Active light-sensitive or radiation-sensitive resin composition, active light-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method

Abstract

To provide an active light-sensitive or radiation-sensitive resin composition which is excellent in resolution and CDU and is small in bake temperature dependence in pattern formation, an active light-sensitive or radiation-sensitive film, a pattern formation method using the active light-sensitive or radiation-sensitive resin composition, and an electronic device manufacturing method.SOLUTION: There are provided an active light-sensitive or radiation-sensitive resin composition that contains a resin (A) having a specific structure, an acid diffusion control agent (Q), and a non-ionic compound (C) for generating acid by being decomposed by active rays or radiation, wherein a molecular weight of an acid generated from the compound (C) is 300 or more, pKa of the acid generated from the compound (C) is -1.9 or more, the compound (C) has a specific structure, a mass ratio of the content of the acid diffusion control agent (Q) to the content of the compound (C) is 6 mass% or more; an active light-sensitive or radiation-sensitive film using the active light-sensitive or radiation-sensitive resin composition; a pattern formation method; and an electronic device manufacturing method.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in ultra-microlithography processes applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes. [Background technology]

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

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

[0004] Patent Document 1 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a compound having a specific structure. Patent Document 2 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a specific resin and a specific basic compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 220189 [Patent Document 2] International Publication No. 2022 / 172597 Summary of the Invention [Problem to be solved by the invention]

[0006] Recently, the performance demands on resist compositions have become increasingly stringent. In particular, there is a demand for further improvements in resolution when forming fine patterns and in critical dimension uniformity (CDU), which indicates the uniformity of pattern dimensions within the wafer surface. Further improvements in the process margin of resist compositions are also expected. The process margin refers to the tolerance range (margin) within which a desired result can be obtained even if various conditions (e.g., heating temperature) in the pattern formation process using the resist composition vary; the wider this tolerance range, the better the process margin. In pattern formation using a resist composition, a resist film formed from the resist composition may be baked (heated) after exposure and before development. The process margin with respect to the temperature during this baking is also referred to as "bake temperature dependency." The smaller the bake temperature dependency, the smaller the change in performance with respect to changes in bake temperature, and the better.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film that are excellent in resolution and CDU and have little bake temperature dependency during pattern formation, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. [Means for solving the problem]

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

[0009] [1] a resin (A) containing a repeating unit represented by the following formula (Pa1) and a repeating unit having a group that decomposes when acted upon by an acid to increase polarity; an acid diffusion controller (Q); a nonionic compound (C) that decomposes when exposed to actinic rays or radiation to generate an acid; An actinic ray-sensitive or radiation-sensitive resin composition comprising: the molecular weight of the acid generated from the compound (C) is 300 or more; The pKa of the acid generated from the compound (C) is −1.9 or more, The compound (C) is a compound represented by any one of the following formulas (1) to (4): the mass ratio of the content of the acid diffusion controller (Q) to the content of the compound (C) in the actinic ray-sensitive or radiation-sensitive resin composition is 6 mass% or more; The resin (A) does not contain a group obtained by removing one or more hydrogen atoms from a compound represented by any one of the following formulas (1) to (4): Actinic ray-sensitive or radiation-sensitive resin composition.

[0010] [ka]

[0011] In formula (Pa1), R A1 ~R A3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L A represents a single bond or a divalent linking group. Ar A represents an aromatic ring group. R A2and Ar A may be bonded to form a ring. nA represents an integer of 1 to 5.

[0012] [ka]

[0013] In formulas (1) to (4), R C each independently represents a substituent. In formula (1), R 11 and R 12 R each independently represents a hydrogen atom or a substituent. 11 and R 12 may be bonded to form a ring. In formula (2), R 21 , R 22 and R 23 R each independently represents a hydrogen atom or a substituent. 21 , R 22 and R 23 At least two of the n may be bonded to form a ring. 21 represents an integer of 1 or greater. In formula (3), R 31 and R 32 R each independently represents a hydrogen atom or a substituent. 31 and R 32 may be bonded to form a ring. 31 represents an aryl group or a heteroaryl group. 31 represents 0 or 1. In formula (4), R 41 and R 42 R each independently represents a hydrogen atom or a substituent. 41 and R 42 may be bonded to form a ring. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the acid generated from the compound (C) has a molecular weight of 500 or more. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the compound (C) is represented by the following formula (2-1):

[0014] [ka]

[0015] In formula (2-1), R 24 represents a hydrogen atom or a substituent. R 25 and R 26 each independently represents a substituent. n 21 represents an integer of 1 or greater. R 1a represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. R 1a If there are multiple R 1a may be the same or different and may be bonded to each other to form a ring. n 22 represents an integer from 0 to 5. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (A) contains a repeating unit represented by the following formula (b-1):

[0016] [ka]

[0017] In formula (b-1), R b1 and R b2 each independently represents a hydrogen atom or an alkyl group. L b1 represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. R p1 and R p2 each independently represents a group that is eliminated by the action of an acid. R b3represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer between 0 and (5+2r-st). R p1 If there are multiple R p1 may be the same or different and may be bonded to each other to form a ring. R p2 If there are multiple R p2 may be the same or different and may be bonded to each other to form a ring. R b3 If there are multiple R b3 may be the same or different and may be bonded to each other to form a ring. R b3 and R p1 , R b3 and R p2 , and R p1 and R p2 may be bonded to each other to form a ring. L b1 The aromatic ring to which R is bonded b1 may be combined with [5] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4]. [6] A pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4]; exposing the resist film; and developing the exposed resist film using a developer. [7] A method for manufacturing an electronic device, comprising the pattern formation method according to [6]. [Effects of the Invention]

[0018] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film that are excellent in resolution and CDU and have little bake temperature dependency during pattern formation, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0020] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV, and the like, but also drawing using particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

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

[0022] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0023] In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, which can be selected from the following substituents T.

[0024] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; cycloalkyloxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; cycloalkyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Examples of the substituent T include acyl groups such as thiazolyl and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamido groups; silyl groups; amino groups; carbamoyl groups; alkylsulfonyl groups; arylsulfonyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0025] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. The compound may be "X-CO-OZ" or "XO-CO-Z".

[0026] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0027] The pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + One method is to calculate the dissociation free energy. + The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian 16.

