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

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition; an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition; a pattern forming method; and an electronic device manufacturing method. The actinic ray-sensitive or radiation-sensitive resin composition comprises: a resin that includes a repeating unit (UA) having a group decomposed by the action of an acid to have increased polarity, includes a repeating unit (UB) having a phenolic hydroxy group, and includes a repeating unit (U1) having at least one group having a specific structure; a photo-acid generator that includes at least one of a sulfonium cation and an iodonium cation; and an acid diffusion control agent that includes at least one of a sulfonium cation and an iodonium cation and is decomposed by actinic ray or radiation irradiation.

Description

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

[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 an ultra-microlithography process 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.

[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, with the increasing integration density of integrated circuits, there has been 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 technique 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 a pattern formation method in which a resist material containing a polymeric compound containing a repeating unit having an acid labile group and sparingly soluble in an alkaline developer, a photoacid generator, a photobase generator that generates an amino group, a quencher that has an amino group and inactivates the acid generated by the photoacid generator by neutralizing it, and an organic solvent is applied to a substrate, and the resist material undergoes baking, exposure, baking (PEB), and development steps to obtain a pattern in which unexposed areas with low exposure dose and overexposed areas with high exposure dose are not dissolved in the developer, while exposed areas with intermediate exposure dose are dissolved in the developer.

[0005] Patent Document 2 describes a resist composition used in step (1) of a resist pattern forming method, which includes the steps of: applying a resist composition containing a base component that generates a base upon exposure and whose solubility in an alkaline developer increases under the action of an acid onto a support to form a resist film; step (2) of exposing the resist film; step (3) of baking the resist film after step (2) to neutralize the base generated from the base component upon exposure with the acid that has been previously supplied to the resist film in the exposed areas of the resist film, and to increase the solubility of the base component in an alkaline developer in the unexposed areas of the resist film by the action of the acid that has been previously supplied to the resist film; and step (4) of alkaline developing the resist film to form a negative resist pattern in which the unexposed areas of the resist film are dissolved and removed.

[0006] Japanese Patent Publication No. 2011-102974 Japanese Patent Publication No. 2013-122570

[0007] Recently, the performance required for resist compositions has been increasing. In particular, there is a demand for improved resolution and exposure latitude (EL) performance when forming fine patterns. Furthermore, there is a demand for actinic ray-sensitive or radiation-sensitive resin compositions whose performance is unlikely to deteriorate even after a certain period of time has elapsed after preparation (excellent stability over time).

[0008] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, EL performance, and stability over time. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0009] The present inventors have found that the above problems can be solved by the following configuration.

[0010] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and an acid diffusion controller, wherein the resin contains a repeating unit (UA) having a group that decomposes under the action of an acid and increases polarity, and a repeating unit (UB) having a phenolic hydroxyl group, and also contains a repeating unit (U1) having at least one group represented by the following formula (1): the photoacid generator contains a compound having at least one of a sulfonium cation and an iodonium cation, and the acid diffusion controller contains a compound having at least one of a sulfonium cation and an iodonium cation.

[0011]

[0012] In formula (1), R １ represents a hydrogen atom or a substituent. １ represents an alkylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a heteroarylene group, an alkenylene group, or an alkynylene group. １ represents a group represented by any one of the following formulas (T-1) to (T-3). １ , S １ and T １ At least two of R may be bonded to form a ring. １ , S １ and T １ At least one of these may be bonded to a group other than the group represented by formula (1) in the repeating unit (U1) to form a ring. * indicates the bonding position.

[0013]

[0014] In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0015]

[0016] In formula (T-2), k3 represents 0 or 1. Ｔ３ and R Ｔ４ each independently represents a hydrogen atom or a substituent. Ｔ２ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0017]

[0018] In formula (T-3), L １ represents an alkenylene group or an alkynylene group. Ｔ５ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. # represents a bonding position to a nitrogen atom. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (UA) is a repeating unit represented by the following formula (b-1):

[0019]

[0020] In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. 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 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. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. 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. ｂ１ Is L ｂ１ [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit (U1) is a repeating unit different from the repeating unit (UA). [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (U1) is a repeating unit represented by the following formula (2):

[0021]

[0022] In formula (2), R ２ represents a hydrogen atom, an alkyl group or a halogen atom. ２ represents a single bond or a divalent linking group. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the above formulas (T-1) to (T-3).２ , R ２ , R ３ , S ２ and T ２ [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the repeating unit (U1) is a repeating unit represented by the following formula (3):

[0023]

[0024] In formula (3), k4 represents 0 or 1. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the above formulas (T-1) to (T-3). [6] T in the above formula (1) １ represents a group represented by the following formula (T-1-1):

[0025]

[0026] In formula (T-1-1), R Ｔ６ and R Ｔ７ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; k2 represents 0 or 1. Ar Ｔ１represents an aryl group or a heteroaryl group. # represents the bonding position with the nitrogen atom. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the content of the acid diffusion controller is 50 mol % or more relative to the content of the photoacid generator. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the content of the acid diffusion controller is 100 mol % or more relative to the content of the photoacid generator. [9] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10] A pattern formation method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8]; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

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

[10] .

[0027] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution, EL performance, and stability over time. The present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0028] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0029] 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" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0030] 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.

[0031] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a 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: differential refractive index detector).

[0032] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0033] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacrylate group, a methyl ... Examples of the substituent T include acyl groups such as phenylsulfanyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; 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.).

[0034] 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 "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0035] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. 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).

[0036] The pKa can also be calculated by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ 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, and Gaussian 16 is an example.

[0037] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be adopted.

[0038] 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.

[0039] <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 an actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and an acid diffusion controller, wherein the resin contains a repeating unit (UA) having a group that decomposes under the action of an acid and increases polarity, and a repeating unit (UB) having a phenolic hydroxyl group, and also contains a repeating unit (U1) having at least one group represented by the following formula (1), the photoacid generator contains a compound having at least one of a sulfonium cation and an iodonium cation, and the acid diffusion controller contains a compound having at least one of a sulfonium cation and an iodonium cation.

