resin may have a repeating unit having a lactone group. The repeating unit having a lactone group may or may not fall under the category of the repeating units described above. For example, a repeating unit having a lactone group may or may not fall under the category of repeating unit a, and may or may not fall under the category of repeating unit b having an acid-decomposable group, so long as it has a lactone group.

[0115] The lactone group may have a lactone structure or a sultone structure. The lactone structure is preferably a 5- to 7-membered ring lactone structure. In particular, it is more preferable that another ring structure is condensed with the 5- to 7-membered ring lactone structure to form a bicyclo structure or a spiro structure. The acid-decomposable resin preferably has a repeating unit having a lactone group formed by removing one or more (for example, one or two) hydrogen atoms from a lactone structure represented by any one of formulae (LC1-1) to (LC1-21). The lactone group may also be directly bonded to the main chain, for example, the ring atoms of the lactone group may constitute the main chain of the acid-decomposable resin.

[0116] [ka]

[0117] The lactone structure may have a substituent (Rb2). Examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxy group, a halogen atom, a hydroxyl group, a cyano group, a group containing an acid-decomposable group (which may be the acid-decomposable group itself), and a group combining these. n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple Rb2s may be different from each other, or multiple Rb2s may be bonded to form a ring. Among the ring atoms of the lactone structure, one or more (for example, 1 to 2) methylene groups that are not adjacent to -COO- or O- may be replaced with a heteroatom such as -O- or S-.

[0118] An example of a repeating unit having a lactone group is a repeating unit represented by formula (AI).

[0119] [ka]

[0120] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. The substituents that the alkyl group may have are preferably a hydroxyl group or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, -COO-, a carbonyl group, a carboxy group, or a combination thereof. Among these, a single bond or a linking group represented by Ab1-CO2- is preferred. Ab1 represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group. Among these, a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group is preferred. V represents a group formed by removing one hydrogen atom from a ring atom of the lactone structure represented by any one of formulae (LC1-1) to (LC1-21).

[0121] The repeating unit having a lactone group may be, for example, a repeating unit represented by formula (AII) or (AIII).

[0122] [ka]

[0123] In formulae (AII) and (AIII), RIII each independently represents a hydrogen atom or a substituent. RIII is preferably a hydrogen atom. In formula (AII), ahd1 represents a group formed by removing one hydrogen atom from each of adjacent ring atoms in a lactone structure represented by any one of formulae (LC1-1) to (LC1-21). In formula (AIII), ahd2 represents a group formed by removing two hydrogen atoms from one of the ring atoms of the lactone structure represented by any one of formulae (LC1-1) to (LC1-21).

[0124] Examples of repeating units having a lactone group are shown below.

[0125] [ka]

[0126] [ka]

[0127] When optical isomers exist in the repeating unit having a lactone group, any optical isomer may be used. In addition, one optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0128] The content of the repeating unit having a lactone group is preferably from 5 to 100 mol %, more preferably from 10 to 80 mol %, and even more preferably from 15 to 65 mol %, based on the total repeating units of the acid-decomposable resin. Of the repeating units having a lactone group, the sum of repeating units having a lactone group corresponding to repeating unit a and repeating units having a lactone group not corresponding to repeating unit a may satisfy the above-mentioned preferred content, or a repeating unit having a lactone group corresponding to repeating unit a may alone satisfy the above-mentioned preferred content, or a repeating unit having a lactone group not corresponding to repeating unit a may alone satisfy the above-mentioned preferred content. The repeating unit having a lactone group may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0129] <Repeating Unit Having a Sultone Group or a Carbonate Group> The acid-decomposable resin may have a repeating unit having a sultone group. The sultone group may have a sultone structure. The sultone structure is preferably a 5- to 7-membered sultone structure. In particular, it is more preferable that another ring structure is fused to the 5- to 7-membered sultone structure to form a bicyclo structure or a spiro structure. The sultone group may also be directly bonded to the main chain, for example, the ring atoms of the sultone group may constitute the main chain of the acid-decomposable resin. The acid-decomposable resin preferably has a repeating unit having a sultone group formed by removing one or more (for example, 1 or 2) hydrogen atoms from ring atoms of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3).

[0130] [ka]

[0131] The sultone structure may have a substituent (Rb2). The substituent (Rb2) in formulae (SL1-1) to (SL1-3) can be explained in the same way as the substituent (Rb2) in the lactone structures represented by formulae (LC1-1) to (LC1-21). Among the ring atoms of the sultone structure, one or more (for example, 1 to 2) methylene groups that are not adjacent to -COO- or O- may be replaced with a heteroatom such as -O- or S-.

[0132] Examples of repeating units having a sultone group include a repeating unit represented by the above formula (AI) in which V is replaced with a group formed by removing one hydrogen atom from a ring atom of a sultone structure represented by any one of the formulae (SL1-1) to (SL1-3); a repeating unit represented by the above formula (AII) in which ahd1 is replaced with a group formed by removing one hydrogen atom from each of adjacent ring atoms of a sultone structure represented by any one of the formulae (SL1-1) to (SL1-3); and a repeating unit represented by the above formula (AIII) in which ahd2 is replaced with a group formed by removing two hydrogen atoms from one ring atom of a sultone structure represented by any one of the formulae (SL1-1) to (SL1-3).

[0133] The carbonate group is preferably a cyclic carbonate group. The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by formula (A-1).

[0134] [ka]

[0135] In formula (A-1), R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, -O-, -COO-, a carbonyl group, a carboxy group, or a divalent group formed by combining these groups. Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0136] Examples of repeating units having a sultone group or a carbonate group are shown below.

[0137] [ka]

[0138] The content of the repeating units having a sultone group or a carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more, based on the total repeating units of the acid-decomposable resin, and the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units of the acid-decomposable resin.

[0139] <Repeating Unit Having an Acid Group> The acid-decomposable resin may have a repeating unit having an acid group. The repeating unit having an acid group is preferably different from the repeating units described above. The acid group preferably has a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the acid-decomposable resin has acid groups with a pKa of 13 or less, the content of the acid groups in the acid-decomposable resin is often 0.2 to 6.0 mmol / g, preferably 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. When the acid group content is within the above range, development proceeds well, and the formed pattern has an excellent shape and resolution. The acid group is preferably, for example, a carboxy group, a hydroxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group or an isopropanol group. In addition, one or more (preferably one to two) fluorine atoms of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF3)(OH)-CF2- thus formed is also preferred as an acid group. In addition, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0140] The repeating unit having an acid group is preferably a repeating unit represented by formula (B).

[0141] [ka]

[0142] R3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. The monovalent organic group optionally having a fluorine atom or an iodine atom is preferably a group represented by -L4-R8. L4 represents a single bond or -COO-. R8 represents an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, an aryl group optionally having a fluorine atom or an iodine atom, or a group formed by combining these.

[0143] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0144] L2 represents a divalent group formed by combining a single bond, -COO- or -CO-, -O-, and an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched, and in which -CH2- may be substituted with a halogen atom). L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include a cycloalkyl ring group, a norbornene ring group, and an adamantane ring group.

[0145] R6 represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a monovalent group represented by formula (3L). *-L 6X -R 6X (3L) L 6X represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -SO-, -SO2-, and -NR A -, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), and divalent linking groups combining a plurality of these. A Examples of R include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkylene group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom) and a hydroxyl group. 6X represents a hexafluoroisopropanol group. When R6 is a hydroxyl group, L3 is also preferably an (n+m+1)-valent aromatic hydrocarbon ring group.

[0146] R7 represents a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. m represents an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably an integer of 1 or 2. n represents an integer of 0 or greater than 1. n is preferably an integer of 1 to 4. It is preferable that (n+m+1) is an integer of 1 to 5.

[0147] The repeating unit having an acid group is also preferably a repeating unit represented by formula (I).

[0148] [ka]

[0149] In formula (I), R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, provided that R 42 may be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO- or CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or an alkylene group. Ar4 represents an (n+1)-valent aromatic ring group, R 42 When it combines with the group to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1 to 5.

[0150] R in formula (I) 41 , R 42 and R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0151] R in formula (I) 41 , R 42 and R 43 The cycloalkyl group may be monocyclic or polycyclic, and among these, monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, are preferred. R in formula (I) 41 , R 42 and R 43Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred. R in formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group of the above R 41 , R 42 , R 43 The same alkyl groups as those in the above are also preferred.

[0152] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

[0153] Ar4 represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent.

[0154] When n is an integer of 2 or more, examples of the (n+1)-valent aromatic ring group include groups obtained by removing any (n-1) hydrogen atoms from the above specific examples of the divalent aromatic ring group. The (n+1)-valent aromatic ring group may further have a substituent.

[0155] Examples of the substituent that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include, for example, R 41 , R 42 and R 43Examples of the alkyl groups include those mentioned above, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy groups, and aryl groups such as phenyl groups. -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 Examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or less carbon atoms are preferred. X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0156] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. The repeating unit represented by formula (I) preferably has a hydroxystyrene structure, that is, Ar4 is preferably a benzene ring group.

[0157] The repeating unit represented by formula (I) is preferably a repeating unit represented by formula (1).

[0158] [ka]

[0159] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are multiple Rs, they may be the same or different. When there are multiple Rs, they may combine with each other to form a ring. R is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0160] Examples of repeating units having an acid group are shown below.

[0161] [ka]

[0162] In the following examples, a represents 1 or 2 in the formula.

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] Among these, the repeating units specifically described below are preferred: In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] The content of the repeating units having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units of the acid-decomposable resin, and the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units of the acid-decomposable resin.

[0172] <Repeating Unit Having a Fluorine Atom or an Iodine Atom> The acid-decomposable resin may have a repeating unit containing a fluorine atom or an iodine atom. The repeating unit having a fluorine atom or an iodine atom is preferably different from the repeating units described above.

[0173] The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by formula (C).

[0174] [ka]

[0175] L5 represents a single bond or -COO-. R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0176] Examples of repeating units containing a fluorine atom or an iodine atom are shown below.

[0177] [ka]

[0178] The content of the repeating units having a fluorine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units of the acid-decomposable resin, and the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on the total repeating units of the acid-decomposable resin.

[0179] <Repeating unit represented by formula (V-1) or formula (V-2)> The acid-decomposable resin may have a repeating unit represented by formula (V-1) or formula (V-2). The repeating units represented by formula (V-1) and formula (V-2) are preferably different from the above repeating units.