[0028] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and known literature values, as described above. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0029] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0030] <Actinic ray-sensitive or radiation-sensitive resin composition> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") is a resin (A) containing a repeating unit represented by the following formula (Pa1) and a repeating unit having a group that decomposes when acted upon by an acid to increase polarity; an acid diffusion controller (Q); a nonionic compound (C) that decomposes when exposed to actinic rays or radiation to generate an acid; An actinic ray-sensitive or radiation-sensitive resin composition comprising: the molecular weight of the acid generated from the compound (C) is 300 or more; The pKa of the acid generated from the compound (C) is −1.9 or more, The compound (C) is a compound represented by any one of the following formulas (1) to (4): the mass ratio of the content of the acid diffusion controller (Q) to the content of the compound (C) in the actinic ray-sensitive or radiation-sensitive resin composition is 6 mass% or more; The resin (A) does not contain a group obtained by removing one or more hydrogen atoms from a compound represented by any one of the following formulas (1) to (4): The resin composition is an actinic ray-sensitive or radiation-sensitive resin composition.

[0031] [ka]

[0032] In formula (Pa1), R A1 ~R A3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L Arepresents a single bond or a divalent linking group. Ar A represents an aromatic ring group. R A2 and Ar A may be bonded to form a ring. nA represents an integer of 1 to 5.

[0033] [ka]

[0034] In formulas (1) to (4), R C each independently represents a substituent. In formula (1), R 11 and R 12 R each independently represents a hydrogen atom or a substituent. 11 and R 12 may be bonded to form a ring. In formula (2), R 21 , R 22 and R 23 R each independently represents a hydrogen atom or a substituent. 21 , R 22 and R 23 At least two of the n may be bonded to form a ring. 21 represents an integer of 1 or greater. In formula (3), R 31 and R 32 R each independently represents a hydrogen atom or a substituent. 31 and R 32 may be bonded to form a ring. 31 represents an aryl group or a heteroaryl group. 31 represents 0 or 1. In formula (4), R 41 and R 42 R each independently represents a hydrogen atom or a substituent. 41 and R 42 may be bonded to form a ring.

[0035] The mechanism by which the composition of the present invention provides the above-mentioned effects has not been clarified, but the present inventors have hypothesized it as follows, although the present invention is not limited in any way by the hypothesized mechanism below. It is known that ionic compounds containing cations and anions are used as photoacid generators in resist compositions. However, ionic compounds can aggregate due to ionic interactions. This aggregation is believed to reduce the uniformity of the material distribution in the resist film and result in a decrease in CDU. Therefore, in the present invention, a nonionic compound is used as the photoacid generator to prevent aggregation of the photoacid generator, thereby improving CDU. Furthermore, by controlling the molecular weight of the acid generated from the photoacid generator to a certain level, it is believed that acid diffusion can be suppressed, thereby improving resolution and CDU. Furthermore, in the present invention, it is believed that the resolution and CDU can be further improved by controlling the mass ratio of the acid diffusion controller content to the photoacid generator content to a certain level. Furthermore, it is believed that by setting the pKa of the acid generated from the photoacid generator to a certain level or higher, the reactivity is not excessively increased and the bake temperature dependency is reduced.

[0036] The composition of the present invention is preferably a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention can be used to form an actinic ray- or radiation-sensitive film. The actinic ray- or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0037] [Nonionic compound (C) that decomposes when exposed to actinic rays or radiation to generate an acid] The composition of the present invention contains a nonionic compound (C) (also simply referred to as "compound (C)") that decomposes when exposed to actinic rays or radiation to generate an acid. The compound (C) is a photoacid generator. Compound (C) is a non-ionic compound, i.e., compound (C) does not contain cations or anions. The compound (C) is a compound represented by any one of the above formulas (1) to (4).

[0038] In formulas (1) to (4), R C represents a substituent. R C The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. R C is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, a formyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents.

[0039] R C The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkyl group may have a substituent. The alkyl group may also contain an ether bond (-O-) in the chain. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0040] R CThe explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy group, alkylthio group and alkoxycarbonyl group represented by are the same as those described above for R C is the same as that in the alkyl group represented by

[0041] R C The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, and is, for example, preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The cycloalkyl group may have a substituent. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a group having a hetero atom such as a carbonyl group. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0042] R C The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxy group, cycloalkylthio group and cycloalkyloxycarbonyl group represented by R C is the same as that in the cycloalkyl group represented by

[0043] R C The number of carbon atoms in the aryl group represented by is not particularly limited, and is, for example, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15. The aryl group may have a substituent. The aryl group may be a monocyclic group or a polycyclic group. The aryl group is an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene), a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane, which may have one or more carbonyl groups as a group constituting the ring), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene, which may have one or more carbonyl groups as a group constituting the ring), a non-aromatic heterocyclic compound (for example, pyrrolidine, pyrroline, Five-membered non-aromatic heterocyclic compounds such as oxazolidone, tetrahydrofuran, 1,3-dioxolane, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring may have at least one group selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group as a group constituting the ring. The ring may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure fused with at least one group selected from the group consisting of Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a phenanthryl group.

[0044] R C The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group, arylthio group and aryloxycarbonyl group represented by C The same applies to the aryl group represented by the formula (I).

[0045] R C The heterocyclic group represented by may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.

[0046] R C The non-aromatic heterocyclic group represented by may be saturated or unsaturated. R CThe non-aromatic heterocyclic group represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring atoms in the non-aromatic heterocyclic group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms in the non-aromatic heterocyclic group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 25, even more preferably 3 to 20, and especially preferably 2 to 6. The non-aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of non-aromatic heterocyclic groups include groups obtained by removing one hydrogen atom from a five-membered non-aromatic heterocyclic compound such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, or tetrahydrothiophene, and groups obtained by removing one hydrogen atom from a six-membered non-aromatic heterocyclic compound such as morpholine, piperidine, piperazine, or tetrahydropyran. The non-aromatic heterocyclic group may also be a group obtained by removing one hydrogen atom from a fused ring compound having a structure in which the above-mentioned five-membered non-aromatic heterocyclic compound or the above-mentioned six-membered non-aromatic heterocyclic compound is fused with at least one selected from the group consisting of a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms such as cyclopentane or cyclohexane), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), the above-mentioned five-membered non-aromatic heterocyclic compound, and the above-mentioned six-membered non-aromatic heterocyclic compound. One or more methylene groups constituting the ring of the non-aromatic heterocyclic group may be replaced by a carbonyl group. When the bond between adjacent atoms contained in the non-aromatic heterocyclic group is a single bond, the single bond may be replaced with a multiple bond (for example, a double bond).

[0047] R CThe heteroaryl group (aromatic heterocyclic group) represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have a substituent. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The heteroaryl group may be any of the five-membered aromatic heterocyclic compounds and six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), non-aromatic heterocyclic compounds (e.g., pyrrolidine, pyrroline, 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.), or a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of: five-membered ring non-aromatic heterocyclic compounds such as benzophenone, tetrahydrofuran, and tetrahydrothiophene; and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran.