[0040]

[0041] In formula (1), R １ represents a hydrogen atom or a substituent. １ represents an alkylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a heteroarylene group, an alkenylene group, or an alkynylene group. １ represents a group represented by any one of the following formulas (T-1) to (T-3). １ , S １ and T １ At least two of R may be bonded to form a ring. １ , S １ and T １ At least one of these may be bonded to a group other than the group represented by formula (1) in the repeating unit (U1) to form a ring. * indicates the bonding position.

[0042]

[0043] In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0044]

[0045] In formula (T-2), k3 represents 0 or 1. Ｔ３ and R Ｔ４ each independently represents a hydrogen atom or a substituent. Ｔ２ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0046]

[0047] In formula (T-3), L １ represents an alkenylene group or an alkynylene group. Ｔ５ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0048] The mechanism by which the composition of the present invention achieves the above-mentioned effects has not been clarified, but the inventors have hypothesized it as follows. However, the present invention is not limited in any way by the hypothesized mechanism below. The composition of the present invention contains a resin, a photoacid generator, and an acid diffusion controller, and the resin contains a repeating unit having a group represented by formula (1). It is believed that the resin containing a repeating unit having a group represented by formula (1) improves compatibility with other materials (such as the photoacid generator and the acid diffusion controller) and makes the resin less likely to aggregate, thereby achieving the above-mentioned effects.

[0049] 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. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0050] [Resin] The composition of the present invention contains a resin (also referred to as "resin (P)") that includes a repeating unit (UA) having a group that decomposes under the action of an acid and increases polarity, and a repeating unit (UB) having a phenolic hydroxyl group, and also includes a repeating unit (U1) that has at least one group represented by the above formula (1).

[0051] The repeating unit (U1) may be the same repeating unit as the repeating unit (UA) or may be a different repeating unit. The repeating unit (U1) is preferably a different repeating unit from the repeating unit (UA). The repeating unit (U1) may be the same repeating unit as the repeating unit (UB) or may be a different repeating unit. The repeating unit (U1) is preferably a different repeating unit from the repeating unit (UB). The repeating unit (UA) and the repeating unit (UB) may be the same repeating unit or may be different repeating units. The repeating unit (UA) and the repeating unit (UB) are preferably different repeating units. The repeating unit (U1), the repeating unit (UA), and the repeating unit (UB) are preferably different repeating units.

[0052] The resin (P) 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.

[0053] (Repeating Unit (U1)) The repeating unit (U1) is a repeating unit having at least one group represented by the above formula (1).

[0054] In formula (1), R １ represents a hydrogen atom or a substituent. １ The substituent represented by is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group.

[0055] R １ 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 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a trifluoromethyl group. R １ The explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy group and alkylthio group represented by R １ is the same as the alkyl group represented by

[0056] R １ The cycloalkyl group represented by may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. 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. The cycloalkyl group may have a substituent. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, or a group having a heteroatom such as an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R １The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxy group and cycloalkylthio group represented by R １ is the same as the cycloalkyl group represented by

[0057] R １ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, further preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent. １ The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group and arylthio group represented by R １ is the same as the aryl group represented by

[0058] R １ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. １ The number of ring atoms of the heteroaryl group represented by is preferably 4 to 20, and more preferably 5 to 15. Examples of the heteroaryl group include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. The heteroaryl group may have a substituent.

[0059] In formula (1), S １ represents an alkylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a heteroarylene group, an alkenylene group, or an alkynylene group. １ The alkylene group represented by 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. １The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, a group having a heteroatom such as an ester bond, or a vinylidene group. Furthermore, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a vinylene group. １ The number of carbon atoms in the cycloalkenylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15, for example. The cycloalkenylene group may be a monocyclic cycloalkenylene group or a polycyclic cycloalkenylene group. One or more methylene groups constituting the cycloalkene ring of the cycloalkenylene group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, a group having a heteroatom such as an ester bond, or a vinylidene group. Furthermore, one or more ethylene groups constituting the cycloalkene ring of the cycloalkenylene group may be replaced with a vinylene group. S １ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. １ The alkynylene group represented by is not particularly limited, but is preferably, for example, an alkynylene group having 2 to 8 carbon atoms. １ The arylene group represented by is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. １The heteroarylene group represented by is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. １ The heteroarylene group represented by the formula (I) preferably has 4 to 20 ring atoms, more preferably 5 to 15 ring atoms.

[0060] In formula (1), T １ represents a group represented by any one of the above formulas (T-1) to (T-3).

[0061] In formula (T-1), k1 and k2 each independently represent 0 or 1. It is preferable that k1 represents 1.

[0062] In formula (T-1), R Ｔ１ and R Ｔ２ R each independently represents a hydrogen atom or a substituent. Ｔ１ and R Ｔ２ The substituent represented by is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group. Ｔ１ and R Ｔ２ The explanation, specific examples and preferred ranges of the substituent represented by R in the above formula (1) are １ It is the same as in R Ｔ１ and R Ｔ２ preferably represents a hydrogen atom.

[0063] In formula (T-1), Ar Ｔ１ represents an aryl group or a heteroaryl group. Ｔ１ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, further preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent. Ｔ１The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. Ｔ１ The heteroaryl group represented by the formula (I) preferably has 4 to 20 ring atoms, more preferably 5 to 15 ring atoms. Examples of the heteroaryl group include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. The heteroaryl group may have a substituent. Ｔ１ preferably represents an aryl group.

[0064] The group represented by formula (T-1) is preferably a group represented by the following formula (T-1-1).

[0065]

[0066] In formula (T-1-1), R Ｔ６ and R Ｔ７ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; k2 represents 0 or 1. Ar Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

[0067] In formula (T-1-1), R Ｔ６ and R Ｔ７ R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Ｔ６ and R Ｔ７ The explanation, specific examples and preferred ranges of the alkyl group, aryl group and heteroaryl group represented by R in the above formula (1) are as follows: １ It is the same as in

[0068] In formula (T-1-1), k2 represents 0 or 1.