[0180] [ka]

[0181] In the formula, R6 and R7 each independently represent 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, -COO- (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxy group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X 4 is a methylene group, an oxygen atom or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954. The content of the repeating unit represented by formula (V-1) or formula (V-2) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0182] <Repeating units for reducing main chain mobility> The acid-decomposable resin may have a repeating unit for reducing the mobility of the main chain as a repeating unit different from the repeating unit a. The acid-decomposable resin preferably has a high glass transition temperature (Tg) in order to prevent excessive diffusion of the generated acid or pattern collapse during development. The Tg is preferably higher than 90°C, more preferably higher than 100°C, even more preferably higher than 110°C, and particularly preferably higher than 125°C. Since an excessively high Tg reduces the dissolution rate in the developer, the Tg is preferably 400°C or lower, more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as an acid-decomposable resin is calculated by the following method. First, the Tg of each homopolymer consisting of only each repeating unit contained in the polymer is calculated using the Bicerano method. Hereinafter, the calculated Tg is referred to as the "Tg of the repeating unit." Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg for each mass proportion is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to obtain the Tg (°C) of the polymer. The Bicerano method is described in, for example, Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0183] To increase the Tg of the acid-decomposable resin (preferably to make the Tg higher than 90°C), it is preferable to reduce the mobility of the main chain of the acid-decomposable resin. Methods for reducing the mobility of the main chain of the acid-decomposable resin include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of a substituent group that induces interactions between acid-decomposable resins near the main chain (d) Main chain formation in a cyclic structure (e) Linking of cyclic structures to the main chain The acid-decomposable resin preferably has a repeating unit that exhibits a homopolymer Tg of 130° C. or higher. The type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher may be any repeating unit exhibiting a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, the repeating unit may be considered to exhibit a homopolymer Tg of 130° C. or higher.

[0184] (Repeating unit represented by formula (A)) A specific example of the above method (a) is a method of introducing a repeating unit represented by formula (A) into an acid-decomposable resin.

[0185] [ka]

[0186] In formula (A), R A represents a group having a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] to

[0119] of WO 2018 / 193954. The content of the repeating unit represented by formula (A) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0187] (Repeating unit represented by formula (B)) A specific example of the above method (b) is a method of introducing a repeating unit represented by formula (B) into an acid-decomposable resin.

[0188] [ka]

[0189] In formula (B), R b1 ~R b4 each independently represents a hydrogen atom or an organic group, R b1 ~R b4 At least two of these represent organic groups. In addition, when at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of the other organic groups are not particularly limited. Furthermore, when none of the organic groups has a ring structure directly connected to the main chain in the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms. Examples of the repeating unit represented by formula (B) include those described in paragraphs

[0113] to

[0115] of WO 2018 / 193954. The content of the repeating unit represented by formula (B) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0190] (Repeating unit represented by formula (C)) A specific example of the above method (c) is a method of introducing a repeating unit represented by formula (C) into an acid-decomposable resin.

[0191] [ka]

[0192] In formula (C), R c1 ~R c4 each independently represents a hydrogen atom or an organic group, R c1 ~R c4 At least one of the groups has a hydrogen-bonding hydrogen atom within three atoms from the main chain carbon. In particular, it is preferable that the hydrogen-bonding hydrogen atom be within two atoms (closer to the main chain) from the viewpoint of inducing interaction between the main chains of the acid-decomposable resin. Examples of the repeating unit represented by formula (C) include those described in paragraphs

[0119] to

[0121] of WO 2018 / 193954. The content of the repeating unit represented by formula (C) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0193] (Repeating unit represented by formula (D)) A specific example of the above (d) is a method of introducing a repeating unit represented by formula (D) into an acid-decomposable resin.

[0194] [ka]

[0195] In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited. Examples of the repeating unit represented by formula (D) include those described in paragraphs

[0126] to

[0027] of WO 2018 / 193954. The content of the repeating unit represented by formula (D) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0196] (Repeating unit represented by formula (E)) A specific example of the above method (e) is a method of introducing a repeating unit represented by formula (E) into an acid-decomposable resin.

[0197] [ka]

[0198] In formula (E), each Re independently represents a hydrogen atom or an organic group, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, each of which may have a substituent. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. There are no particular restrictions on the number of atoms contained in the cyclic group. Examples of the repeating unit represented by formula (E) include those described in paragraphs

[0131] to

[0133] of WO 2018 / 193954. The content of the repeating unit represented by formula (E) is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0199] <Repeating Unit Having a Hydroxyl Group or a Cyano Group> The acid-decomposable resin may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and / or the affinity for the developer. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs

[0153] to

[0158] of WO 2020 / 004306. The content of repeating units having a hydroxyl group or a cyano group is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin.

[0200] <Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition> The acid-decomposable resin may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposition. This reduces the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl(meth)acrylate, diadamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate. The content of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units in the acid decomposable resin.

[0201] <Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group> The acid-decomposable resin may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0202] [ka]

[0203] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group, where Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0204] The cyclic structure of R5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms. Detailed definitions of each group and repeating units in formula (III) include, for example, those described in paragraphs

[0169] to

[0173] of WO 2020 / 004306. The content of the repeating unit represented by formula (III) which has neither a hydroxyl group nor a cyano group is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on all repeating units in the acid-decomposable resin.

[0205] <Other repeating units> The acid-decomposable resin may have other repeating units in addition to the repeating units described above. The other repeating units are not particularly limited as long as they are other than the above repeating units. The other repeating units may include, for example, repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, repeating units having a hydantoin ring group, and repeating units having a sulfolane ring group. The content of the other repeating units is preferably from 1 to 65 mol %, more preferably from 5 to 45 mol %, based on the total repeating units of the acid-decomposable resin. Other examples of repeating units are shown below.

[0206] [ka]

[0207] In addition to the above repeating units, the acid-decomposable resin may have various repeating units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0208] The acid-decomposable resin can be synthesized according to a conventional method (for example, radical polymerization). The weight-average molecular weight of the acid-decomposable resin, as measured by the GPC method in terms of polystyrene, is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By adjusting the weight-average molecular weight of the acid-decomposable resin to 1,000 to 200,000, deterioration in heat resistance and dry etching resistance can be further suppressed. In addition, deterioration in developability and deterioration in film-formability due to increased viscosity can be further suppressed. The dispersity (molecular weight distribution) of the acid-decomposable resin is typically 1 to 5, preferably 1.00 to 3.00, more preferably 1.20 to 3.00, and even more preferably 1.20 to 2.00. The smaller the dispersity, the better the resolution and resist shape, and further the smoother the sidewalls of the resist pattern and the better the roughness.

[0209] In the resist composition, the content of the acid-decomposable resin is preferably 10.0 to 99.0 mass %, more preferably 20.0 to 98.0 mass %, and even more preferably 25.0 to 95.0 mass %, based on the total solid content of the resist composition. The acid-decomposable resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0210] [Photoacid generator] The resist composition may contain one or more compounds (hereinafter also referred to as "specific photoacid generators") selected from the group consisting of compounds (I) and (II) as compounds that generate acid upon irradiation with actinic rays or radiation (photoacid generators). As will be described later, the resist composition may further contain a photoacid generator other than the specific photoacid generator (hereinafter simply referred to as "another photoacid generator"). The resist composition may also contain compound (III). The photoacid generator does not include the compound (1). First, the specific photoacid generators (compounds (I) and (II)) will be described below.

[0211] <Compound (I)> Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which, upon irradiation with actinic rays or radiation, generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y: Structural site X: Anion site A1 - and cationic moiety M1 + and a structural portion that forms a first acidic site represented by HA1 upon irradiation with actinic rays or radiation. Structural site Y: Anionic site A2 - and cationic moiety M2 + and a structural portion that forms a second acidic site represented by HA2 upon irradiation with actinic rays or radiation. However, compound (I) satisfies the following condition I.

[0212] Condition I: In the compound (I), the cation moiety M1 in the structural moiety X + and the cationic moiety M2 in the structural moiety Y. + H + The compound PI in which the cationic moiety M1 in the structural moiety X is replaced by + H + and the cationic moiety M2 in the structural moiety Y. + H + and an acid dissociation constant a2 derived from the acidic site represented by HA2 in which HA is replaced by HA, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0213] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic moieties derived from the structural moiety X and one of the second acidic moieties derived from the structural moiety Y, compound PI corresponds to a "compound having HA1 and HA2." More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined by determining whether the compound PI is "A1 - The pKa at which the compound is formed is the acid dissociation constant a1, and the above "A1 - and HA2" is "A1 - and A2 - The pKa at which the compound becomes "a compound having the above formula" is the acid dissociation constant a2.

[0214] Furthermore, when compound (I) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI corresponds to a "compound having two HA1s and one HA2." When the acid dissociation constant of such a compound PI is calculated, it is found that the compound PI is "one A1 - The acid dissociation constant when "a compound having one HA1 and one HA2" is formed and "a compound having one A1 - and one HA1 and one HA2" is "a compound with two A1 - The acid dissociation constant when the compound is a "compound having two A1 - and one HA2" is "a compound with two A1 - and A2 - In other words, in the case of such a compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M1 in the structural moiety X corresponds to the acid dissociation constant a2. + H + When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by HA1, the value of the acid dissociation constant a2 is greater than the largest value of the plurality of acid dissociation constants a1. - The acid dissociation constant when "aa" is used is a compound having one HA1 and one HA2. - and one HA1 and one HA2" is "a compound with two A1 -When the acid dissociation constant when it becomes "a compound having one HA2" is ab, the relationship between aa and ab satisfies aa < ab.

[0215] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - and two or more of the above M1 + may be the same or different from each other. Also, in the compound (I), the above A1 - and the above A2 - , and also the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0216] From the point that the LWR performance of the formed pattern is more excellent, in the above compound PI, the difference between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. In addition, the upper limit of the difference between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 16 or less.

[0217] Also, from the point that the LWR performance of the formed pattern is more excellent, in the above compound PI, the acid dissociation constant a2 is, for example, 20 or less, and preferably 15 or less. In addition, the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.

[0218] In order to obtain a more excellent LWR performance of the formed pattern, the acid dissociation constant a1 of the compound PI is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0219] Anionic site A1 - and anionic site A2 - is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6). - As the anionic moiety A2, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and any of formulas (AA-1) to (AA-3) is more preferred. - As the anion moiety A1 - Preferably, it is one that can form an acidic moiety with a larger acid dissociation constant than the above, and more preferably any of formulas (BB-1) to (BB-6). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R A represents a monovalent organic group. A Examples of the monovalent organic group represented by the formula include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0220] [ka] JPEG0007756117000042.jpg25167

[0221] In addition, the cationic moiety M1 + and cationic moiety M2 + is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. Examples of organic cations include M in formula (Ia-1) described below. 11 + and M 12 + The organic cations may be the same as those represented by the following formula:

[0222] Specific structures of compound (I) include, for example, compounds represented by formulae (Ia-1) to (Ia-5) described below. First, the compound represented by formula (Ia-1) will be described below. The compound represented by formula (Ia-1) is as follows.