[0048] R C The acyl group represented by R C1 -C(=O)-, R C1 R preferably represents an organic group. C1 The organic group represented by R is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. C1 The description, specific examples and preferred ranges of the organic group represented by are the same as those of the R C It is the same as in

[0049] R C The heterocyclic oxy group represented by R C2 R is a group represented by -O-. C2 represents a heterocyclic group. C2 The description, specific examples and preferred range of the heterocyclic group represented by R C It is the same as in

[0050] RC represents preferably a cycloalkyl group, an aryl group, or a heterocyclic group, more preferably an aryl group, and even more preferably an aryl group having a substituent. Examples of the substituent in the substituted aryl group include the aforementioned substituent T, and are preferably a halogen atom or an organic group, more preferably a halogen atom or an organic group having 1 to 30 carbon atoms, and even more preferably a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, a heterocyclic group, a heterocyclicoxy group, a cyano group, an ester group, or a group formed by combining two or more of these. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The ester group is preferably -COOR E1 or -OCOR E1 It is preferable that R E1 represents an organic group, and preferably represents an alkyl group, a cycloalkyl group, or an aryl group. E1 The description, specific examples and preferred ranges of the organic group represented by R C The explanations, specific examples, and preferred ranges of each group described as a substituent in a substituted aryl group are the same as those in the above-mentioned R C It is the same as in

[0051] R in formula (1) 11 and R 12 each independently represents a hydrogen atom or a substituent. R 11 and R 12 The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. R 11 and R 12The substituent represented by is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, a formyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are respectively described in the above-mentioned R C It is the same as in R 11 R preferably represents an acyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and more preferably represents an acyl group. 11 But R C1 -C(=O)-, R C1 It is more preferred that is an aryl group. R 12 preferably represents a cycloalkyl group, an aryl group or a heterocyclic group, and more preferably represents an aryl group.

[0052] R in formula (1) 11 and R 12 may be bonded to form a ring. R 11 represents an acyl group, and R 12 represents an aryl group, and R 11 and R 12 In a preferred embodiment of the compound (C),

[0053] R in equation (2) 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent. R 21 , R 22 and R 23 The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. R 21 , R 22and R 23 The substituent represented by is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are respectively described in the above-mentioned R C It is the same as in

[0054] R 21 is preferably a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these, and more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are described above in the R C It is the same as in

[0055] R 22 represents a substituent, and is preferably an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are respectively described above in R C It is the same as in

[0056] R 23represents a substituent, preferably an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, more preferably an aryl group or a heterocyclic group, and even more preferably an aryl group having a substituent. Examples of the substituent include the aforementioned substituent T.

[0057] R 21 , R 22 and R 23 At least two of these may be bonded to form a ring.

[0058] n in equation (2) 21 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0059] R in equation (3) 31 and R 32 each independently represents a hydrogen atom or a substituent. R 31 and R 32 The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. R 31 and R 32 The substituent represented by is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are respectively described in the above-mentioned R C It is the same as in

[0060] R 31 and R 32is preferably a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these, and more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are described above in the R C It is the same as in

[0061] R 31 and R 32 may be bonded to form a ring.

[0062] Ar in formula (3) 31 represents an aryl group or a heteroaryl group, and preferably represents an aryl group. Ar 31 The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by R C It is the same as in Ar 31 The aryl group and heteroaryl group represented by may have a substituent, and examples of the substituent include the aforementioned substituent T.

[0063] n in equation (3) 31 represents 0 or 1.

[0064] R in equation (4) 41 and R 42 each independently represents a hydrogen atom or a substituent. R 31 and R 32 The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. R 31 and R 32The substituent represented by is preferably a cyano group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, a heterocyclicoxy group, or a group formed by combining two or more of these. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are respectively described in the above-mentioned R C It is the same as in

[0065] R 41 and R 42 may be bonded to form a ring.

[0066] The compound (C) is preferably represented by formula (2), and particularly preferably represented by the following formula (2-1).

[0067] [ka]

[0068] In formula (2-1), R 24 represents a hydrogen atom or a substituent. R 25 and R 26 each independently represents a substituent. n 21 represents an integer of 1 or greater. R 1a represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. R 1a If there are multiple R 1a may be the same or different and may be bonded to each other to form a ring. n 22 represents an integer from 0 to 5.

[0069] R in formula (2-1) 24 represents a hydrogen atom or a substituent. R 24 The explanation, specific examples and preferred ranges of R in the above formula (2) are 21 It is the same as in

[0070] R in formula (2-1) 25 represents a substituent. R 25 The explanation, specific examples and preferred range of the substituent represented by R 22 It is the same as in

[0071] R in formula (2-1) 26 represents a substituent. R 26 The explanation, specific examples and preferred range of the substituent represented by R 23 It is the same as in

[0072] n in formula (2-1) 21 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0073] R in formula (2-1) 1a represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The ester group is preferably -COOR E1 or -OCOR E1 It is preferable that R E1 represents an organic group, and preferably represents an alkyl group, a cycloalkyl group, or an aryl group. E1 The description, specific examples and preferred ranges of the organic group represented by R C It is the same as in R 1arepresents preferably an aryloxy group, an arylthio group, an aryl group, or a heteroaryl group, more preferably an aryl group, and even more preferably an aryl group having a substituent. Examples of the substituent in the aryl group having a substituent include the aforementioned substituent T, and are preferably a halogen atom or an organic group, more preferably a halogen atom or an organic group having 1 to 30 carbon atoms, and even more preferably a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, a heterocyclic group, a heterocyclicoxy group, a cyano group, an ester group, or a group formed by combining two or more of these. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The ester group is preferably -COOR E1 or -OCOR E1 It is preferable that R E1 represents an organic group, and preferably represents an alkyl group, a cycloalkyl group, or an aryl group. E1 The description, specific examples and preferred ranges of the organic group represented by R C The explanations, specific examples, and preferred ranges of each group described as a substituent in a substituted aryl group are the same as those in the above-mentioned R C It is the same as in

[0074] n in formula (2-1) 22 represents an integer of 0 to 5, and preferably an integer of 1 to 3.

[0075] The compound (C) is decomposed by actinic rays or radiation to generate an acid. The acid generated from the compound (C) (also referred to as "acid (CA)") is represented by the following formula (5).

[0076] [ka]

[0077] In formula (5), R Crepresents a substituent. R in equation (5) C is R in formulas (1) to (4). C is the same as:

[0078] The molecular weight of the acid (CA) is 300 or more, preferably 400 or more, and more preferably 500 or more. The molecular weight of the acid (CA) is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less.