[0069] In formula (T-1-1), Ar Ｔ１ represents an aryl group or a heteroaryl group. Ｔ１The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by Ar in the above formula (T-1) are Ｔ１ It is the same as in

[0070] In formula (T-2), k3 represents 0 or 1. Preferably, k3 represents 1.

[0071] In formula (T-2), R Ｔ３ and R Ｔ４ R each independently represents a hydrogen atom or a substituent. Ｔ３ and R Ｔ４ The substituent represented by is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group. Ｔ３ and R Ｔ４ The explanation, specific examples and preferred ranges of the substituent represented by R in the above formula (1) are １ It is the same as in R Ｔ３ and R Ｔ４ preferably represents a hydrogen atom.

[0072] In formula (T-2), Ar Ｔ２ represents an aryl group or a heteroaryl group. Ｔ２ The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by Ar in the above formula (T-1) are Ｔ１ It is the same as in

[0073] In formula (T-3), L １ represents an alkenylene group or an alkynylene group. １ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. １ The alkynylene group represented by is not particularly limited, but is preferably, for example, an alkynylene group having 2 to 8 carbon atoms.

[0074] In formula (T-3), R Ｔ５ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Ｔ５The explanation, specific examples and preferred ranges of the alkyl group, aryl group and heteroaryl group represented by R in the above formula (1) are as follows: １ It is the same as in

[0075] In formula (1), R １ , S １ and T １ At least two of these may be bonded to form a ring. When these are bonded, they may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, 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. For example, R １ and S １ is a preferred embodiment in which these are bonded to form a ring.

[0076] In formula (1), R １ , S １ and T １ At least one of these may bond to a group other than the group represented by formula (1) in the repeating unit (U1) to form a ring. When these are bonded, they may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, 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. Examples of groups other than the group represented by formula (1) in the compound having a group represented by formula (1) include, for example, R ２ and L ２ Examples include:

[0077] The repeating unit (U1) is preferably a repeating unit represented by the following formula (2).

[0078]

[0079] In formula (2), R ２represents a hydrogen atom, an alkyl group or a halogen atom. ２ represents a single bond or a divalent linking group. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the above formulas (T-1) to (T-3). ２ , R ２ , R ３ , S ２ and T ２ At least two of these may be bonded to form a ring.

[0080] In formula (2), R ２ represents a hydrogen atom, an alkyl group, or a halogen atom. ２ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. ２ 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 6. The alkyl group is preferably a methyl group or an ethyl group, more preferably a methyl group. The alkyl group may have a substituent. R ２ preferably represents a hydrogen atom or an alkyl group, and more preferably represents a hydrogen atom.

[0081] In formula (2), L ２ represents a single bond or a divalent linking group. ２ The divalent linking group represented by the formula (I) is not particularly limited, but examples thereof include —O—, —S—, —CO—, —CO ２ -, -SO-, -SO ２ -, -NR ４ -, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), arylene groups (preferably having 6 to 20 carbon atoms), and groups formed by combining two or more of these. ４ represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms). ２ The divalent linking group represented by the formula: ２Preferably, it is an alkylene group, an arylene group, or a group formed by combining two or more of these.

[0082] In formula (2), S ２ represents an alkylene group, an arylene group, or a heteroarylene group. ２ The explanation, specific examples and preferred ranges of the alkylene group, arylene group and heteroarylene group represented by are as described above in relation to S in formula (1). １ It is the same as in

[0083] In formula (2), R ３ represents a hydrogen atom or a substituent. ３ The explanation, specific examples and preferred ranges of the substituent represented by R in the above formula (1) are １ It is the same as in

[0084] In formula (2), T ２ represents a group represented by any one of formulas (T-1) to (T-3). ２ The explanation, specific examples and preferred ranges of T in the above formula (1) are １ The same as in T in formula (2) ２ is preferably a group represented by the above formula (T-1-1).

[0085] The repeating unit (U1) is particularly preferably a repeating unit represented by the following formula (3).

[0086]

[0087] In formula (3), k4 represents 0 or 1. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the above formulas (T-1) to (T-3).

[0088] In formula (3), S ２ represents an alkylene group, an arylene group, or a heteroarylene group. ２The explanation, specific examples and preferred ranges of the alkylene group, arylene group and heteroarylene group represented by are as described above in relation to S in formula (1). １ It is the same as in

[0089] In formula (3), R ３ represents a hydrogen atom or a substituent. ３ The explanation, specific examples and preferred ranges of the substituent represented by R in the above formula (1) are １ It is the same as in

[0090] In formula (3), T ２ represents a group represented by any one of formulas (T-1) to (T-3). ２ The explanation, specific examples and preferred ranges of T in the above formula (1) are １ The same as in T in equation (3). ２ is preferably a group represented by the above formula (T-1-1).

[0091] Specific examples of the repeating unit (U1) are shown below, but the present invention is not limited to these.

[0092]

[0093]

[0094]

[0095]

[0096] The content of the repeating unit (U1) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units in the resin (P), and the content of the repeating unit (UA) is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, based on the total repeating units in the resin (P).

[0097] The repeating unit (U1) can be introduced into the resin by referring to a known method.

[0098] (Repeating Unit (UA)) The repeating unit (UA) is a repeating unit having a group that decomposes under the action of an acid and increases its 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 by a group that leaves under the action of an acid (leaving group). Typically, the polarity of the resin (P) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group 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.

[0099] 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(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0100] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents 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). １ ~Rx３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to each other to form a ring (which may be either a monocyclic or polycyclic ring). １ ~Rx ３ The alkyl group of Rx 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. １ ~Rx ３ The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. １ ~Rx ３ The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３ The aryl group in Rx 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. １ ~Rx ３ The aralkyl group of Rx １ ~Rx ３ A group in which one hydrogen atom in the alkyl group is substituted with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms is preferred, and examples thereof include a benzyl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １~Rx ３ The cycloalkyl group formed by combining the two 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. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, 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. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0101] 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. 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. In addition, 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.