[0223] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0224] Compound (Ia-1) can be used to treat HA by irradiation with actinic rays or radiation. 11 -L1-A 12 It generates an acid represented by H.

[0225] In formula (Ia-1), M 11 + and M 12 + each independently represents an organic cation. A 11 - and A 12 - each independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12 + may be the same or different. A 11 - and A 12 - may be the same or different, but are preferably different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The organic cation represented by H +Compound PIa (HA 11 -L1-A 12 In H), A 12 The acid dissociation constant a2 derived from the acidic site represented by H is HA 11 The acid dissociation constant a1 is larger than the acid dissociation constant a1 derived from the acidic moiety represented by the formula (Ia-1). The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. The acid generated from the compound PIa and the compound represented by the formula (Ia-1) upon irradiation with actinic rays or radiation is the same. Also, M 11 + , M 12 + , A 11 - , A 12 - At least one of L1 and L2 may have an acid-decomposable group as a substituent.

[0226] In formula (Ia-1), M1 + and M2 + The organic cation represented by the formula (I) is as described below.

[0227] A 11 - The monovalent anionic functional group represented by the following formula is the anionic moiety A1 - In addition, A 12 - The monovalent anionic functional group represented by the above anionic moiety A2 - means a monovalent group containing A 11 - and A 12 - The monovalent anionic functional group represented by the formula (II) is preferably a monovalent anionic functional group containing an anionic moiety of any one of the formulae (AA-1) to (AA-3) and (BB-1) to (BB-6) above, and more preferably a monovalent anionic functional group selected from the group consisting of the formulae (AX-1) to (AX-3) and (BX-1) to (BX-7). A 11 -The monovalent anionic functional group represented by formula (AX-1) to (AX-3) is preferred as the monovalent anionic functional group represented by formula (AX-1). 12 - As the monovalent anionic functional group represented by formula (BX-1), a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7) is preferred, and a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-6) is more preferred.

[0228] [ka]

[0229] In formulas (AX-1) to (AX-3), R A1 and R A2 each independently represents a monovalent organic group. * represents a bonding position.

[0230] R A1 Examples of the monovalent organic group represented by the formula (I) include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0231] R A2 The monovalent organic group represented by the formula (I) is preferably a linear, branched or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0232] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent, which is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) or a cyano group, more preferably a fluorine atom, an iodine atom or a perfluoroalkyl group.

[0233] In formulas (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bonding position. R B The monovalent organic group represented by the formula (I) is preferably a linear, branched or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atom that is the bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), the carbon atom that is directly bonded to —CO— specified in the formula in the alkyl group corresponds to this, in the case of formulas (BX-2) and (BX-3), the carbon atom that is directly bonded to —SO2— specified in the formula in the alkyl group corresponds to this, and in the case of formula (BX-6), the carbon atom that is directly bonded to —SO2— specified in the formula in the alkyl group corresponds to this - When ) has a substituent, it is also preferable that the substituent is a fluorine atom or a cyano group. In addition, the alkyl group may have a carbon atom substituted with a carbonyl carbon.

[0234] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms), and more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

[0235] In formula (Ia-1), the divalent linking group represented by L1 includes -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure), Examples of R include a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring, divalent aromatic heterocyclic group (a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring), divalent aromatic hydrocarbon ring group (a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group combining two or more of these. Examples of R include a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group (preferably having 1 to 6 carbon atoms), for example. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0236] The divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).

[0237] [ka]

[0238] In formula (L1), L 111 represents a single bond or a divalent linking group. L 111 Examples of the divalent linking group represented by the formula (I) include -CO-, -NH-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, and more preferably having a straight or branched chain), an optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), an optionally substituted aryl (preferably having 6 to 10 carbon atoms), and a divalent linking group that is a combination of two or more of these. Examples of the substituent include a halogen atom. p represents an integer of 0 to 3, and preferably an integer of 1 to 3. v represents an integer of 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group. Among these, Xf1 and Xf2 are preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and particularly preferably both Xf1 and Xf2 are fluorine atoms. * indicates the bond position. L in formula (Ia-1) 11represents a divalent linking group represented by formula (L1), L in formula (L1) 111 The bond (*) on the side of the A 12 - It is preferred to combine with

[0239] (Ia-1)M 11 + and M 12 + Preferred forms of the organic cation represented by the formula (I) will be described in detail. M 11 + and M 12 + The organic cations represented by the formulas below are each independently preferably an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)).

[0240] [ka]

[0241] In the formula (ZaI), R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The number of carbon atoms in the organic group represented by R is usually 1 to 30, and preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, -COO-, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0242] Suitable embodiments of the organic cation in formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), an organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0243] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 may all be aryl groups, or R 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 one of which is an aryl group, and R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, -COO-, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, -COO-, an amide group, and / or a carbonyl group (e.g., a butylene group, a pentylene group, or -CH-CH-O-CH-CH-). Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0244] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0245] R 201 ~R 203 The substituents which the aryl group, alkyl group and cycloalkyl group may have are each independently preferably an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxyl group, a carboxy group, -COO-, a sulfinyl group, a sulfonyl group, an alkylthio group or a phenylthio group. The above-mentioned substituent may further have a substituent if possible. For example, it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any desired manner to form an acid-decomposable group. The acid-decomposable group is intended to be a group that decomposes under the action of an acid to generate an acid group, and preferably has a structure in which the acid group is protected with a leaving group that is released under the action of an acid. The acid group and leaving group are as described above.

[0246] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 are each independently a cation representing an organic group having no aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. R 201 ~R 203 The organic group having no aromatic ring as the aromatic ring generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms. R 201 ~R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0247] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. Also, R 201 ~R 203 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0248] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the formula (ZaI-3b).

[0249] [ka]

[0250] In 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 hydroxyl 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 (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Also, R 1c ~R 7c , and R x and R y It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0251] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0252] R 1c ~R 5c Two or more of the following, R 6c and R 7c and R x and R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c and R 5c and R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0253] R 1c ~R 5c , R 6c , R 7c , R x , R y , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x and R x and R y The ring formed by bonding together may have a substituent.

[0254] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the formula (ZaI-4b).

[0255] [ka]

[0256] In the formula (ZaI-4b), l represents an integer of 0 to 2. r represents an integer of 0 to 8. R 13 represents a group having a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may further have a substituent. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 When a plurality of groups are present, each independently represents the above group such as a hydroxyl group. R 15 Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 may be bonded to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R 15 are preferably alkylene groups and bond together to form a ring structure. 15 The ring formed by bonding together may have a substituent.

[0257] R 13 , R 14 and R 15The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group. Also, R 13 ~R 15 , and R x and R y It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0258] Next, formula (ZaII) will be explained. In formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0259] R 204 and R 205 The aryl group, alkyl group and cycloalkyl group in R may each independently have a substituent. 204 and R 205Examples of the 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. 204 and R 205 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0260] Next, the formulas (Ia-2) to (Ia-4) will be explained.

[0261] [ka]

[0262] In formula (Ia-2), A 21a - and A 21b - Each independently represents a monovalent anionic functional group. 21a - and A 21b - The monovalent anionic functional group represented by the following formula is the anionic moiety A1 - A means a monovalent group containing 21a - and A 21b - Examples of the monovalent anionic functional group represented by the formula (AX-1) include monovalent anionic functional groups selected from the group consisting of the above formulae (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. 22 - The divalent anionic functional group represented by the above anionic moiety A2 - A means a divalent group containing 22 - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) shown below can be given.

[0263] [ka]

[0264] M 21a + , M 21b + and M 22 + Each independently represents an organic cation. 21a + , M 21b + and M 22 + As the organic cation represented by the formula, the above M1 + The same definition and preferred embodiments are also the same. L 21 and L 22 each independently represents a divalent organic group.

[0265] In addition, in the above formula (Ia-2), M 21a + , M 21b + and M 22 + The organic cation represented by H + In compound PIa-2, A is replaced by 22 The acid dissociation constant a2 derived from the acidic site represented by H is A 21a Acid dissociation constants a1-1 and A1 derived from H 21b It is larger than the acid dissociation constant a1-2 derived from the acidic site represented by H. The acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the above acid dissociation constant a1. In addition, A 21a - and A 21b - may be the same or different. 21a + , M 21b + and M 22 + may be the same or different from each other. Also, M21a + , M 21b + , M 22 + , A 21a - , A 21b - , L 21 and L 22 At least one of them may have an acid-decomposable group as a substituent.

[0266] In formula (Ia-3), A 31a - and A 32 - Each independently represents a monovalent anionic functional group. 31a - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - The same definition and preferred embodiments are also the same. A 32 - The monovalent anionic functional group represented by the following formula is the anionic moiety A2 - A means a monovalent group containing 32 - Examples of the monovalent anionic functional group represented by the formula (BX-1) include monovalent anionic functional groups selected from the group consisting of the above formulae (BX-1) to (BX-7). A 31b - represents a divalent anionic functional group. 31b - The divalent anionic functional group represented by the following formula is the anionic moiety A1 - A means a divalent group containing 31b - Examples of the divalent anionic functional group represented by formula (AX-4) include divalent anionic functional groups represented by formula (AX-4) shown below.

[0267] [ka]

[0268] M 31a + , M 31b + and M 32 + Each independently represents a monovalent organic cation. 31a + , M 31b + and M 32 + As the organic cation, the above M1 + The same definition and preferred embodiments are also the same. L 31 and L 32 each independently represents a divalent organic group.

[0269] In addition, in the above formula (Ia-3), M 31a + , M 31b + and M 32 + The organic cation represented by H + In compound PIa-3, A is replaced by 32 The acid dissociation constant a2 derived from the acidic site represented by H is A 31a Acid dissociation constants a1-3 and A2 derived from the acidic site represented by H 31b It is larger than the acid dissociation constant a1-4 derived from the acidic site represented by H. The acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1. In addition, A 31a - and A 32 - may be the same or different. 31a + , M 31b + and M 32 + may be the same or different from each other. Also, M 31a + , M 31b + , M 32 + , A 31a -, A 32 - , L 31 and L 32 At least one of them may have an acid-decomposable group as a substituent.

[0270] In formula (Ia-4), A 41a - , A 41b - and A 42 - Each independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - Also, A 42 - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-3) is 32 - The same definition and preferred embodiments are also the same. M 41a + , M 41b + and M 42 + each independently represents an organic cation. L 41 represents a trivalent organic group.