[0079] The pKa of the acid (CA) is −1.9 or higher, and more preferably −1.5 or higher. The pKa of the acid (CA) is preferably 2.0 or less, and more preferably 1.0 or less. The pKa can be determined by the method described above.

[0080] The molecular weight of the compound (C) is preferably 350 to 3,500, more preferably 400 to 3,000, and even more preferably 500 to 2,000.

[0081] Compound (C) can be synthesized by referring to known methods, such as the method described in "Yu, J., Cui, J., Hou, X.-S., Liu, S.-S., Gao, W.-C., Jiang, S., Tian, ​​J., Zhang, C. (2011). Enantioselective α-tosyloxylation of ketones catalyzed by spirobiindane scaffold-based chiral iodoarenes. Tetrahedron: Asymmetry, 22(23), 2039-2055. doi:10.1016 / j.tetasy.2011.12.003".

[0082] Specific examples of the compound (C) are shown below, but the present invention is not limited to these: Me represents a methyl group.

[0083] [ka]

[0084] [ka]

[0085] The content of compound (C) in the composition of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition of the present invention. The content of compound (C) in the composition of the present invention is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total solid content of the composition of the present invention. The compound (C) may be used alone or in combination of two or more. When two or more compounds are used, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0086] The composition of the present invention may further contain, in addition to compound (C), a photoacid generator other than compound (C). When the composition of the present invention contains a photoacid generator other than compound (C), the content of compound (C) is preferably 55 mass% or more, more preferably 70 mass% or more, and even more preferably 85 mass% or more, based on the total amount of photoacid generators in the composition of the present invention.

[0087] Resin (A) The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") that includes a repeating unit represented by formula (Pa1) and a repeating unit having a group that decomposes under the action of an acid to increase polarity.

[0088] The resin (A) does not contain a group obtained by removing one or more hydrogen atoms from a compound represented by any one of the above formulas (1) to (4). The resin (A) is a component separate from the compound (C).

[0089] (Repeating unit having a group that decomposes under the action of an acid to increase polarity) The resin (A) contains a repeating unit having a group that decomposes under the action of an acid to increase polarity (also referred to as an "acid-decomposable group"). The acid-decomposable group is preferably 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 a polar group is protected with a group (leaving group) that is released under the action of an acid. Typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. Resin (A) is an acid-decomposable resin, and in the pattern formation method using the composition of the present invention, 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. The polar group generated by decomposition of the acid-decomposable group by the action of an acid is preferably an alkali-soluble group, and examples thereof 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, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0090] 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)

[0091] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to each other to form a ring (which may be either a monocyclic ring or a polycyclic ring). The alkyl group represented by Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. The number of carbon atoms in the cycloalkyl group of Rx1 to Rx3 is preferably 3 to 20, and more preferably 4 to 15. The cycloalkyl group of Rx1 to Rx3 may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aralkyl group of Rx1 to Rx3 is preferably a group in which one hydrogen atom in the alkyl group of the above-mentioned Rx1 to Rx3 is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples thereof include a benzyl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0092] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. Also, R 38 may bond with another substituent on the main chain of the repeating unit to form a ring. 38The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0093] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0094] The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (b-1): The resin (A) preferably contains a repeating unit represented by the following formula (b-1).

[0095] [ka]

[0096] In formula (b-1), R b1 and R b2 each independently represents a hydrogen atom or an alkyl group. L b1 represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. R p1 and R p2 each independently represents a group that is eliminated by the action of an acid. R b3 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer between 0 and (5+2r-st). R p1 If there are multiple R p1 may be the same or different and may be bonded to each other to form a ring. R p2If there are multiple R p2 may be the same or different and may be bonded to each other to form a ring. R b3 If there are multiple R b3 may be the same or different and may be bonded to each other to form a ring. R b3 and R p1 , R b3 and R p2 , and R p1 and R p2 may be bonded to each other to form a ring. R b1 L b1 may be bonded to the aromatic ring to which

[0097] In formula (b-1), R b1 and R b2 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The alkyl group may further have a substituent. R b1 and R b2 is preferably a hydrogen atom.

[0098] In formula (b-1), L b1 represents a single bond or -C(=O)O-, and is preferably a single bond.

[0099] In formula (b-1), r represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. The aromatic ring in formula (b-1) is benzene when r represents 0, naphthalene when r represents 1, and anthracene when r represents 2.

[0100] In formula (b-1), s represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0101] In formula (b-1), R p1represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid is not particularly limited, but examples thereof include the groups represented by the above formulae (Y1) to (Y4). -OR in formula (b-1) p1 is converted to R by the action of acid. p1 is eliminated to produce a hydroxyl group.

[0102] In formula (b-1), t represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. At least one of s and t is an integer of 1 or greater.

[0103] In formula (b-1), R p2 represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid is not particularly limited, but examples thereof include the groups represented by the above formulae (Y1) to (Y4). -COOR in formula (b-1) p2 is converted to R by the action of acid. p2 is eliminated to produce a carboxyl group.

[0104] In formula (b-1), R b3 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. R b3 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. R b3 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. b3 The methylene group contained in the alkyl group represented by may be substituted with at least one of -CO- and -O-. R b3 The number of carbon atoms in the cycloalkyl group represented by R is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. b3The cycloalkyl group represented by 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. R b3 The alkyl group contained in the alkoxy group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. R b3 The number of carbon atoms in the aryl group contained in the aryloxy group represented by R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. b3 The aryl group contained in the aryloxy group represented by is most preferably a phenyl group.

[0105] R b3 The alkyl group contained in the alkylthio group represented by R may be either linear or branched. b3 The number of carbon atoms in the alkyl group contained in the alkylthio group represented by is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. R b3 The number of carbon atoms in the aryl group contained in the arylthio group represented by R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. b3 The aryl group contained in the arylthio group represented by the formula (I) is most preferably a phenyl group. R b3 The number of carbon atoms in the aryl group represented by R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. b3 The aryl group represented by is most preferably a phenyl group. R b3 The heteroaryl group represented by preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15. The heteroaryl group may be monocyclic or polycyclic. Rb3 Examples of the heteroaryl group represented by include a thienyl group, a furanyl group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, an isothiazolyl group, and a thiadiazolyl group.

[0106] R b3 may be a carboxyl group.

[0107] R b3 The ester group represented by is a group containing -COO-, and is preferably an alkoxycarbonyl group or an alkylcarbonyloxy group. The alkyl group contained in the alkoxycarbonyl group or alkylcarbonyloxy group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group or alkylcarbonyloxy group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6.

[0108] R b3 may be a group formed by combining two or more of the above groups. The group formed by combining two or more of the above groups is not particularly limited, and examples thereof include a group formed by combining an ester group with at least one group selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, and a carboxyl group.