[0102] 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.

[0103] The repeating unit (UA) is preferably a repeating unit represented by the following formula (b-1):

[0104]

[0105] In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. 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. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. ｂ３ and R ｐ１ , R ｂ３ and R ｐ２ , and R ｐ１ and R ｐ２may be bonded to each other to form a ring. ｂ１ Is L ｂ１ may be bonded to the aromatic ring to which

[0106] In formula (b-1), R ｂ１ and R ｂ２ The alkyl group in R 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. ｂ１ and R ｂ２ is preferably a hydrogen atom.

[0107] In formula (b-1), L ｂ１ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0108] 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.

[0109] 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.

[0110] In formula (b-1), R ｐ１ 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). ｐ１ is converted to R by the action of an acid. ｐ１ is eliminated to produce a hydroxyl group.

[0111] 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.

[0112] In formula (b-1), R ｐ２represents 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). ｐ２ is converted to R by the action of an acid. ｐ２ is eliminated to produce a carboxyl group.

[0113] 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. ｂ３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. ｂ３ The alkyl group in R 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 may be substituted with at least one of —CO— and —O—. ｂ３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. ｂ３ The cycloalkyl group of R 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. ｂ３ The alkyl group contained in the alkoxy group 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. ｂ３ The number of carbon atoms in the aryl group contained in the aryloxy group 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 is most preferably a phenyl group.

[0114] R ｂ３The alkyl group contained in the alkylthio group may be either linear or branched. ｂ３ The number of carbon atoms in the alkyl group contained in the alkylthio group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. ｂ３ The number of carbon atoms in the aryl group contained in the arylthio group 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 of R is most preferably a phenyl group. ｂ３ The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. ｂ３ The aryl group in R is most preferably a phenyl group. ｂ３ The heteroaryl group 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. R ｂ３ Examples of the heteroaryl group 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.

[0115] R ｂ３ may be a carboxyl group.

[0116] R ｂ３ The ester group 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, and more preferably 1 to 6.

[0117] R ｂ３may 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, but 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.

[0118] R ｂ３ can further have one or more substituents, R ｂ３ may have a substituent.

[0119] In formula (b-1), u represents an integer of 0 to (5+2r-s-t). u is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. When u is 2 or more, a plurality of 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). ｂ３ and R ｐ１ , 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 Is L ｂ１ may be bonded to the aromatic ring to which

[0120] Specific examples of the repeating unit (UA) are shown below, but the present invention is not limited to these. In the following structural formula, Me represents a methyl group, and Rx represents H, CH ３ , C.F. ３ or CH ２ 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; １ is H, CH ３ , C.F. ３ or CH ２ Z represents a substituent, and when there are a plurality of Z's, they may be the same or different.

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] The content of the repeating unit (UA) 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 (P), and the content of the repeating unit (UA) 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 (P).

[0127] The repeating unit (UA) contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units (UA), it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0128] (Repeating unit (UB)) The repeating unit (UB) is a repeating unit having a phenolic hydroxyl group. The repeating unit (UB) is preferably a repeating unit different from the repeating unit (UA) described above. The repeating unit (UB) is preferably a repeating unit represented by the following formula (Pa3):

[0129]

[0130] In formula (Pa3), R １０１ , R １０２ and R １０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic ring group, and k represents an integer of 1 to 5.

[0131] R in formula (Pa3) １０１ , R １０２ and R１０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０１ , R １０２ and R １０３ The alkyl group in R 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. １０１ , R １０２ and R １０３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３ The cycloalkyl group of R 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. １０１ , R １０２ and R １０３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group 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.

[0132] Ar in formula (Pa3) Ａrepresents an aromatic ring group, more specifically, a (k+1)-valent aromatic ring group. When k 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. When k is an integer of 2 or more, specific examples of the (k+1)-valent aromatic ring group include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (k+1)-valent aromatic ring group may further have a substituent. The substituent that the (k+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. Ａ preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0133] L in formula (Pa3) Ａ represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ 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 １０４When 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.

[0134] The repeating unit represented by formula (Pa3) preferably has a hydroxystyrene structure. Ａ preferably represents a benzene ring group. k preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0135] Specific examples of the repeating unit (UB) are shown below, but the present invention is not limited to these. In the following structural formula, a represents an integer of 1 to 3.

[0136]

[0137]

[0138]

[0139] The content of the repeating unit (UB) in the resin (P) 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 (P). The content of the repeating unit (UB) 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 (P).

[0140] The repeating unit (UB) contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units (UB), it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0141] Resin (P) may contain other repeating units different from repeating units (U1), (UA), and (UB). Regarding the other repeating units, the contents of paragraphs

[0112] to

[0172] of WO 2022 / 024928 are incorporated by reference.

[0142] Resin (P) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (P), as a polystyrene equivalent value measured by GPC, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Pd, Mw / Mn) of resin (P) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0143] In the composition of the present invention, the content of resin (P) is preferably 40.0 to 99.9 mass% and more preferably 60.0 to 90.0 mass% based on the total solid content of the composition of the present invention. Resin (P) may be used alone or in combination of two or more. When two or more resins (P) are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0144] [Photoacid Generator] The composition of the present invention contains a photoacid generator (also referred to as "compound (A)") containing at least one of a sulfonium cation and an iodonium cation. The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. Compound (A) is preferably a compound that generates an acid having a pKa of less than 1.5 upon irradiation with actinic rays or radiation.

[0145] The compound (A) is preferably an ionic compound, and more preferably a compound containing at least one of a sulfonium cation and an iodonium cation and an anion (counter anion).

[0146] Examples of the compound (A) include "M ＋ X －", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methide acids, and sulfonic acids are preferred.