[0271] In addition, in the above formula (Ia-4), M 41a + , M 41b + and M 42 + The organic cation represented by H + In compound PIa-4, A is replaced by 42 The acid dissociation constant a2 derived from the acidic site represented by H is A 41a Acid dissociation constants a1-5 and A2 derived from the acidic site represented by H 41bIt is larger than the acid dissociation constant a1-6 derived from the acidic site represented by H. The acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1. In addition, A 41a - , A 41b - and A 42 - may be the same or different. 41a + , M 41b + and M 42 + may be the same or different from each other. Also, M 41a + , M 41b + , M 42 + , A 41a - , A 41b - , A 42 - and L 41 At least one of them may have an acid-decomposable group as a substituent.

[0272] L in formula (Ia-2) 21 and L 22 and L in formula (Ia-3). 31 and L 32Examples of the divalent organic group represented by the formula (I) include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and more preferably a 6-membered ring), and a divalent organic group formed by combining two or more of these. The above R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0273] L in formula (Ia-2) 21 and L 22 and L in formula (Ia-3). 31 and L 32 The divalent organic group represented by the formula (L1) is preferably, for example, a divalent organic group represented by the formula (L2).

[0274] [ka]

[0275] In formula (L2), q represents an integer of 1 to 3. * represents a bonding position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf's are fluorine atoms.

[0276] L A represents a single bond or a divalent linking group. L A Examples of the divalent linking group represented by the formula (I) include -CO-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group formed by combining two or more of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0277] Examples of the divalent organic group represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group. Preferred substituents include an alkyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms). L in formula (Ia-2) 21 and L22 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 21 - and A 21b - It is preferred to combine with Furthermore, L in formula (Ia-3) 31 and L 32 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 31a - and A 32 - It is preferred to combine with

[0278] L in formula (Ia-4) 41 Examples of the trivalent organic group represented by formula (L1) include a trivalent organic group represented by formula (L3).

[0279] [ka]

[0280] In formula (L3), L B represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a bonding position.

[0281] The hydrocarbon ring group may be either an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14. The heterocyclic group may be either an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The heterocycle is preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring. L Bis preferably a trivalent hydrocarbon ring group, more preferably a benzene ring group or an adamantane ring group. The benzene ring group or the adamantane ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

[0282] In addition, in formula (L3), L B1 ~L B3 L each independently represents a single bond or a divalent linking group. B1 ~L B3 Examples of the divalent linking group represented by the formula (I) include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and more preferably a 6-membered ring), and a divalent linking group formed by combining these. The above R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom). L B1 ~L B3 The divalent linking group represented by the formula (I) is preferably -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group which may have a substituent, or a divalent linking group which is a combination of these.

[0283] L B1 ~LB3 As the divalent linking group represented by formula (L3-1), a divalent linking group represented by formula (L3-1) is more preferred.

[0284] [ka]

[0285] In formula (L3-1), L B11 represents a single bond or a divalent linking group. L B11 Examples of the divalent linking group represented by the formula (I) include -CO-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, and may be linear or branched) which may have a substituent, and a divalent linking group formed by combining these. Examples of the substituent include a halogen atom. r represents an integer of 1 to 3. Xf has the same meaning as Xf in the above formula (L2), and the preferred embodiments are also the same. * indicates the bond position.

[0286] L B1 ~L B3 Examples of the divalent linking group represented by the formula include *-O-*, *-O-SO2-CF2-*, *-O-SO2-CF2-CF2-*, *-O-SO2-CF2-CF2-CF2-*, and *-COO-CH2-CH2-*. L in formula (Ia-4) 41 contains a divalent organic group represented by formula (L3-1), and the divalent organic group represented by formula (L3-1) and A 42 - When the bond is formed with A in formula (Ia-4), the bond (*) on the carbon atom side shown in formula (L3-1) is 42 - It is preferred to combine with

[0287] Next, formula (Ia-5) will be described.

[0288] [ka]

[0289] In formula (Ia-5), A 51a - , A 51b - and A 51c - Each independently represents a monovalent anionic functional group. 51a - , A 51b - and A 51c - The monovalent anionic functional group represented by the following formula is the anionic moiety A1 - A means a monovalent group containing 51a - , A 51b - and A 51c - Examples of the monovalent anionic functional group represented by the formula (AX-1) include monovalent anionic functional groups selected from the group consisting of the above formulae (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. 52a - and A 52b - The divalent anionic functional group represented by the above anionic moiety A2 - A means a divalent group containing 22 - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) include divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).

[0290] M 51a + , M 51b + , M 51c + , M 52a + and M 52b + Each independently represents an organic cation. 51a + , M51b + , M 51c + , M 52a + and M 52b + As the organic cation represented by the formula, the above M1 + The same definition and preferred embodiments are also the same. L 51 and L 53 L each independently represents a divalent organic group. 51 and L 53 The divalent organic group represented by the formula (Ia-2) is 21 and L 22 The same definition and preferred embodiments are also the same. L 52 represents a trivalent organic group. 52 The trivalent organic group represented by the formula (Ia-4) is 41 The same definition and preferred embodiments are also the same.

[0291] In addition, in the above formula (Ia-5), M 51a + , M 51b + , M 51c + , M 52a + and M 52b + The organic cation represented by H + In compound PIa-5, A is replaced by 52a The acid dissociation constants a2-1 and A2-1 derived from the acidic site represented by H 52b The acid dissociation constant a2-2 derived from the acidic site represented by H is A 51a Acid dissociation constant a1-1, A 51b The acid dissociation constants a1-2 and A2 derived from the acidic site represented by H 51c It is larger than the acid dissociation constant a1-3 derived from the acidic site represented by H. The acid dissociation constants a1-1 to a1-3 correspond to the above acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above acid dissociation constant a2. In addition, A 51a - , A 51b- and A 51c - may be the same or different. 52a - and A 52b - may be the same or different. 51a + , M 51b + , M 51c + , M 52a + and M 52b + may be the same or different from each other. Also, M 51b + , M 51c + , M 52a + , M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 and L 53 At least one of them may have an acid-decomposable group as a substituent.

[0292] <Compound (II)> Compound (II) is a compound having two or more of the structural moieties X described above and one or more of the structural moieties Z described below, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation. Structural site Z: a ​​non-ionic site capable of neutralizing acids

[0293] In compound (II), the definition of the structural moiety X and A1 - and M1 + The definition of the structural moiety X in the compound (I) and A1 - and M1 + The definition and preferred embodiments are also the same.

[0294] In the compound (II), the cation moiety M1 in the structural moiety X + H + In the compound PII, the cationic moiety M1 in the structural moiety X is replaced by + H + The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the acid dissociation constant a1 is substituted with HA1 is the same as the acid dissociation constant a1 in the compound PI. In addition, when compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, it is considered that compound PII has "one A1 - and one HA1" and the acid dissociation constant when "a compound having one A1" - and one HA1" is "a compound with two A1 - The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0295] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. - and two or more of the above M1 + may be the same or different.

[0296] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is preferably, for example, a moiety containing a functional group having an electron or a group capable of electrostatically interacting with a proton. Examples of functional groups having a group or electrons capable of electrostatically interacting with a proton include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the formula:

[0297] [ka]

[0298] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and a primary to tertiary amine structure is preferred.

[0299] Examples of compound (II) include compounds represented by formula (IIa-1) and formula (IIa-2).

[0300] [ka]

[0301] In the above formula (IIa-1), A 61a - and A 61b - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 61a + and M 61b + respectively represent M in the above formula (Ia-1). 11 + The same definition and preferred embodiments are also the same. In the above formula (IIa-1), L 61 and L 62 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0302] In formula (IIa-1), R 2X represents a monovalent organic group. 2X Examples of the monovalent organic group represented by the formula (I) include an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched) in which -CH2- may be substituted with one or a combination of two or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-, a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an alkenyl group (preferably having 2 to 6 carbon atoms). The alkylene group, cycloalkylene group, and alkenylene group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0303] In addition, in the above formula (IIa-1), M 61a + and M 61b + The organic cation represented by H + In the compound PIIa-1, A is replaced by 61a Acid dissociation constants a1-7 and A2 derived from the acidic site represented by H 61b The acid dissociation constant a1-8 derived from the acidic site represented by H corresponds to the above acid dissociation constant a1. In the compound (IIa-1), the cationic moiety M in the structural moiety X 61a + and M 61b + H + Compound PIIa-1, which is substituted with HA 61a -L 61 -N(R 2X )-L 62 -A 61b The compound PIIa-1 corresponds to H. The acid generated from the compound represented by formula (IIa-1) upon irradiation with actinic rays or radiation is the same as that generated from the compound PIIa-1. Also, M 61a + , M 61b + , A 61a - , A 61b- , L 61 , L 62 and R 2X At least one of them may have an acid-decomposable group as a substituent.

[0304] In the above formula (IIa-2), A 71a - , A 71b - and A 71c - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 71a + , M 71b + , and M 71c + respectively represent M in the above formula (Ia-1). 11 + The same definition and preferred embodiments are also the same. In the above formula (IIa-2), L 71 , L 72 and L 73 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0305] In addition, in the above formula (IIa-2), M 71a + , M 71b + , and M 71c + The organic cation represented by H + In the compound PIIa-2, A is replaced by 71a Acid dissociation constant a1-9, A, derived from the acidic site represented by H 71b The acid dissociation constants a1-10 and A2 derived from the acidic site represented by H 71c The acid dissociation constant a1-11 derived from the acidic site represented by H corresponds to the above acid dissociation constant a1. In the compound (IIa-1), the cationic moiety M in the structural moiety X 71a + , M 71b + , and M 71c+ Compound PIIa-2, which is substituted with HA 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b The compound PIIa-2 corresponds to H. The acid generated from the compound represented by formula (IIa-2) upon irradiation with actinic rays or radiation is the same as that generated from the compound PIIa-2. Also, M 71a + , M 71b + , M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 and L 73 At least one of them may have an acid-decomposable group as a substituent.

[0306] Examples of organic cations and other moieties that the specific photoacid generator may have are shown below. The organic cation is, for example, M in the compounds represented by formulas (Ia-1) to (Ia-5). 11 + , M 12 + , M 21a + , M 21b + , M 22 + , M 31a + , M 31b + , M 32 + , M 41a + , M 41b + , M 42 + At M 51a + , M 51b + , M 51c + , M 52a +or M 52b + It can be used as. The other moiety is, for example, M in the compounds represented by formulae (Ia-1) to (Ia-5). 11 + , M 12 + , M 21a + , M 21b + , M 22 + , M 31a + , M 31b + , M 32 + , M 41a + , M 41b + , M 42 + At M 51a + , M 51b + , M 51c + , M 52a + and M 52b + It can be used as other parts. The organic cations shown below and other moieties can be used in appropriate combination as specific photoacid generators.