[0109] R b3 can further have one or more substituents, R b3 may have a substituent.

[0110] In formula (b-1), u represents an integer of 0 to (5+2r-st), preferably an integer of 0 to 4, and more preferably an integer of 0 to 2. If u is 2 or more, multiple R b3 may be the same or different and may be bonded to each other to form a ring (which may be a monocyclic or polycyclic ring). R b3 and Rp1 , R b3 and R p2 , R p1 and R p2 may be bonded to each other to form a ring (which may be a monocyclic or polycyclic ring). b1 L b1 may be bonded to the aromatic ring to which

[0111] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited to these. In the following structural formula, Me represents a methyl group, Rx represents H, CH3, CF3, or CH2OH, Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, p represents an integer of 0 or more, Xa1 represents H, CH3, CF3, or CH2OH, Z represents a substituent, and when there are multiple Zs, they may be the same or different.

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] The content of repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all repeating units in the resin (A). The content of repeating units having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on all repeating units in the resin (A).

[0118] The repeating unit having an acid-decomposable group contained in the resin (A) may be one type or two or more types. When the resin (A) contains two or more types of repeating units having an acid-decomposable group, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0119] (Repeating unit represented by formula (Pa1)) The resin (A) contains a repeating unit represented by the following formula (Pa1).

[0120] [ka]

[0121] In formula (Pa1), R A1 ~R A3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L A represents a single bond or a divalent linking group. Ar A represents an aromatic ring group. R A2 and Ar A may be bonded to form a ring. nA represents an integer of 1 to 5.

[0122] The repeating unit represented by formula (Pa1) is preferably a repeating unit different from the repeating unit having an acid-decomposable group described above.

[0123] R in formula (Pa1) A1 , R A2 and RA3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R A1 , R A2 and R A3 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. R A1 , R A2 and R A3 The number of carbon atoms in the cycloalkyl group represented by R is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. A1 , R A2 and R A3 The cycloalkyl group represented by 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. R A1 , R A2 and R A3 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferred. R A1 , R A2 and R A3 The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0124] Ar in formula (Pa1) A represents an aromatic ring group, more specifically, an aromatic ring group having a valence of (nA+1). Ar AThe aromatic ring group represented by may be an aromatic hydrocarbon group such as a benzene ring group or a naphthalene ring group, or may be an aromatic heterocyclic group. The aromatic heterocyclic group is preferably a group containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group preferably has 4 to 20 ring atoms. The aromatic heterocyclic group preferably has 1 to 18 carbon atoms. When nA 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. Specific examples of the (nA+1)-valent aromatic ring group when nA is an integer of 2 or greater include groups obtained by removing any (nA-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (nA+1)-valent aromatic ring group may further have a substituent. The substituent that the (nA+1)-valent aromatic ring group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl. Ar A preferably represents an aromatic ring group having 6 to 18 carbon atoms, more preferably represents an aromatic hydrocarbon group, and further preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0125] L in formula (Pa1) A represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited, but examples thereof include -COO-, -CONR A4-, an alkylene group, or a group formed by combining two or more of these groups. A4 represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but 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. R A4 When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0126] R A2 and Ar A may be bonded to form a ring. A2 and Ar A When they are bonded to form a ring, R A2 and Ar A may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO2-, -SO-, -SO2-, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these.

[0127] The repeating unit represented by formula (Pa1) preferably has a hydroxystyrene structure. A preferably represents a benzene ring group. nA preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0128] Specific examples of the repeating unit represented by formula (Pa1) are shown below, but the present invention is not limited to these. 1 and G 2 each independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group. f1 represents an integer of 1 to 3.

[0129] [ka]

[0130] The content of the repeating unit represented by formula (Pa1) in the resin (A) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit represented by formula (Pa1) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (A).

[0131] The repeating unit represented by formula (Pa1) contained in resin (A) may be one type or two or more types. When resin (A) contains two or more types of repeating units represented by formula (Pa1), it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0132] The resin (A) may contain other repeating units in addition to the repeating unit represented by formula (Pa1) and the repeating unit having an acid-decomposable group.

[0133] (Repeating units having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit having a lactone group, a sultone group, or a carbonate group (hereinafter also referred to as "unit Y"). It is also preferred that the unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0134] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among these, a 5- to 7-membered cyclic lactone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure, or a 5- to 7-membered cyclic sultone structure is more preferably fused with another ring structure to form a bicyclo structure or a spiro structure. The carbonate group is preferably a cyclic carbonate group. For repeating units having a cyclic carbonate group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928, the disclosures of which are incorporated herein by reference.

[0135] Resin (A) preferably has a repeating unit having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-22), a sultone structure represented by any one of the following formulae (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any one of the following formulae (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of Resin (A). The lactone group, sultone group, and carbonate group may have a substituent.

[0136] R in the following structural formula L represents a substituent. L If there are multiple R L may be the same or different. L Examples of the R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple RL may be the same or different, and multiple R L They may be bonded to each other to form a ring.

[0137] [ka]

[0138] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0139] [ka]

[0140] In formula (AI-2), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. The alkyl group of Rb0 may have a substituent, such as a hydroxyl group or a halogen atom. Examples of the halogen atom of Rb0 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, an ester group, a carbonyl group, or a divalent linking group combining these. Among these, Ab is preferably a single bond or a linking group represented by -Ab1-CO2-. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any one of formulas (CC1-1) to (CC1-2).

[0141] When the resin (A) contains the unit Y, the content of the unit Y may be 1 mol % or more, or 10 mol % or more, based on all repeating units in the resin (A), and the content of the unit Y may be 80 mol % or less, or 70 mol % or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain any Y units.

[0142] (Repeating unit having a photoacid generating group) The resin (A) may have a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid-generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0143] [ka]

[0144] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 represents a divalent linking group. 40 represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0145] L 41 represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).

[0146] L 42is preferably at least one linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an arylene group, -O-, -CO-, -S-, -SO-, -SO2-, and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. The alkylene group, cycloalkylene group and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0147] R 40 is preferably a group represented by the following formula (S4-1).

[0148] [ka]

[0149] In equation (S4-1), Q - represents the residue of an acid, and M + represents a cation. * represents L 41 represents the bonding position with The acid residue is a group formed by dissociating a proton from an acid. Q - is a carboxylate anion group (COO - ), sulfonate anion group (SO3 - ), or a sulfonamide group (N - -SO2R N1 It is expressed as R N1represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. M + The explanation, specific examples and preferred ranges of M in the explanation of the compound (QD) described below. + is the same as:

[0150] Specific examples of repeating units having a photoacid generating group include the repeating units described in

[0094] to

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

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

[0138] of WO 2022 / 024928 A. The above descriptions are incorporated herein by reference.