[0147] "M ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation. As the organic cation, 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)") is preferred.

[0148]

[0149] In formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group 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 (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are listed.

[0150] R ２０１ , R ２０２ , and R ２０３The organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group 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 5. 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.

[0151] In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. 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 in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５The 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 (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0152] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples 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.

[0153] "M ＋ X － In the compound represented by the formula "X － represents an anion. － is preferably a sulfonate anion. Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphorsulfonate anion.

[0154] The compound (A) may be at least one selected from the group consisting of the following compounds (I) to (II):

[0155] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M１ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0156] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic moiety represented by the formula (1), wherein the acid dissociation constant a2 is greater than the acid dissociation constant a1. It is preferable that at least one of the acid dissociation constants a1 is less than 1.5.

[0157] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A. ２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." １ － and H.A. ２The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0158] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having two HAs. １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1 described above. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0159] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0160] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0161] For example, when compound (II) is an acid-generating compound having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII is "two HA １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0162] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. At least one of the acid dissociation constants a1 is preferably less than 1.5. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. The two or more A １ － and two or more of the above M １ ＋ may be the same or different.

[0163] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0164]

[0165] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0166] With regard to the cation, compound (I) and compound (II), the contents of paragraphs

[0207] to

[0278] of WO 2022 / 024928 can be cited.

[0167] More preferably, compound (A) is a compound containing a sulfonium cation.

[0168] Compound (A) preferably contains a sulfonate anion as the anion. Examples of sulfonate anions include aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions. The aliphatic moiety in the aliphatic sulfonate 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). The aryl group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group. The alkyl groups, cycloalkyl groups, and aryl groups listed above may have a substituent. The substituent is not particularly limited, and 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).

[0169] The compound (A) preferably contains an anion represented by the following formula (ca1):

[0170]

[0171] In formula (ca1), Ar ａ２ represents an aromatic ring. ａ２ represents a substituent. p represents an integer of 0 to 7. When p is 2 or more, a plurality of E ａ２ When p is 2 or more, a plurality of Eａ２ may be bonded to each other to form a ring.

[0172] Ar ａ２ The aromatic ring represented by may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic hydrocarbon ring preferably has 6 to 20 ring-membered carbon atoms, more preferably 6 to 15 ring-membered carbon atoms. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic heterocycle preferably has 4 to 20 ring-membered atoms, more preferably 5 to 10 ring-membered atoms. The aromatic heterocycle preferably contains at least one of a sulfur atom, a nitrogen atom, and an oxygen atom. Examples of aromatic heterocycles include five-membered aromatic heterocycles such as a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, a thiophene ring, and a furan ring; six-membered aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a thiazine ring, and an oxazine ring; and fused-ring aromatic heterocycles such as an indole ring, a quinoline ring, and an isoquinoline ring. Ar ａ２ The aromatic ring represented by is preferably an aromatic hydrocarbon ring.

[0173] E ａ２ The substituent represented by is not particularly limited, but examples thereof include the above-mentioned substituent T, and a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, and a halogen atom are preferred.

[0174] p represents an integer of 0 to 7, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.

[0175] It is preferable that compound (A) generates an acid having a pKa of less than 1.5 upon irradiation with actinic rays or radiation. The acid generated from compound (A) upon irradiation with actinic rays or radiation is also referred to as "acid (AA)." The acid (AA) is preferably a conjugate acid of a counter anion contained in compound (A), and more preferably a conjugate acid of a sulfonate anion.

[0176] The molecular weight of the acid (AA) is preferably 300 to 2000, more preferably 400 to 1500, and even more preferably 500 to 1200. The pKa of the acid (AA) is not particularly limited, but is preferably -2.0 or higher, more preferably -1.5 or higher, and even more preferably -1.0 or higher. The pKa of the acid (AA) is preferably less than 1.5, more preferably 1.0 or lower, and even more preferably 0.5 or lower.

[0177] The molecular weight of the compound (A) is not particularly limited, but is preferably 350 to 3,500, more preferably 400 to 3,000.

[0178] The content of compound (A) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the composition of the present invention.In addition, the content of compound (A) in the composition of the present invention is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition of the present invention.Only one type of compound (A) may be used, or two or more types may be used.When two or more types are used, it is preferable that their total content is within the above-mentioned preferred content range.

[0179] The composition of the present invention may contain, in addition to compound (A), a photoacid generator other than compound (A). The content of compound (A) in the composition of the present invention is preferably 30 to 100 mass %, more preferably 40 to 100 mass %, and even more preferably 50 to 100 mass %, based on the total amount of photoacid generators in the composition of the present invention.

[0180] [Acid Diffusion Controller] The composition of the present invention contains an acid diffusion controller (also referred to as "compound (B)") containing at least one of a sulfonium cation and an iodonium cation. The acid diffusion controller can act as a quencher that traps acid generated, for example, from a photoacid generator during exposure, and suppresses the reaction of the acid-decomposable resin in unexposed areas due to excess acid generated. Compound (B) is preferably a compound that decomposes upon irradiation with actinic rays or radiation. Compound (B) preferably absorbs energy from irradiation with actinic rays or radiation, causing cleavage (decomposition) of a bond contained in at least one of the sulfonium cation and the iodonium cation. Compound (B) is preferably a compound that decomposes upon irradiation with actinic rays or radiation, thereby reducing or eliminating its acid diffusion control ability. Compound (B) is preferably a compound that changes, upon irradiation with actinic rays or radiation, to an acid with a pKa greater than that of the aforementioned acid (AA) (an acid that is relatively weaker than acid (AA)).

[0181] Examples of the compound (B) include "E ＋ G － ", and it is preferably a compound that changes into an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), phenols, carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methide acids. Carboxylic acids or phenols are preferred, and carboxylic acids are more preferred.

[0182] "E ＋ G － In the compound represented by E ＋ represents an organic cation. As the organic cation, 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)") is preferred.