[0307] First, examples of organic cations that the specific photoacid generator may have will be given.

[0308] [ka]

[0309] [ka]

[0310] [ka]

[0311] Next, examples of moieties other than the organic cation that the specific photoacid generator may have will be given.

[0312] [ka]

[0313] [ka]

[0314] The molecular weight of the specific photoacid generator is preferably from 100 to 10,000, more preferably from 100 to 2,500, and even more preferably from 100 to 1,500.

[0315] The content of the specific photoacid generator (the total content of compounds (I) and (II)) is preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 40% by mass or more, based on the total solid content of the resist composition. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total solid content of the resist composition. The specific photoacid generator may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0316] <Compound (III)> Compound (III) is "M + X - It is preferable that the compound is an onium salt represented by the formula: "" and that the compound generates an organic acid upon exposure to light. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids such as fluoroaliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0317] M + represents an organic cation. The organic cation is preferably an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)). "M + X - In the compound represented by ", X - represents an organic anion. The organic anion is preferably a non-nucleophilic anion (an anion with a significantly low ability to cause a nucleophilic reaction).

[0318] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0319] The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it may also be a perfluoroalkyl group).

[0320] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0321] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. Specific examples of the substituent include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 12 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 18 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), an alkylaminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0322] The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0323] Preferred non-nucleophilic anions are aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom.

[0324] The non-nucleophilic anion is also preferably an anion represented by formula (AN1).

[0325] [ka]

[0326] In formula (AN1), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0327] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and further preferably both Xf's are fluorine atoms.

[0328] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R4s and R5s are present, they may be the same or different. The number of carbon atoms in the alkyl group represented by R4 and R5 is preferably 1 to 4. The alkyl group may have a substituent. R4 and R5 are preferably hydrogen atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (AN1).

[0329] L represents a divalent linking group. When a plurality of L's are present, each L may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining these. Among these, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0330] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl, are preferred.

[0331] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, polycyclic heterocyclic groups can better suppress the diffusion of acids. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0332] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0333] The anion represented by formula (AN1) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q and W are the same as those in formula (AN1). q' represents an integer of 0 to 10.

[0334] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0335] [ka]

[0336] In formula (AN2), X B1 and X B2 each independently represents a hydrogen atom or a monovalent organic group that does not contain a fluorine atom. X B1 and X B2 is preferably a hydrogen atom. X B3 and X B4 each independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is preferably a fluorine atom or a monovalent organic group having a fluorine atom, B3 and X B4 It is more preferable that both of X and X are fluorine atoms or monovalent organic groups having a fluorine atom. B3 and X B4 It is more preferable that both of the groups are alkyl groups substituted with fluorine. L, q, and W are the same as in formula (AN1).

[0337] The non-nucleophilic anion is preferably an anion represented by formula (AN3).

[0338] [ka]

[0339] In formula (AN3), each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Each Xb independently represents a hydrogen atom or an organic group having no fluorine atoms. The definitions and preferred embodiments of o, p, q, R4, R5, L, and W are the same as those in formula (AN1).

[0340] The non-nucleophilic anion is also preferably an anion represented by formula (AN4).

[0341] [ka]

[0342] In formula (AN4), R 1 and R 2 each independently represents a substituent that is not an electron-withdrawing group or a hydrogen atom. Examples of the substituent that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonyl hydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. Furthermore, the substituents that are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', where R' is a monovalent hydrocarbon group.

[0343] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0344] In formula (AN4), L represents a divalent linking group formed by a combination of one or more linking groups S and one or more alkylene groups which may have a substituent, or a divalent linking group formed by one or more linking groups S. The linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , and * A -SO2-* B is a group selected from the group consisting of: However, when L is a "divalent linking group formed by a combination of one or more linking groups S and one or more alkylene groups which may have one or more substituents", which is one form of "a divalent linking group formed by a combination of one or more linking groups S and one or more alkylene groups which may have one or more substituents", the linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , and * A -SO2-* B In other words, when all of the alkylene groups in the "divalent linking group formed by combining one or more linking groups S and one or more alkylene groups which may have a substituent" are unsubstituted alkylene groups, the linking group S is preferably a group selected from the group consisting of: A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-*B , and * A -SO2-* B It is preferable that the group is a group selected from the group consisting of: * A is R in formula (AN4) 3 represents the bond position on the side, and * B is -SO3 in formula (AN4) - represents the bonding position on the side.

[0345] In a divalent linking group formed by a combination of one or more linking groups S and one or more alkylene groups which may have a substituent, there may be only one linking group S, or there may be two or more alkylene groups which may have a substituent. Similarly, there may be only one or two or more alkylene groups which may have a substituent. When a plurality of the linking groups S are present, the plurality of linking groups S may be the same or different. When a plurality of the alkylene groups are present, the plurality of alkylene groups may be the same or different. In addition, the linking groups S may be bonded to each other consecutively. A -CO-* B , * A -O-CO-* B , and * A -O-* B Groups selected from the group consisting of are consecutively bonded to form "*" A -O-CO-O-* B It is preferable that " is not formed. A -CO-* B and* A -O-* B Groups selected from the group consisting of are consecutively bonded to form "*" A -O-CO-* B " and "* A -CO-O-* B It is preferred that neither of the following is formed.

[0346] In a divalent linking group consisting of one or more linking groups S, there may be only one linking group S, or two or more linking groups S. When there are multiple linking groups S, the multiple linking groups S may be the same or different. in this case,* A -CO-* B , * A -O-CO-* B , and * A -O-* B Groups selected from the group consisting of are consecutively bonded to form "*" A -O-CO-O-* B It is preferable that " is not formed. A -CO-* B and* A -O-* B Groups selected from the group consisting of are consecutively bonded to form "*" A -O-CO-* B " and "* A -CO-O-* B It is preferred that neither of the following is formed.

[0347] However, in either case, -SO3 - The atom at the β-position to is not a carbon atom having a fluorine atom as a substituent. When the atom at the β-position is a carbon atom, the carbon atom may have a substituent having a fluorine atom (for example, a fluoroalkyl group such as a trifluoromethyl group), as long as the carbon atom is not directly substituted with a fluorine atom. The atom at the β-position is, in other words, the atom at the —C(R 1 )(R 2 )- is the atom in L that is directly bonded to

[0348] In particular, it is preferable that L has only one linking group S. That is, L preferably represents a divalent linking group formed by a combination of one linking group S and an alkylene group which may have one or more substituents, or a divalent linking group formed by one linking group S.

[0349] L is preferably, for example, a group represented by formula (AN4-2). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN4-2)

[0350] In formula (AN4-2), * a is R in formula (AN4) 3 represents the bonding position with * b is -C(R 1 )(R 2 )- represents the bonding position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, there are multiple instances of R 2a and R 2b may be the same or different. However, when Y is 1 or more, -C(R 1 )(R 2 )- and CR 2b R in 2 2b is other than a fluorine atom. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. However, X+Y in formula (AN4-2) is 1 or more, and R in formula (AN4-2) 2a and R 2b are all hydrogen atoms, Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. * A is R in formula (AN4) 3 represents the bond position on the side, and * B is -SO3 in formula (AN4) - represents the bonding position on the side.

[0351] In formula (AN4), R 3 represents an organic group. The organic group is not limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (e.g., an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0352] Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN4). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom), and the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring member atom constituting the lactone structure or sultone structure in any of the structures represented by the above formulae (LC1-1) to (LC1-21) and the structures represented by the above formulae (SL1-1) to (SL1-3) is preferred.

[0353] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0354] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by formula (AN5).

[0355] [ka]

[0356] In formula (AN5), Ar represents an aryl group (e.g., a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom or a hydroxyl group.

[0357] n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 or 3, and even more preferably 3.

[0358] D represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, sulfonic acid -COO-, -COO-, and groups formed by combining two or more of these.

[0359] B represents a hydrocarbon group.

[0360] B is preferably an aliphatic hydrocarbon structure, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0361] The non-nucleophilic anion is also preferably a disulfonamide anion. Disulfonamide anions are, for example, N - (SO2-R q )2 is an anion. where R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. q may be bonded to each other to form a ring. q The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0362] Compound (III) may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer, or may be in the form of a low molecular weight compound and in the form of a polymer in combination. When compound (III) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. When compound (III) is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the acid-decomposable resin, or it may be incorporated into a resin different from the acid-decomposable resin. Compound (III) is preferably in the form of a low molecular weight compound.

[0363] As compound (III), it is also preferable to use, for example, a photoacid generator disclosed in paragraphs

[0135] to

[0171] of WO 2018 / 193954, paragraphs

[0077] to

[0116] of WO 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of WO 2017 / 154345.

[0364] When the resist composition contains compound (III), the content thereof is preferably 0.5% by mass or more, and more preferably 1% by mass or more, based on the total solid content of the resist composition, and the upper limit thereof is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total solid content of the resist composition. The other photoacid generators may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0365] [Acid diffusion controller] The resist composition may contain an acid diffusion controller. The acid diffusion controller acts as a quencher that traps the acid generated from the photoacid generator or the like during exposure and inhibits the reaction of the acid-decomposable resin in the unexposed areas caused by excess acid generated. As the acid diffusion controller, a basic compound having a nitrogen atom (nitrogen-containing basic compound) is preferred because it provides a better LWR after storage over time. Examples of the nitrogen-containing basic compound include a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter also simply referred to as "compound (DB)"), a low molecular weight compound (DC) having a nitrogen atom and a group that is cleaved by the action of an acid (hereinafter also simply referred to as "compound DC"), and an onium salt compound (DD) having a nitrogen atom in the cation moiety (hereinafter also simply referred to as "compound DD").

[0366] <Basic Compounds (DA)> The basic compound (DA) is preferably a compound having a structure represented by any one of formulas (A) to (E).

[0367] [ka]

[0368] In formulas (A) and (E), R 200 , R 201 , and R 202 may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 , and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0369] The alkyl groups in formulae (A) and (E) may be substituted or unsubstituted. The alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl groups in formulae (A) and (E) are more preferably unsubstituted.

[0370] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine, and more preferably a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether group, or an aniline derivative having a hydroxyl group and / or an ether group.