[0151] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of WO 2018 / 193954 A.

[0152] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (A). It is also preferred that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0153] (Repeating unit represented by formula (V-1) or formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). It is also preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the repeating units described above.

[0154] [ka]

[0155] In formulas (V-1) and (V-2), 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, an ester group (-OCOR or -COOR: R represents an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X4 represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0156] (Repeating unit to reduce the mobility of the main chain) Resin (A) may have a high glass transition temperature (Tg) to prevent excessive diffusion of generated acid or pattern collapse during development. Tg may be higher than 90°C, higher than 100°C, higher than 110°C, or higher than 125°C. To improve the dissolution rate in the developer, Tg may be 400°C or lower, or 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of a repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of each repeating unit contained in the polymer is calculated using the Bicerano method. 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 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.).

[0157] For repeating units for reducing the mobility of the main chain, the contents of

[0144] to

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

[0158] (a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>.

[0159] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves adhesion to the substrate and 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

[0081] to

[0084] of JP 2014-098921 A.

[0160] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) substituted at the α-position with an electron-withdrawing group, with carboxyl groups being preferred. Resin (A) containing a repeating unit having an alkali-soluble group improves resolution, particularly in contact hole applications. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0161] (Repeating units that have an alicyclic hydrocarbon structure and are not acid decomposable) Resin (A) may have an alicyclic hydrocarbon structure and a repeating unit that is not acid-decomposable. This reduces the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and are not acid-decomposable include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, and cyclohexyl(meth)acrylate.

[0162] (Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group) The resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.

[0163] [ka]

[0164] 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. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP-A No. 2014-098921.

[0165] (Other repeating units) Furthermore, the resin (A) may have repeating units other than the repeating units described above. Resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in

[0170] of WO 2022 / 024928.

[0166] Regarding the resin (A), the contents of

[0112] to

[0118] ,

[0171] to

[0172] of WO 2022 / 024928 can be further cited.

[0167] The resin (A) can be synthesized by a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, as determined by GPC in terms of polystyrene. The dispersity (molecular weight distribution, Pd, Mw / Mn) of the resin (A) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.0 to 3.0, and particularly preferably from 1.1 to 2.0. 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.

[0168] In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9 mass %, more preferably 50.0 to 95.0 mass %, and more preferably 60.0 to 90.0 mass %, based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more resins (A) are used, the total content thereof is preferably within the above-mentioned suitable content range.

[0169] [Acid diffusion controller (Q)] The composition of the present invention contains an acid diffusion controller (Q) (also referred to as "compound (Q)"). Compound (Q) can act as a quencher that traps the acid generated from a photoacid generator such as compound (C) during exposure, and suppresses the reaction of resin (A) in unexposed areas caused by excess generated acid. The type of compound (Q) is not particularly limited, and examples thereof include a basic compound (QA), a low molecular weight compound (QB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (QC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation. Examples of the compound (QC) include an onium salt compound (QD) of an acid that is weaker than the acid (acid (CA)) generated from the compound (C), and a basic compound (QE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.

[0170] (Basic Compounds (QA)) As the basic compound (QA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0171] [ka]

[0172] In formulas (A) and (E), R D0 , R D1 and R D2 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). R D1 and R D2 may be bonded to each other to form a ring. R D3 , R D4 , R D5 and R D6 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0173] R in formulas (A) and (E) D0 , R D1 , R D2 , R D3 , R D4 , R D5 and R D6 The alkyl group or cycloalkyl group represented by may be substituted or unsubstituted. With regard to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R in formulas (A) and (E) D0 , R D1 , R D2 , R D3 , R D4 , R D5 and R D6 The alkyl group or cycloalkyl group represented by is more preferably unsubstituted.

[0174] In formulae (B), (C), (D) and (E), * represents a bonding position.

[0175] The basic compound (QA) also includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and the like. The basic compound (QA) may be a compound having at least one structure selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (QA) may be an alkylamine derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond.

[0176] The difference between the pKa of the conjugate acid of the basic compound (QA) and the pKa of the acid (CA) (the value obtained by subtracting the pKa of the acid (CA) from the pKa of the conjugate acid of the basic compound (QA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (QA) is, for example, preferably from 1.00 to 14.00, and more preferably from 2.00 to 13.00.

[0177] (Onium salt compounds (QD) of acids that are weaker acids than the acids generated by photoacid generators) The compound (QD) may be a compound that generates an acid when irradiated with actinic rays or radiation. The compound (QD) is preferably a compound that generates an acid having a pKa that is at least 1.00 higher than that of the acid generated from the photoacid generator. The difference between the pKa of the acid generated from compound (QD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from compound (QD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 8.00, and particularly preferably 1.00 to 6.00. The pKa of the acid generated from the compound (QD) is, for example, preferably 1.00 to 10.00, and more preferably 2.00 to 8.00.

[0178] The compound (QD) is preferably an onium salt compound consisting of an anion and a cation. As the compound (QD), for example, "M + X - Examples of compounds (onium salts) include those represented by the formula "M + represents an organic cation, and X - represents an organic anion. M + The organic cation represented by is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. Among these, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0179] [ka]

[0180] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0181] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0182] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. R 201 ~R 203 one of which is an aryl group, and R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-). Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0183] 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 heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. 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 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.

[0184] R 201 ~R 203 The substituent that the aryl group, alkyl group, and cycloalkyl group may have is 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 and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above substituents may further have a substituent, if possible, and it is also preferred that the above alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any 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 a polar group, and preferably has a structure in which the polar group is protected by a group that leaves under the action of an acid. The polar group and leaving group are as described above.

[0185] 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 not having an aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. R 201 ~R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0186] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and a cycloalkyl group 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. R 201 ~R 203 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0187] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0188] [ka]

[0189] 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 (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0194] [ka]

[0195] In formula (ZaI-4b), l represents an integer of 0 to 2; r represents an integer of 0 to 8; R 13 represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 When a plurality of groups are present, 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.

[0196] In formula (ZaI-4b), 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 preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. 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.

[0197] 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 or 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).

[0198] 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.

[0199] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0200] [ka]

[0201] [ka]

[0202] "M + X - In the compound represented by ", X - represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0203] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0204] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0205] 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.

[0206] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl 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 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0207] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0208] An example of the sulfonylimide anion is a saccharin anion.

[0209] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. 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.

[0210] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are listed.

[0211] Examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4), and an anion represented by formula (d1-1) or an anion represented by formula (d1-2) is preferred.