[0183]

[0184] In formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group 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 (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are listed.

[0185] R ２０１ , R ２０２ , and R ２０３The organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group 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 5. 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.

[0186] In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. 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 in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５The 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 (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0187] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples 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.

[0188] "E ＋ G － In the compound represented by ", G － represents an anion. － is preferably a carboxylate anion or a phenoxide anion, more preferably a carboxylate anion.

[0189] More preferably, compound (B) is a compound containing a sulfonium cation.

[0190] Compound (B) preferably contains a carboxylate anion or a phenoxide anion as the anion, and more preferably a carboxylate anion. Examples of carboxylate anions include aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylate anions. The aliphatic moiety in 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). The aryl group in the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group. The aryl group in the phenoxide anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group. The alkyl group, cycloalkyl group, and aryl group listed above may have a substituent. The substituent is not particularly limited, and 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). 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.

[0191] The compound (B) preferably contains an anion represented by the following formula (xa1) or (xa2).

[0192]

[0193] In formulas (xa1) and (xa2), Ar ａ１ represents an aromatic ring. ａ１ represents a substituent; q represents an integer of 0 to 7; when q is 2 or more, a plurality of E ａ１ When q is 2 or more, a plurality of E ａ１ may be bonded to each other to form a ring.

[0194] Ar ａ１ The aromatic ring represented by may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic hydrocarbon ring preferably has 6 to 20 ring-membered carbon atoms, more preferably 6 to 15 ring-membered carbon atoms. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic heterocycle preferably has 4 to 20 ring-membered atoms, more preferably 5 to 10 ring-membered atoms. The aromatic heterocycle preferably contains at least one of a sulfur atom, a nitrogen atom, and an oxygen atom. Examples of aromatic heterocycles include five-membered aromatic heterocycles such as a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, a thiophene ring, and a furan ring; six-membered aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a thiazine ring, and an oxazine ring; and fused-ring aromatic heterocycles such as an indole ring, a quinoline ring, and an isoquinoline ring.

[0195] E ａ１ The substituent represented by is not particularly limited, but examples thereof include the above-mentioned substituent T, and a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, and a halogen atom are preferred.

[0196] q represents an integer of 0 to 7, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.

[0197] It is preferable that compound (B) is converted into an acid (also referred to as "acid (BA)") having a pKa of 1.5 or more upon irradiation with actinic rays or radiation. The acid (BA) is preferably a conjugate acid of a counter anion contained in compound (B), more preferably a conjugate acid of a carboxylate anion or a conjugate acid of a phenoxide anion, and even more preferably a conjugate acid of a carboxylate anion.

[0198] The molecular weight of the acid (BA) is not particularly limited, but is preferably 50 to 1,000, more preferably 100 to 800, and even more preferably 100 to 500. The pKa of the acid (BA) is not particularly limited, but is preferably 1.5 or higher, more preferably 2.0 or higher, and even more preferably 2.5 or higher. The pKa of the acid (BA) is preferably less than 10, more preferably 8 or lower, and even more preferably 6 or lower.

[0199] The molecular weight of the compound (B) is not particularly limited, but is preferably 300 to 3,000, more preferably 350 to 2,000.

[0200] The content of compound (B) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the composition of the present invention.In addition, the content of compound (B) in the composition of the present invention is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition of the present invention.Only one type of compound (B) may be used, or two or more types may be used.When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0201] The composition of the present invention may contain, in addition to compound (B), an acid diffusion controller other than compound (B). The content of compound (B) in the composition of the present invention is preferably 30 to 100 mass %, more preferably 40 to 100 mass %, and even more preferably 50 to 100 mass %, based on the total amount of acid diffusion controllers in the composition of the present invention.

[0202] The content of the acid diffusion controller in the composition of the present invention is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more, relative to the content of the photoacid generator. That is, (content of acid diffusion controller / content of photoacid generator) x 100 is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more. The higher the content of the acid diffusion controller relative to the photoacid generator, the more effectively acid diffusion can be suppressed, and excellent resist properties can be obtained.

[0203] The content of compound (B) in the composition of the present invention is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more relative to the content of compound (A). That is, (content of compound (B) / content of compound (A)) x 100 is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more. The higher the content of compound (B) relative to compound (A), the more effectively acid diffusion can be suppressed, and excellent resist properties can be obtained.

[0204] [Hydrophobic Resin (Resin (T))] The composition of the present invention may further contain a hydrophobic resin (also referred to as "Resin (T)") different from Resin (P). The hydrophobic resin is preferably designed so as 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 the polar and non-polar substances.

[0205] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0206] 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% and more preferably 0.1 to 15.0 mass% based on the total solid content of the composition of the present invention. One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0207] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, 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 the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0208] 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%, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0209] [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, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0210] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in 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 component (M1) and component (M2) are described in paragraphs

[0218] to

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

[0211] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0212] 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% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0213] [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 phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0214] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0215] It is preferred that the composition of the present invention has an increased solubility in an alkaline developer in the exposed area as the exposure dose increases.

[0216] <Actinic ray- or radiation-sensitive film, pattern forming 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 forming method. The pattern forming method of the present invention is preferably a pattern forming method comprising the steps of forming an actinic ray- or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention, exposing the actinic ray- or radiation-sensitive film, and developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably comprises the following steps: Step 1: Forming a resist film on a substrate using the composition of the present invention; Step 2: Exposing the resist film; Step 3: Developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0217] (Step 1: Resist Film Forming Step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0218] A method for forming a resist film on a substrate using the composition of the present invention includes, for example, applying the composition of the present invention to a substrate. It is preferable to filter the composition of the present invention before application, if necessary. 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.

[0219] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0220] 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, and may also 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 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0221] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming 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.

[0222] 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 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 JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the resist film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain 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.

[0223] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film. Examples of exposure methods include 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, and preferably have a wavelength of 250 nm or less, more preferably 220 nm or less, and far ultraviolet light having a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam are particularly preferred.