[0371] <Compound (DB)> Compound (DB) is a compound that has a proton acceptor functional group and decomposes upon irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or change from a proton acceptor property to an acidic property.

[0372] The proton acceptor functional group is a group or functional group having electrons that can interact electrostatically with a proton, and for example, it means a functional group having a macrocyclic structure such as a cyclic polyether and / or a functional group having a nitrogen atom with a non-bonding electron pair that does not contribute to π-conjugation. The nitrogen atom having a non-bonding electron pair that does not contribute to π-conjugation is as described above.

[0373] As a partial structure of the proton acceptor functional group, a crown ether, an azacrown ether, a primary to tertiary amine, pyridine, imidazole, or pyrazine structure is preferable.

[0374] Compound (DB) decomposes upon irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property decreases or disappears, or changes from a proton acceptor property to an acidic property. Here, the decrease or disappearance of the proton acceptor property, or the change from a proton acceptor property to an acidic property, is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by measuring the pH.

[0375] The pKa of the compound generated by the decomposition of Compound (DB) upon irradiation with actinic rays or radiation is preferably pKa < -1, more preferably -13 < pKa < -1, and still more preferably -13 < pKa < -3. The compound generated in this way may undergo intramolecular neutralization so that the pKa becomes -1 or more.

[0376] The compound (DB) is preferably a compound represented by formula (b-1). RBXA-W1-N - -W2-R f [C + ] (b-1)

[0377] In formula (b-1), W1 and W2 each independently represent -SO2- or -CO-. R f represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. A represents a single bond or a divalent linking group. X represents a single bond, -SO2- or -CO-. B is a single bond, an oxygen atom, or -N(R x )R y - represents. R x represents a hydrogen atom or an organic group. R y represents a single bond or a divalent organic group. R represents a monovalent organic group having a proton acceptor functional group. R x is R y may be bonded to form a ring, or may be bonded to R to form a ring. [C + ] represents a counter cation.

[0378] At least one of W1 and W2 is preferably -SO2-, and both are more preferably -SO2-.

[0379] Rf is preferably an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

[0380] The divalent linking group for A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. Of these, an alkylene group having at least one fluorine atom is preferred. The alkylene group preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkylene group may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably the carbon atom bonded to the Q moiety has a fluorine atom. The divalent linking group for A is preferably a perfluoroalkylene group, and more preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group.

[0381] The monovalent organic group for Rx preferably has 2 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group which may have an oxygen atom in the ring, an aryl group, an aralkyl group, and an alkenyl group. The alkyl group for Rx may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl chain may contain an oxygen atom, a sulfur atom, and / or a nitrogen atom. Examples of the alkyl group having a substituent include a group in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, and a camphor residue). The cycloalkyl group for Rx may have a substituent, and is preferably a cycloalkyl group having a carbon number of 3 to 20. The cycloalkyl group may have an oxygen atom in the ring. The aryl group in Rx may have a substituent. The aryl group preferably has 6 to 14 carbon atoms. The aralkyl group in Rx may have a substituent. The aralkyl group preferably has 7 to 20 carbon atoms. The alkenyl group in Rx may have a substituent. Examples of the alkenyl group include groups having a double bond at any position of the alkyl groups listed as Rx.

[0382] When B represents -N(Rx)Ry-, the divalent organic group in Ry is preferably an alkylene group. In this case, the ring that can be formed by bonding Rx and Ry together is preferably a 5- to 8-membered ring containing a nitrogen atom, more preferably a 6-membered ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

[0383] When B represents -N(Rx)Ry-, it is preferable that R and Rx are bonded to each other to form a ring. Forming a ring improves stability, and improves the storage stability of a composition using this. The ring preferably has 4 to 20 carbon atoms, may be a monocyclic or polycyclic ring, and may contain an oxygen atom, a sulfur atom, and / or a nitrogen atom in the ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

[0384] Examples of monocyclic rings include 4-, 5-, 6-, 7-, and 8-membered rings containing a nitrogen atom. Examples of such ring structures include a piperazine ring and a piperidine ring. Examples of polycyclic rings include structures formed by combining two or more monocyclic structures. The monocyclic ring and polycyclic ring may each have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 15 carbon atoms), an acyloxy group (preferably having 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), or an aminoacyl group (preferably having 2 to 20 carbon atoms). These substituents may further have a substituent, if possible. Examples of when the aryl group and cycloalkyl group further have a substituent include an alkyl group (preferably having 1 to 15 carbon atoms). Examples of the substituent that the aminoacyl group may further have include an alkyl group (preferably having 1 to 15 carbon atoms).

[0385] The proton acceptor functional group in R is as described above, and the partial structure preferably has, for example, a crown ether, a primary to tertiary amine, or a nitrogen-containing heterocycle (for example, pyridine, imidazole, pyrazine, etc.) structure. The proton-accepting functional group is preferably a functional group having a nitrogen atom, more preferably a group having a primary, secondary, or tertiary amino group or a nitrogen-containing heterocyclic group. In these structures, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. It is also preferred that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom. The monovalent organic group in such a monovalent organic group (group R) containing a proton acceptor functional group preferably has 2 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, each of which may have a substituent.

[0386] Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group containing a proton acceptor functional group for R include the same groups as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group exemplified as Rx, respectively.

[0387] Examples of the substituent that each of the above groups may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having 3 to 10 carbon atoms, which may be partially substituted with a heteroatom or a group having a heteroatom (such as an ester group)), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), and an aminoacyl group (preferably having 2 to 20 carbon atoms). Examples of the substituent that cyclic groups in aryl groups and cycloalkyl groups may have include an alkyl group (preferably having 1 to 20 carbon atoms). Examples of the substituent that aminoacyl groups may have include an alkyl group (preferably having 1 to 20 carbon atoms).

[0388] [C + In the formula (ZaI), the counter cation is preferably a sulfonium cation or an iodonium cation. As the sulfonium cation and the iodonium cation, for example, the sulfonium cation and the iodonium cation in the cation that the photoacid generator may have (specifically, the cation in the compound represented by formula (ZaI) and the cation in the compound represented by formula (ZaII)) can be similarly used.

[0389] <Compound (DC)> The nitrogen-containing compound may be a low molecular weight compound (DC) (hereinafter also referred to as "compound (DC)") having a nitrogen atom and a group that is cleaved by the action of an acid. Compound (DC) is preferably an amine derivative having, on the nitrogen atom, a group that is cleaved by the action of an acid. The group that is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. The molecular weight of the compound (DC) is preferably 100-1,000, more preferably 100-700, and even more preferably 100-500. Compound (DC) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is preferably a group represented by formula (c-1).

[0390] [ka]

[0391] In formula (c-1), each Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rbs may be linked to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may each independently be substituted with a functional group such as a hydroxy group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group, an alkoxy group, or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

[0392] Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group. Examples of the ring formed by two Rb's bonding together include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. Specific examples of the structure of the group represented by formula (c-1) include the structure disclosed in paragraph

[0466] of US Patent Publication US2012 / 0135348A1.

[0393] The compound (DC) is preferably a compound having a structure represented by formula (6).

[0394] [ka]

[0395] In formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l + m = 3 is satisfied. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a ralkyl group. When l is 2, the two Ra may be the same or different, and the two Ra may be linked to each other to form a heterocycle together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula. Rb has the same meaning as Rb in the above formula (c-1), and the preferred embodiments are also the same. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra may each independently be substituted with a group similar to the groups described above as the groups with which the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb may be substituted.

[0396] Examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (which may be substituted with the above groups) for Ra include the same groups as the specific examples given above for Rb.

[0397] <Compound (DD)> Compound (DD) is an onium salt compound having a nitrogen atom in the cation moiety. However, when compound (DD) generates an acid upon irradiation with actinic rays or radiation, the pKa of the generated acid is smaller than the pKa of the acid generated from photoacid generator A plus 1.00. The compound (DD) is preferably a compound having a basic site containing a nitrogen atom in the cationic moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. Furthermore, it is preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom.

[0398] Furthermore, an onium salt that is a relatively weak acid to the photoacid generating component (including the specific photoacid generator and other photoacid generators) can also be used as the acid diffusion controller. When a photoacid generator and an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator are used together, when the acid generated by the photoacid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with lower catalytic activity, and the acid appears to be deactivated, thereby controlling acid diffusion.

[0399] As the onium salt that is a weak acid relative to the photoacid generating component, the compounds represented by formulae (d1-1) to (d1-3) are preferred.

[0400] [ka]

[0401] In formula (d1-1), R 51 represents an organic group, and the organic group preferably has 1 to 30 carbon atoms. Z 2c represents an organic group. The number of carbon atoms in the organic group is preferably 1 to 30. However, Z 2c The organic group represented by the formula is SO 3- When a carbon atom is adjacent to Z, this carbon atom (α carbon atom) does not have a fluorine atom and / or a perfluoroalkyl group as a substituent. The α carbon atom is other than a ring member atom of a cyclic structure, and is preferably a methylene group. 2c Medium, SO3 - When the atom at the β-position to the above is a carbon atom (β carbon atom), the β carbon atom does not have a fluorine atom and / or a perfluoroalkyl group as a substituent. R 52 represents an organic group (such as an alkyl group), and Y 3 represents -SO2-, a linear, branched or cyclic alkylene group, or an arylene group; Y 4represents -CO- or -SO2-, and Rf represents a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group).

[0402] M + Each of M in formulae (d1-1) to (d1-3) independently represents an ammonium cation, a sulfonium cation, or an iodonium cation. + As the organic cation, for example, M 11 + (organic cations represented by the formula: In one embodiment, these cations preferably have an acid-decomposable group. The acid-decomposable group is as described above.

[0403] The acid diffusion controller may be a zwitterion. The zwitterion acid diffusion controller preferably has a carboxylate anion, and more preferably has a sulfonium cation or an iodonium cation.

[0404] In the resist composition of the present invention, a known acid diffusion controller can be appropriately used. For example, the known compounds disclosed in U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] can be suitably used as the acid diffusion controller.

[0405] When the resist composition contains an acid diffusion controller, the content of the acid diffusion controller (if multiple types are present, the total content of all the acid diffusion controllers) is preferably 0.1 to 20.0 mass%, more preferably 0.1 to 15.0 mass%, even more preferably 0.1 to 10.0 mass%, and particularly preferably 1.0 to 10.0 mass%, relative to the total solid content of the resist composition. The acid diffusion controller may be used alone or in combination of two or more kinds.

[0406] [Hydrophobic resin] The resist composition may contain, in addition to the acid-decomposable resin, a hydrophobic resin different from the acid-decomposable resin. The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, and unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include, for example, control of the static and dynamic contact angle of the resist film surface with water, and suppression of outgassing.