[0212] [ka]

[0213] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0214] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). Z 2c The hydrocarbon group in the formula (I) may be linear or branched, or may have a cyclic structure. Furthermore, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. Z in formula (d1-2) 2c Preferably, Z represents an alkyl group or a cycloalkyl group. 2c In -SO3 - It is preferred that the atoms at the α- and β-positions relative to the aryl group do not have fluorine atoms as substituents.

[0215] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0216] In formula (d1-4), R 53 and R 54 R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). 53 and R 54 may be bonded to each other to form a ring.

[0217] The organic anions may be used alone or in combination of two or more.

[0218] Specific examples of basic compounds (QA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824. Specific examples of basic compounds (QE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

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

[0164] of WO 2020 / 066824. Specific examples of low molecular weight compounds (QB) having a nitrogen atom and a group that is cleaved by the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of onium salt compounds (QDs) that are weaker acids than the acids generated from photoacid generators and the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0219] In addition to the above, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[0220] The molecular weight of the compound (Q) is not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000.

[0221] Compound (Q) is also preferably a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0222] The content of compound (Q) in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention, and is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, based on the total solid content of the composition of the present invention. The compound (Q) may be used alone 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.

[0223] The mass ratio of the content of the acid diffusion controller (Q) to the content of the compound (C) in the composition of the present invention (also referred to as "(Q) / (C)") is 6 mass% or more. (Q) / (C) is calculated by (content of the acid diffusion controller (Q) / content of the compound (C)) x 100(%). When (Q) / (C) is 6 mass% or more, acid diffusion can be suppressed, and excellent resist properties can be obtained. (Q) / (C) is more preferably 20% by mass or more, and even more preferably 50% by mass or more, and is preferably 500% by mass or less, and more preferably 300% by mass or less.

[0224] [Hydrophobic resin] The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances.

[0225] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin, and more preferably has two or more of these. 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 WO 2020 / 004306.

[0226] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass %, more preferably 0.1 to 15.0 mass %, based on the total solid content of the composition of the present invention. The hydrophobic resin may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0227] [Surfactants] The composition of the present invention may contain a surfactant. When the composition contains a surfactant, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0228] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the composition of the present invention. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0229] [solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0230] The combination of the above-mentioned solvent and the above-mentioned resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0231] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % relative to the total amount of the solvent.

[0232] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass %, more preferably 1 to 20 mass %, which further improves the coatability of the composition of the present invention.

[0233] [Other additives] The composition of the present invention 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 (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0234] The "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0235] <Actinic ray- or radiation-sensitive film and pattern formation method> The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The present invention also relates to a pattern formation method. The pattern formation method of the present invention is preferably a pattern formation method comprising the steps of forming an actinic ray-sensitive or radiation-sensitive film (typically a resist film) on a substrate from the composition of the present invention, exposing the actinic ray-sensitive or radiation-sensitive film, and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. The procedure for the pattern formation method using the composition of the present invention is not particularly limited, but it is preferable that the method comprises the following steps. Step 1: Forming a resist film on a substrate using the composition of the present invention Step 2: Step of 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.

[0236] (Step 1: Resist film formation step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0237] An example of a method for forming a resist film on a substrate using the composition of the present invention is a method in which the composition of the present invention is applied onto a substrate. The composition of the present invention is preferably filtered as needed before application. 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.

[0238] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated silicon) used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spinning using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After coating the composition of the present invention, 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.

[0239] 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.

[0240] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm in order to form a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0241] 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 such as that described in JP-A-2013-61648 on the resist film. Specific examples of the basic compound that the top coat may contain include the basic compounds that may be contained in the composition of the present invention. 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.

[0242] (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. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0243] 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 step is also called post-exposure baking.

[0244] (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).

[0245] 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 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.

[0246] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.

[0247] 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.

[0248] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0249] (Other processes) The pattern formation method preferably includes, after step 3, a step of washing with a rinse liquid.

[0250] 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.

[0251] 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.

[0252] 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 a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method). The pattern formation method 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 to 120 seconds).

[0253] 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. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but 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.

[0254] The composition of the present invention and various materials used in the pattern formation method (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 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0255] 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.

[0256] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as the raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0257] 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 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferred.

[0258] 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. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing properties, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For example, SUS (stainless steel), or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used as the chemical liquid pipe. Similarly, antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the filter and O-ring.

[0259] <Electronic device manufacturing method> The present specification also relates to a method for manufacturing an electronic device, including the above-described pattern formation method, and an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present specification is one that is installed in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0260] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0261] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0262] <Resin (A)> As the resin (A), MP-1 to MP-12 were used. MP-1 to MP-10 contain the repeating units shown in Table 1 below in the amounts shown in Table 1. Table 1 also lists the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each resin. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units contained in each resin. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). 13 Measurement was performed by C-NMR (nuclear magnetic resonance).

[0263] [Table 1]

[0264] The structural formula of the repeating unit is shown below.

[0265] [ka]

[0266] <Photoacid generator> The structural formulas of the compounds used as photoacid generators are shown below. C-1 to C-14 correspond to compound (C). RC-1 to RC-3 do not correspond to compound (C).

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] The pKa of the acid generated from the photoacid generator (generated acid) and the molecular weight of the generated acid are shown in Table 2 below.

[0271] [Table 2]

[0272] <Acid diffusion control agent> Q-1 and Q-2 were used as acid diffusion controllers. The structural formulas of Q-1 and Q-2 are shown below. Q-1 and Q-2 are compounds that decompose when exposed to actinic rays or radiation to generate an acid. The pKa of the acid generated from Q-1 is 3.01, and the pKa of the acid generated from Q-2 is 4.79.

[0273] [ka]

[0274] <Hydrophobic resin> The structural formula, content (mol %) of each repeating unit, and weight average molecular weight (Mw) of the hydrophobic resin used are shown below. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units.

[0275] [ka]

[0276] <Surfactant> The surfactants used are shown below. W-1: Megafac R08 (DIC Corporation)

[0277] <Solvent> The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane) S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) S-3: Ethyl lactate S-4: γ-butyrolactone

[0278] <Preparation of Resist Composition> The components shown in Tables 3 and 4 below were dissolved in the solvents shown in the tables to prepare solutions with the solid content concentrations shown in Tables 3 and 4. These were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions (R-1 to R-32, RR-1 to RR-4). In the table, the column "Content (mass %)" indicates the content (mass ratio) of each component relative to the total solid content in the resist composition, where solid content refers to components other than the solvent. In the resist composition using a hydrophobic resin, the content of the hydrophobic resin was set to 5.0 mass %. In the resist composition using a surfactant, the surfactant content was set to 0.1 mass %. The "mass ratio" of a solvent is the content of each solvent listed in the "Type" column relative to the total amount of solvents (total amount of solvents listed in the "Type" column). When two or more types of each component are used, the type and mass ratio of each is separated by a " / ". The types and mass ratios correspond from left to right. The mass ratio of the acid diffusion controller content to the photoacid generator content in each resist composition is shown in the column "(Q) / (C)" in Tables 3 and 4. (Q) / (C) was calculated by (acid diffusion controller content / photoacid generator content) x 100(%).