[0224] After exposure, it is preferable to bake (heat) the film before developing. Baking 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 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0225] (Step 3: Development Step) 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).

[0226] 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 a 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 dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0227] 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 usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0228] 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.

[0229] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0230] In the pattern forming method of the present invention, it is preferable that the solubility of the exposed area in an alkaline developer increases with an increase in the exposure dose.

[0231] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0232] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0233] 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.

[0234] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (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 by 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 typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0235] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0236] 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.

[0237] 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.

[0238] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0239] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter 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 a content of 0 ppt by mass or more is preferred.

[0240] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic 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 characteristics, 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 the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0241] <Method for manufacturing an electronic device> This specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0242] 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.

[0243] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0244] <Resins> MP-1 to MP-22 were used as resins (P). RP-1 to RP-3 were also used as resins other than resin (P). However, for convenience, RP-1 to RP-3 may also be listed in the resin (P) column in the tables below. Each resin contains the repeating units shown in Table 1 below in the amounts shown in Table 1. In Table 1, "repeating unit having a phenolic hydroxyl group" corresponds to repeating unit (UB), "repeating unit having an acid-decomposable group" corresponds to repeating unit (UA), and "repeating unit having a group represented by formula (1)" corresponds to repeating unit (U1). However, MC-8 is also a repeating unit having an acid-decomposable group. MC-9 is also a repeating unit having a phenolic hydroxyl group. 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).

[0245]

[0246] The structural formula of the repeating unit is shown below.

[0247]

[0248]

[0249] <Photoacid generator and acid diffusion controller> Compounds containing a cation and anion in a molar ratio of 1:1, as shown in Tables 4 to 6 below, were used as photoacid generators and acid diffusion controllers. The structural formulas of the cations and anions are shown below. Me represents a methyl group.

[0250]

[0251] Photoacid generators containing a cation and an anion are compounds that generate an acid upon irradiation with actinic rays or radiation. Furthermore, acid diffusion controllers containing a cation and an anion are compounds that change into an acid upon irradiation with actinic rays or radiation. The acid generated from the photoacid generator and the acid into which the acid diffusion controller changes are the conjugate acid of the anion contained in each compound. The pKa of the conjugate acid of each anion is shown in Table 2 below.

[0252]

[0253] The following compound (RQ-3) was also used as an acid diffusion controller. Although RQ-3 is not a compound containing a cation and anion, for convenience, RQ-3 is also listed in the column for types of cations and anions in the table below.

[0254]

[0255] <Hydrophobic Resin> The structural formula, the content (mol %) of each repeating unit, and the 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.

[0256]

[0257] <Surfactant> The surfactants used are as follows: W-1: Megafac R08 (manufactured by DIC Corporation)

[0258] <Solvents> The solvents used are as follows: 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

[0259] <Preparation of Resist Compositions> The components shown in Tables 3 and 4 were dissolved in the solvents shown in each table to prepare solutions with the solid content concentrations shown in the respective tables. These solutions were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions. The resulting resist compositions were used in the examples and comparative examples. In the tables, the "mass %" column indicates the content (mass ratio) of each component relative to the total solid content in the resist composition. The solid content refers to all components other than the solvent. When multiple photoacid generators were used, the table is divided into multiple rows. For example, resist composition R-33 contains 5.0 mass% of a compound composed of cation RC-1 and anion RA-1, and 5.0 mass% of a compound composed of cation RC-2 and anion RA-1 as photoacid generators. In resist compositions that use a surfactant, the surfactant content was 0.1 mass%. The "mass ratio" of the solvent is the content of each solvent listed in the "Type" column relative to the total solvent (the total amount of the solvents listed in the "Type" column). When two or more solvents were used, the type and mass ratio of each solvent was separated by a " / ". The types and mass ratios correspond from left to right.

[0260]

[0261]

[0262] <Pattern Forming Method (1): EB Exposure, Alkali Development (EB-Positive)> The resist composition was applied to 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. Note that similar results were obtained even if the Si wafer was 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). Writing was performed so as to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with a 2.38 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 1:1 line and space resist pattern with a line width of 50 nm.

[0263] <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 irradiation dose) required to resolve a 1:1 line and space resist pattern with a line width of 50 nm was taken as sensitivity (Eop). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose that exhibited the above sensitivity (Eop) was taken as resolution (nm). The smaller this value, the higher the resolution.

[0264] [Exposure Latitude (EL)] The exposure dose (electron beam dose) when resolving a 1:1 line and space pattern with a line width of 50 nm using a critical dimension scanning electron microscope (Hitachi S-9380II) was taken as the sensitivity (Eop). Using the above sensitivity (Eop) as a reference, the exposure dose when the target value of 50 nm was ±10% (i.e., 45 nm and 55 nm) was obtained was determined. Then, the exposure latitude (EL, unit: %) defined by the following formula was calculated. The larger the EL value, the smaller the change in performance due to changes in exposure dose, and the better (superior EL performance). EL (%) = [[(exposure dose at which the line width becomes 55 nm) - (exposure dose at which the line width becomes 45 nm)] / Eop] × 100

[0265] [Stability over time] The exposure dose (electron beam irradiation dose) when a 1:1 line and space pattern with a line width of 50 nm obtained by the method described above was formed was measured and designated as the "exposure dose before aging." Next, each resist composition used above was stored at 40°C for 3 months, and a 1:1 line and space pattern with a line width of 50 nm was formed using the same pattern formation method as described above. The exposure dose (electron beam irradiation dose) when the pattern was formed was measured and designated as the "exposure dose after aging." The sensitivity change rate was calculated and evaluated based on the following formula. In the formula, "|(exposure dose after aging - exposure dose before aging) / exposure dose before aging|" means the absolute value of "(exposure dose after aging - exposure dose before aging) / exposure dose before aging." From the viewpoint of stability over time, the evaluation result of the sensitivity change rate is preferably B or higher in practical terms, and A is more preferable. Sensitivity change rate (%) = |(exposure amount after aging - exposure amount before aging) / exposure amount before aging| x 100 A: Sensitivity change rate is less than 2% B: Sensitivity change rate is 2% or more but less than 4% C: Sensitivity change rate is 4% or more but less than 7% D: Sensitivity change rate is 7% or more

[0266] Table 5 below shows the resist compositions used in each of the Examples and Comparative Examples, as well as the evaluation results of each of the Examples and Comparative Examples.