[0407] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more, more preferably two or more, of the following: a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0408] When the resist composition contains a hydrophobic resin, the content thereof is preferably from 0.01 to 20 mass%, more preferably from 0.1 to 15 mass%, even more preferably from 0.1 to 10 mass%, and particularly preferably from 0.1 to 8.0 mass%, relative to the total solid content of the resist composition. The hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0409] [Surfactant] The resist composition may contain a surfactant. When a surfactant is contained, a pattern having superior adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. As the fluorine-based and / or silicone-based surfactant, for example, the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 19395 can be used. When the resist composition contains a surfactant, the content thereof is preferably from 0.0001 to 2 mass %, and more preferably from 0.0005 to 1 mass %, relative to the total solid content of the resist composition. The surfactants may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0410] 〔solvent〕 The resist composition may contain a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0411] The present inventors have found that when such a solvent is used in combination with the above resin, the coating properties of the composition are improved and a pattern with fewer development defects can be formed. Although the reason for this is not entirely clear, the inventors believe that this is because these solvents have a good balance of solubility, boiling point, and viscosity for the resin, and therefore can suppress unevenness in the film thickness of the composition film and the occurrence of precipitates during spin coating. Details of the component (M1) and the component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306.

[0412] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0413] The solvent content in the resist composition is preferably set so that the solids concentration is 30% by mass or less, more preferably 10% by mass or less, and even more preferably 2% by mass or less. The lower limit is preferably set so that the solids concentration is 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. Within the above range, the coatability of the resist composition can be further improved. The content of the solvent is preferably from 70 to 99.95 mass %, more preferably from 90 to 99.9 mass %, and even more preferably from 98 to 99.5 mass %, relative to the total mass of the resist composition. The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0414] [Other additives] The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (an alicyclic or aliphatic compound containing a carboxylic acid group).

[0415] The resist composition may further contain a dissolution inhibiting compound. Here, the term "dissolution inhibiting compound" refers to a compound with a molecular weight of 3000 or less that decomposes under the action of acid and reduces its solubility in an organic developer.

[0416] The resist composition of the present invention can also be suitably used as an EUV light-sensitive composition. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), and therefore the number of incident photons is smaller when exposed at the same sensitivity. As a result, the effect of "photon shot noise," which is the stochastic variation in the number of photons, is significant, leading to deterioration of LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose and the number of incident photons, but this comes at a trade-off with the demand for higher sensitivity.

[0417] When the value A calculated by formula (1) is high, the resist film formed from the resist composition will have a high absorption efficiency of EUV light and electron beams, which is effective in reducing photon shot noise. The value A represents the absorption efficiency of EUV light and electron beams by mass of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) The value A is preferably 0.120 or greater. If the value A is too large, the EUV light and electron beam transmittance of the resist film decreases, deteriorating the optical image profile in the resist film and making it difficult to obtain a good pattern shape, so the upper limit is preferably 0.240 or less, and more preferably 0.220 or less.

[0418] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of 0 to 10 atoms in the actinic ray-sensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from all solids to all atoms in all solids, [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition. For example, when a resist composition contains an acid-decomposable resin, compound (1), and a solvent, the acid-decomposable resin and compound (1) correspond to the solid content. In other words, the total atoms of the total solid content correspond to the sum of all atoms derived from the acid-decomposable resin and all atoms derived from compound (1). For example, [H] represents the molar ratio of hydrogen atoms derived from all solid content to all atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the acid-decomposable resin and compound (1) to the sum of all atoms derived from the acid-decomposable resin and compound (1).

[0419] The A value can be calculated by calculating the atomic ratio of the components contained in the resist composition when the structures and contents of the components of the total solid content of the resist composition are known. Even when the components are unknown, the atomic ratio of the components can be calculated by analytical techniques such as elemental analysis of the resist film obtained by evaporating the solvent component of the resist composition.

[0420] [Resist film and pattern forming method] The procedure for the pattern formation method using the above resist composition preferably includes the following steps. Step 1: Forming a resist film on a substrate using a resist composition Step 2: Exposing the resist film Step 3: Developing the exposed resist film using a developer The procedures for each of the above steps will be described in detail below.

[0421] <Step 1: Resist film formation step> Step 1 is a step of forming a resist film on a substrate using a resist composition. The resist composition is defined as above.

[0422] An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto the substrate. Before coating, the resist composition is preferably filtered as needed. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0423] The resist composition can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit elements by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spinning using a spinner is preferably 1000 to 3000 rpm. After coating the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic films, organic films, anti-reflective films) may be formed under the resist film.

[0424] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0425] The thickness of the resist film is preferably 10 to 120 nm, since this allows for the formation of finer patterns with higher accuracy. 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.

[0426] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound on the resist film, such as that described in JP 2013-61648 A. Specific examples of the basic compound that the top coat may contain include basic compounds that may be contained in the resist composition. The top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0427] <Step 2: Exposure step> Step 2 is a step of exposing the resist film. The exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask. Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. The wavelength of the actinic ray or radiation is preferably far ultraviolet light. The wavelength of far ultraviolet light is preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm. Specific examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV light (13 nm), X-rays, and electron beams.

[0428] After exposure, it is preferable to bake (heat) the film before developing, as this promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. This process is also called post-exposure bake (PEB).

[0429] <Process 3: Development process> Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an "organic developer").

[0430] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C.

[0431] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. Examples of the alkaline aqueous solution include aqueous alkaline solutions containing quaternary ammonium salts, such as tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is typically 0.1 to 20% by mass. The pH of the alkaline developer is typically 10.0 to 15.0. The water content of the alkaline developer is preferably 51 to 99.95% by mass.

[0432] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0433] The developer as a whole preferably contains less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, based on the total mass of the developer, and particularly preferably contains substantially no water. The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total mass of the developer.

[0434] <Other processes> The pattern formation method preferably includes, after step 3, a step of washing with a rinse liquid.

[0435] The rinse liquid used in the rinse step after the development step using an alkaline developer is, for example, pure water, to which an appropriate amount of surfactant may be added. A suitable amount of a surfactant may be added to the rinse solution.

[0436] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0437] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method in which the rinsing liquid is sprayed onto the surface of the substrate (spray method). The pattern formation method of the present invention may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 seconds to 2 minutes).

[0438] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlying film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. Although the method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, a preferred method is to form a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask. The dry etching is preferably oxygen plasma etching.

[0439] The resist composition and various materials used in the pattern formation method of the present invention (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 parts per trillion by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less, based on the total solid content of the resist composition or various materials. 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.

[0440] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0441] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal contents as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0442] In addition to filtration, impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0443] A conductive compound may be added to an organic processing liquid such as a rinse liquid to prevent breakdown of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge. An example of a conductive compound is methanol. The amount of the compound added is preferably 10% by mass or less, more preferably 5% by mass or less, in order to maintain favorable development or rinsing properties. For example, SUS (stainless steel) or various pipes coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) can be used as the chemical liquid piping. Similarly, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) can be used for the filter and O-ring.

[0444] [Electronic device manufacturing method] The present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitably mounted in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0445] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0446] [Components of the resist composition] The components contained in the resist compositions used in the examples and comparative examples are shown below.

[0447] 〔resin〕 The resins (A-1 to A-22 (corresponding to resin A), a-1 to a-9) used in preparing the resist compositions are shown below. In Table 1, the "molar ratio" column indicates the content (mol %) of each repeating unit relative to all repeating units. The "Mw" column indicates the weight average molecular weight. The "Mw / Mn" column indicates the dispersity.

[0448] [Table 1]

[0449] The structures of the monomers corresponding to the respective repeating units in the resin are shown below. M-37 to M-51 correspond to the compound (1).

[0450] [ka]

[0451] [ka]

[0452] [ka]

[0453] [ka]

[0454] [ka]

[0455] <Synthesis of Resin A-1> Cyclohexanone (62 g) was heated to 85 °C under a nitrogen stream. While stirring this solution, a mixture (100.7 g) of a cyclohexanone solution (10% by mass) of 2,2'-azobisisobutyrate dimethyl ester (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) in cyclohexanone (10 wt%), 25 g of a monomer represented by formula (M-1), 8.6 g of a monomer represented by formula (M-29), 46 g of a monomer represented by formula (M-37), 21 g of a monomer represented by formula (M-14), 248 g of cyclohexanone, and 2,2'-azobisisobutyrate dimethyl ester (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours to obtain a reaction solution. After the addition was completed, the reaction solution was stirred at 85 °C for an additional 3 hours. The resulting reaction solution was allowed to cool and then reprecipitated using a large amount of a 1 / 9 (mass ratio) ethyl acetate / heptane mixed solvent. The mixture was then filtered, and the resulting solid was vacuum dried to obtain Resin A-1 (83 g). The synthesis of the above resin A-1 was all carried out under yellow light. Resins other than Resin A-1 were synthesized according to the synthesis method for Resin A-1.

[0456] [ka]

[0457] [Photoacid generator] The structures of the photoacid generators (B-1 to B-11 (corresponding to compound (1)), b-1 to b-10) used in preparing the resist compositions are shown below.

[0458] [ka]

[0459] [ka]

[0460] [Acid diffusion controller] The structures of the acid diffusion controllers used in preparing the resist compositions are shown below.

[0461] [ka]

[0462] [Hydrophobic resin] The structures of the hydrophobic resins used in preparing the resist compositions are shown below.

[0463] [ka]

[0464] The composition ratio (mass ratio, corresponding from left to right) of each repeating unit of the hydrophobic resin, the weight average molecular weight (Mw) and the dispersity (Mw / Mn) are shown below. The hydrophobic resin was synthesized according to the synthesis method for Resin A-1 (Synthesis Example 1) described above.

[0465] [Table 2]

[0466] [Surfactant] The surfactants used in preparing the resist composition are shown below. W-1: Megafac R08 (DIC, fluorine and silicone surfactant) W-2: Megafac F176 (DIC, fluorine-based surfactant) W-3: Troisol S-366 (manufactured by Trois Chemical Co., Ltd., fluorine-based surfactant) W-4: PF656 (OMNOVA, fluorine-based surfactant)

[0467] 〔solvent〕 The solvents used in preparing the resist compositions are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Propylene glycol monoethyl ether (PGEE) S-4: Cyclohexanone S-5: Cyclopentanone S-6: 2-heptanone S-7: Ethyl lactate S-8: γ-butyrolactone S-9: Propylene carbonate

[0468] [Preparation of Resist Composition] The components shown in the table below were mixed to a solids concentration of 1.4% by mass, and the resulting mixture was then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare each resist composition. "Solids" means all components other than the solvent. In the table, the "amount" column indicates the content (mass %) of each solid component relative to the total solid content. The "Mixing ratio" column of "Solvent" indicates the mixing ratio (mass ratio) of each solvent.