[0279] [Table 3]

[0280] [Table 4]

[0281] <Pattern formation method (1): EB exposure, alkaline development (EB-positive)> The resist composition was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. It should be noted that the same results can be obtained even if the Si wafer is replaced with a chromium substrate. The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (HL750 manufactured by Hitachi, Ltd., accelerating voltage 50 keV). The lithography was performed so as to form a 1:1 line and space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds as post-exposure baking, then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a 1:1 line and space pattern with a line width of 50 nm.

[0282] <Performance evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) The exposure dose (electron beam dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolving power (the minimum line width at which a line and a space (line:space = 1:1) are resolved) at the exposure dose that shows the above sensitivity (Eop) was taken as the resolution (nm). The smaller this value, the higher the resolution.

[0283] [CDU] At an exposure dose that results in a line width of 50 nm for a 1:1 line and space pattern, the line widths of 100 lines in each line pattern were measured, and the line width uniformity (CDU) (nm) was evaluated by calculating three times the standard deviation (σ) of the average value calculated from the measurement results (3σ). The smaller the 3σ calculated above, the higher the CDU of each line CD formed on the resist film. The 3σ value was taken as CDU (nm). The smaller the 3σ value, the smaller the dimensional variation, indicating better performance.

[0284] [Bake temperature dependency] In the above-described pattern formation method (1), the optimal exposure dose was the dose at which a 1:1 line-and-space pattern with a width of 50 nm was reproduced when post-exposure baking was performed at 110°C for 90 seconds instead of 100°C for 60 seconds. Next, after irradiation at the optimal exposure dose, post-exposure baking was performed at two temperatures, +5°C and -5°C relative to the post-exposure baking temperature (i.e., 115°C and 105°C), and the resulting line-and-space patterns were measured to determine their line widths L1 and L2. The bake temperature dependency was defined as the change in line width per 1°C temperature change during baking and was calculated using the following formula. Bake temperature dependence (nm / ℃)=|L1-L2| / 10 The smaller the value of the bake temperature dependency, the smaller the change in performance with respect to temperature change, which indicates a good performance.

[0285] Table 5 below shows the resist compositions used in each of the examples and comparative examples, as well as the evaluation results for each of the examples and comparative examples.

[0286] [Table 5]

[0287] <Patterning method (2): EUV exposure, alkaline development (EUV-positive)> An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 6 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 50 nm. The silicon wafer with the resist film was patterned using an EUV exposure tool (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 50 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 100°C for 60 seconds as post-exposure baking, then developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[0288] The resists obtained were evaluated in the same manner as above, and the evaluation results are shown in Table 6.

[0289] [Table 6]

[0290] The results in Tables 5 and 6 show that the resist compositions used in the examples exhibit excellent resolution and CDU during pattern formation, and have little dependency on the bake temperature.

Claims

1. a resin (A) containing a repeating unit represented by the following formula (Pa1) and a repeating unit having a group that decomposes when acted upon by an acid to increase polarity; an acid diffusion controller (Q); a nonionic compound (C) that decomposes when exposed to actinic rays or radiation to generate an acid; An actinic ray-sensitive or radiation-sensitive resin composition comprising: the molecular weight of the acid generated from the compound (C) is 300 or more; the pKa of the acid generated from the compound (C) is −1.9 or more; The compound (C) is a compound represented by any one of the following formulas (1) to (4): a mass ratio of the content of the acid diffusion controller (Q) to the content of the compound (C) in the actinic ray-sensitive or radiation-sensitive resin composition is 6 mass% or more, The resin (A) does not contain a group obtained by removing one or more hydrogen atoms from a compound represented by any one of the following formulas (1) to (4): Actinic ray-sensitive or radiation-sensitive resin composition. 【Chemical 1】 In formula (Pa1), R Ａ１ ~R Ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L Ａ represents a single bond or a divalent linking group. Ar Ａ represents an aromatic ring group. R Ａ２ and Ar Ａ may be bonded to form a ring. nA represents an integer of 1 to 5. 【Chemistry 2】 In formulas (1) to (4), R Ｃ each independently represents a substituent. In formula (1), R １１ and R １２ R each independently represents a hydrogen atom or a substituent. １１ and R １２ may be bonded to form a ring. In formula (2), R ２１ , R ２２ and R ２３ R each independently represents a hydrogen atom or a substituent. ２１ , R ２２ and R ２３ At least two of the n may be bonded to form a ring. ２１ represents an integer of 1 or more. In formula (3), R ３１ and R ３２ R each independently represents a hydrogen atom or a substituent. ３１ and R ３２ may be bonded to form a ring. ３１ represents an aryl group or a heteroaryl group. ３１ represents 0 or 1. In formula (4), R ４１ and R ４２ R each independently represents a hydrogen atom or a substituent. ４１ and R ４２ may be bonded to form a ring.

2. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid generated from the compound (C) has a molecular weight of 500 or more.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (C) is represented by the following formula (2-1): 【Chemistry 3】 In formula (2-1), R ２４ represents a hydrogen atom or a substituent. R ２５ and R ２６ each independently represents a substituent. n ２１ represents an integer of 1 or more. R １ａ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. R １ａ If there are multiple R １ａ may be the same or different and may be bonded to each other to form a ring. n ２２ represents an integer of 0 to 5.

4. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit represented by the following formula (b-1): 【Chemistry 4】 In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. L ｂ１ represents a single bond or —C(═O)O—. r represents an integer of 0 to 2; R ｐ１ and R ｐ２ each independently represents a group that is eliminated by the action of an acid. R ｂ３ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer of 0 to (5+2r−s−t). R ｐ１ If there are multiple R ｐ１ may be the same or different and may be bonded to each other to form a ring. R ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. R ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. R ｂ３ and R ｐ１ , R ｂ３ and R ｐ２ , and R ｐ１ and R ｐ２ may be bonded to each other to form a ring. L ｂ１ The aromatic ring to which R is bonded ｂ１ may be combined with

5. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4.

6. A pattern forming method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4; exposing the resist film; and developing the exposed resist film using a developer.

7. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.

Images