[0267]

[0268] <Pattern Forming Method (2): EUV Exposure, Alkali Development (EUV-Positive)> The resist composition was applied to a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and then 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 similar results were obtained even if the Si wafer was replaced with a chrome substrate. The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After the exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds and heated at 95°C for 60 seconds to obtain a 1:1 line and space resist pattern with a line width of 50 nm.

[0269] <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 (EUV irradiation dose) required to resolve a 1:1 line and space resist pattern with a line width of 50 nm was taken as sensitivity (Eop). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose that exhibited the above sensitivity (Eop) was taken as resolution (nm). The smaller this value, the higher the resolution.

[0270] [Exposure Latitude (EL)] The exposure dose (EUV irradiation dose) when resolving a 1:1 line and space pattern with a line width of 50 nm using a critical dimension scanning electron microscope (Hitachi S-9380II) was taken as the sensitivity (Eop). Using the above sensitivity (Eop) as a reference, the exposure dose when the target value of 50 nm was ±10% (i.e., 45 nm and 55 nm) was obtained was determined. Then, the exposure latitude (EL, unit: %) defined by the following formula was calculated. The larger the EL value, the smaller the change in performance due to changes in exposure dose, and the better (superior EL performance). EL (%) = [[(exposure dose at which the line width becomes 55 nm) - (exposure dose at which the line width becomes 45 nm)] / Eop] × 100

[0271] [Stability over time] The exposure dose (EUV irradiation dose) when a 1:1 line and space pattern with a line width of 50 nm obtained by the method described above was formed was measured and designated as the "exposure dose before aging." Next, each resist composition used above was stored at 40°C for 3 months, and a 1:1 line and space pattern with a line width of 50 nm was formed using the same pattern formation method as described above. The exposure dose (EUV irradiation dose) when the pattern was formed was measured and designated as the "exposure dose after aging." The sensitivity change rate was calculated and evaluated based on the following formula. In the formula, "|(exposure dose after aging - exposure dose before aging) / exposure dose before aging|" means the absolute value of "(exposure dose after aging - exposure dose before aging) / exposure dose before aging." From the viewpoint of stability over time, the evaluation result of the sensitivity change rate is preferably B or higher in practical terms, and A is more preferable. Sensitivity change rate (%) = |(exposure amount after aging - exposure amount before aging) / exposure amount before aging| x 100 A: Sensitivity change rate is less than 1% B: Sensitivity change rate is 1% or more but less than 2% C: Sensitivity change rate is 2% or more but less than 5% D: Sensitivity change rate is 5% or more

[0272] Table 6 below shows the resist compositions used in each of the Examples and Comparative Examples, as well as the evaluation results of each of the Examples and Comparative Examples.

[0273]

[0274] The results in Tables 5 and 6 show that the resist compositions used in the examples are excellent in resolution, EL performance, and stability over time.

[0275] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution, EL performance, and stability over time. The present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0276] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-025699) filed on February 22, 2024, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and an acid diffusion controller, wherein the resin contains a repeating unit (UA) having a group that decomposes under the action of an acid and increases polarity, and a repeating unit (UB) having a phenolic hydroxyl group, and also contains a repeating unit (U1) having at least one group represented by the following formula (1): the photoacid generator contains a compound having at least one of a sulfonium cation and an iodonium cation, and the acid diffusion controller contains a compound having at least one of a sulfonium cation and an iodonium cation. In formula (1), R １ represents a hydrogen atom or a substituent. １ represents an alkylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a heteroarylene group, an alkenylene group, or an alkynylene group. １ represents a group represented by any one of the following formulas (T-1) to (T-3). １ , S １ and T １ At least two of R may be bonded to form a ring. １ , S １ and T １ At least one of these may be bonded to a group other than the group represented by formula (1) in the repeating unit (U1) to form a ring. * indicates the bonding position. In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom. In formula (T-2), k3 represents 0 or 1. Ｔ３ and R Ｔ４ each independently represents a hydrogen atom or a substituent. Ｔ２ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom. In formula (T-3), L １ represents an alkenylene group or an alkynylene group. Ｔ５ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. # represents the bonding position to the nitrogen atom.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (UA) is a repeating unit represented by the following formula (b-1): In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. 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. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. 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. ｂ１ Is L ｂ１ may be bonded to the aromatic ring to which 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (U1) is a repeating unit different from the repeating unit (UA).

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (U1) is a repeating unit represented by the following formula (2): In formula (2), R ２ represents a hydrogen atom, an alkyl group or a halogen atom. ２ represents a single bond or a divalent linking group. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the formulas (T-1) to (T-3). ２ , R ２ , R ３ , S ２ and T ２ At least two of these may be bonded to form a ring.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (U1) is a repeating unit represented by the following formula (3): In formula (3), k4 represents 0 or 1. ２ represents an alkylene group, an arylene group, or a heteroarylene group. ３ represents a hydrogen atom or a substituent. ２ represents a group represented by any one of the formulae (T-1) to (T-3).

6. T in the formula (1) １ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein: represents a group represented by the following formula (T-1-1): In formula (T-1-1), R Ｔ６ and R Ｔ７ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; k2 represents 0 or 1. Ar Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position to the nitrogen atom.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the acid diffusion controller is 50 mol % or more based on the content of the photoacid generator.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the acid diffusion controller is 100 mol % or more based on the content of the photoacid generator.

9. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8.

10. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

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

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