[0469] [Table 3]

[0470] [test] [Pattern formation (1): EB exposure, alkaline development] A 6-inch silicon wafer (or chrome wafer) was treated with hexamethyldisilazane (HMDS). Each resist composition shown in the table below was applied to the resulting surface-treated silicon wafer using a spin coater Mark 8 (Tokyo Electron Ltd.), and the wafer was dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. In addition, a chrome substrate may be used instead of the silicon wafer in the above-described resist film preparation method. For the obtained resist film, pattern exposure was performed using an electron beam lithography apparatus (manufactured by Advantest, F7000S, acceleration voltage 50 keV) with an exposure mask (line: space = 1:1). Next, it was heated on a hot plate at a temperature of 100 °C for 60 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Finally, after rotating the silicon wafer at a rotation speed of 4000 rpm for 30 seconds, baking was performed at a temperature of 95 °C for 60 seconds to dry it, and a silicon wafer having a predetermined pattern was obtained.

[0471] <Sensitivity> The line width of the line and space pattern formed while changing the exposure dose (electron beam irradiation dose) was measured, and the exposure dose when the line width became 50 nm was determined, and this was defined as the sensitivity (Eop, μC / cm 2 ). The smaller the value of the sensitivity, the better the sensitivity.

[0472] <Resolution> At the exposure dose showing the above sensitivity (Eop), the minimum dimension of the pattern (line: space = 1:1) that resolves without collapsing was determined using a length measurement scanning electron microscope (SEM, S-9380II, manufactured by Hitachi, Ltd.) and defined as the resolution (L / S) (nm). The smaller the value of the resolution, the better the resolution.

[0473] <LWR (Roughness Performance)> For the pattern resolved at a line width of 50 nm and a line: space = 1:1 at the exposure dose showing the above sensitivity (Eop), the line width was measured at an arbitrary point from the top of the pattern using a length measurement scanning electron microscope (SEM, S-9380II, manufactured by Hitachi, Ltd.). The variation in each obtained line width was evaluated by 3σ (nm). The smaller the value of 3σ, the better the LWR.

[0474] <LWR after Storage over Time> After storing each of the resist compositions obtained above at 23°C for one year, except for use in the LWR test, LWR was evaluated in the same procedure as the above <LWR (roughness performance)> to obtain 3σ (nm), which was taken as the LWR (nm) after storage over time.

[0475] <Results>

[0476] In the table, each description indicates the following. 「R 4 is an aromatic ring group」 in the 「Resin」 column is 「A」 when it is a residue formed by removing one hydrogen atom from the compound (1) in which R 4 is an aromatic ring group, and 「B」 otherwise. 「R 4 is an aromatic ring group」 in the 「Photoacid generator」 column is 「A」 when R in the compound (photoacid generator) represented by the formula (1) 4 represents an aromatic ring group, and 「B」 otherwise. In the 「Nitrogen-containing basic compound」 column, 「A」 is used when the resist composition contains a nitrogen-containing basic compound, and 「B」 otherwise. In the 「Content of repeating unit b is 15 mol% or more」 column, 「A」 is used when the content of repeating unit b is 15 mol% or more based on all repeating units, and 「B」 otherwise. In the 「Formulas (M4) and (M5)」 column, 「A」 is used when repeating unit b contains at least one selected from the group consisting of repeating units represented by formulas (M4) and (M5), and 「B」 otherwise.

[0477]

Table 4

[0478] From the results shown in the table, it was confirmed that when EB exposure and alkali development were carried out using the resist composition of the present invention, the desired effects of the present invention were obtained. The resin has a residue formed by removing one hydrogen atom from the compound (1) in which R 4 is an aromatic ring group, or R in the compound (1) 4It was confirmed that when R represents an aromatic ring group, the sensitivity was superior (comparison between Example 1a etc. and Examples 7a to 8a). 4 has a residue formed by removing one hydrogen atom from compound (1), which is an aromatic ring group, and R 4 It was confirmed that when represents an aromatic ring group, the sensitivity was further improved (comparison of Example 1a etc. with Examples 2a, 3a, 5a, 6a, 10a, and 22a to 28a). It was confirmed that when the resist composition further contained a nitrogen-containing basic compound, the LWR after storage was even better (comparison of Example 1a etc. with Examples 9a to 10a, 22a to 23a, and 28a). It was confirmed that when the content of repeating unit b is 15 mol % or more based on all repeating units, the resolution and LWR were better (comparison of Example 1a etc. with Examples 5a, 15a, 19a, 20a and 33a). It was confirmed that when the repeating unit b contains at least one selected from the group consisting of repeating units represented by formula (M4) and repeating units represented by formula (M5), the LWR is more excellent (comparison of Examples 7a, 13a to 18a, 22a, 24a, 26a, 28a, 31a to 36a with Example 1a, etc.).

[0479] [Pattern formation (2): EUV exposure, alkaline development] A 6-inch silicon wafer (or chrome wafer) was treated with hexamethyldisilazane (HMDS). Each resist composition shown in the table below was applied to the resulting surface-treated silicon wafer using a spin coater Mark 8 (Tokyo Electron Ltd.), and the wafer was dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. In addition, a chrome substrate may be used instead of the silicon wafer in the above-described resist film preparation method. The obtained resist film was subjected to pattern exposure using an EUV exposure device (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). Next, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Finally, the silicon wafer was rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried to obtain a silicon wafer with the desired pattern. Using the obtained patterns, the sensitivity, resolution (L / S), LWR (roughness performance), and LWR after storage were evaluated in the same manner as in the above [Pattern formation (1): EB exposure, alkali development].

[0480] <Result> In the table, each description is the same as in Table 4.

[0481] [Table 5]

[0482] The results shown in the table confirm that the desired effects of the present invention can be obtained when the resist composition of the present invention is used and subjected to EUV exposure and alkaline development. Resin is R 4 has a residue formed by removing one hydrogen atom from compound (1) in which R 4 It was confirmed that when R represents an aromatic ring group, the sensitivity was superior (comparison of Example 1b etc. with Examples 7b and 8b). 4 has a residue formed by removing one hydrogen atom from compound (1), which is an aromatic ring group, and R 4 It was confirmed that when represents an aromatic ring group, the sensitivity was further improved (comparison of Example 1b etc. with Examples 2b, 3b, 5b, 6b, 10b, and 22b to 28b). It was confirmed that when the resist composition further contained a nitrogen-containing basic compound, the LWR after storage was even better (comparison of Example 1b etc. with Examples 9b to 10b, 22b to 23b, and 28b). It was confirmed that when the content of repeating unit b is 15 mol % or more based on all repeating units, the resolution and LWR are better (comparison of Example 1b etc. with Examples 5b, 15b, 19b, 20b and 33b). It was confirmed that when the repeating unit b contains at least one selected from the group consisting of repeating units represented by formula (M4) and repeating units represented by formula (M5), the LWR is more excellent (comparison of Examples 7b, 13b to 18b, 22b, 24b, 26b, 28b, 31b to 36b with Example 1b, etc.).

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes under the action of an acid to increase its polarity, Further, the compound may contain a compound represented by formula (1), and the resin that is decomposed by the action of an acid to increase its polarity has a residue formed by removing one hydrogen atom from the compound represented by formula (1), The actinic ray-sensitive or radiation-sensitive resin composition, wherein the residue is a group formed by removing one hydrogen atom from R 1 or R 4 in the compound represented by formula (1). 【Chemical 1】 In formula (1), R １ and R ４ R each independently represents a substituent. ２ and R ３ each independently represents a hydrogen atom or a substituent. １ represents a single bond. n represents an integer of 1 or more.

2. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the residue comprises at least one selected from the group consisting of a group represented by formula (2a) and a group represented by formula (2b): 【Chemistry 2】 In formula (2a), R ５ and R ６ R each independently represents a hydrogen atom or a substituent. ７ represents a substituent. ２ represents a divalent linking group. ３ represents a single bond. n represents an integer of 1 or more. * represents a bonding position. 【Chemistry 3】 In formula (2b), R ８ and R ９ R each independently represents a hydrogen atom or a substituent. １０ represents a substituent. ４ represents a single bond. ５ represents a divalent linking group. n represents an integer of 1 or more. * represents a bonding position.

3. The R ４ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein represents an aromatic ring group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, further comprising a nitrogen-containing basic compound.

5. the resin that is decomposed by the action of an acid to increase its polarity contains a repeating unit b having a group that is decomposed by the action of an acid to increase its polarity, 5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the repeating unit b is 15 mol % or more based on all repeating units.

6. the resin that is decomposed by the action of an acid to increase its polarity contains a repeating unit b having a group that is decomposed by the action of an acid to increase its polarity, The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the repeating unit b comprises at least one selected from the group consisting of repeating units represented by formulas (M1) to (M5): 【Chemistry 4】 In formula (M1), R ５ ~R ７ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０ represents a single bond or a divalent linking group. ８ ~R １０ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ８ ~R １０ At least two of these may be bonded to each other to form a ring. In formula (M2), R １１ ~R １４ each independently represents a hydrogen atom or an organic group. １１ and R １２ At least one of X represents an organic group. １ is —CO—, —SO— or —SO ２ - represents Y １ is -O-, -S-, -SO-, -SO ２ -or-NR ３４ - represents. ３４ represents a hydrogen atom or an organic group. １１ represents a single bond or a divalent linking group. １５ ~R １７ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. １５ ~R １７ At least two of these may be bonded to each other to form a ring. In formula (M3), R １８ and R １９ R each independently represents a hydrogen atom or an organic group. ２０ and R ２１ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. １８ ~R ２１ At least two of these may be bonded to each other to form a ring. In formula (M4), R ２２ ~R ２４ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １２ represents a single bond or a divalent linking group. １ represents an aromatic ring group. ２５ ~R ２７ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ２５ ~R ２７ At least two of these may be bonded to each other to form a ring. In formula (M5), R ２８ ~R ３０ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １３ represents a single bond or a divalent linking group. ３１ and R ３２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３３ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３１ ~R ３３ At least two of these may be bonded to each other to form a ring.

7. 7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the repeating unit b comprises at least one selected from the group consisting of a repeating unit represented by formula (M4) and a repeating unit represented by formula (M5):

8. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7.

9. A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7; exposing the resist film to light; and developing the exposed resist film using a developer.

10. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 9.

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