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

Abstract

The present invention provides an active-ray-sensitive or radiation-sensitive resin composition comprising a resin (A) which comprises: a repeating unit (a-1) that contains at least a phenolic hydroxyl group and an aromatic ring in which two or more aromatic rings are fused together or an aromatic ring in which two or more aromatic rings are linked via a single bond; and a repeating unit (a-2) that contains at least an aromatic ring in which two or more aromatic rings are fused together or an aromatic ring in which two or more aromatic rings are linked via a single bond, and a structure which is protected by a group from which a phenolic hydroxyl group or a carboxyl group is detachable by the action of acid. In the resin (A), the sum of the repeating units (a-1) and the repeating units (a-2) is not less than 80 mol% of the sum of all repeating units. The resin (A) has a weight-average molecular weight of 5000 or less.

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] For example, Patent Document 1 describes a resist composition using a polymer compound containing a repeating unit derived from vinylnaphthalene having a carboxyl group substituted with an acid labile group, and Patent Document 2 describes a resist composition containing a compound containing a phenolic hydroxyl group and a group in which the hydrogen atom of the phenolic hydroxyl group is substituted with a protecting group having a specific acetal structure.

[0005] Japanese Patent Publication No. 2007-254495 Japanese Patent Publication No. 2013-214053

[0006] However, in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less), there is a strong demand for improvements in resolution and line width roughness (LWR) performance. LWR performance refers to the ability to reduce the LWR of a pattern. In addition, in the formation of ultrafine patterns, there is also a demand for improvements in PEB temperature dependency, which is the difference in line width depending on the temperature of post-exposure bake (PEB) after exposure to actinic rays or radiation.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can suppress pattern line width fluctuations that depend on PEB temperature when forming ultrafine patterns (e.g., line widths or space widths of 50 nm or less). Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method that use the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] An actinic ray- or radiation-sensitive resin composition containing a resin (A) having the following repeating units (a-1) and (a-2), wherein the sum of the repeating units (a-1) and (a-2) accounts for 80 mol % or more of all repeating units, and the resin (A) has a weight-average molecular weight of 5,000 or less: (a-1) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a phenolic hydroxyl group; (a-2) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a structure in which the phenolic hydroxyl group or carboxyl group is protected by a group that is cleaved by the action of an acid.

[0010] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a-2) is a repeating unit having a structure in which a phenolic hydroxyl group in the repeating unit (a-1) is protected with a group that leaves under the action of an acid. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit (a-1) is a repeating unit represented by the following general formula (b-1), and the repeating unit (a-2) is a repeating unit represented by the following general formula (b-2):

[0011]

[0012] In general formula (b-1), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ represents a single bond or —C(═O)O—. １ represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｂ４ represents a substituent other than a hydroxyl group. p represents an integer of 1 or more. q represents an integer of 0 or more. When q is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ１ , R ｂ２ , or R ｂ３may be linked to form a ring. ｂ２ or R ｂ３ And, Ar １ may be bonded to each other to form a ring.

[0013]

[0014] In general formula (b-2), R ｂ５ ~R ｂ７ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ２ represents a single bond or —C(═O)O—. ２ represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ is -OR Ｐ１ represents a substituent other than the group represented by the formula: r represents an integer of 1 or more; s represents an integer of 0 or more; when s is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , and R ｂ７ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ And, Ar ２ may be bonded to each other to form a ring.

[0015] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the sum of the repeating units (a-1) and the repeating units (a-2) is 90 mol % or more of all repeating units.

[0016] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (A) is a resin constituted only by the repeating unit (a-1) and the repeating unit (a-2).

[0017] [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the repeating unit (a-1) is a repeating unit represented by the following general formula (b-11), and the repeating unit (a-2) is a repeating unit represented by the following general formula (b-21):

[0018]

[0019] In general formula (b-11), R ｂ１ ~R ｂ３ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ４ represents a substituent other than a hydroxyl group. p11 represents an integer of 1 to 7. q11 represents an integer of 0 to (7-p11). When q11 is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ２ or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ The naphthalene rings bonded to the main chain may be bonded to each other to form a ring.

[0020]

[0021] In general formula (b-21), R ｂ５ ~R ｂ７ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ Ha-OR ｐ１ represents a substituent other than the group represented by the formula: r11 represents an integer of 1 to 7. s11 represents an integer of 0 to (7-r11). When s11 is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７The naphthalene rings bonded to the main chain may be bonded to each other to form a ring.

[0022] [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the repeating unit (a-2) contains one structure in which a phenolic hydroxyl group is protected with a group that is cleaved by the action of an acid.

[0023] [8] R in the above general formula (b-2) ｐ１ is a group represented by the following formula (ALG1) or formula (ALG2):

[0024]

[0025] In formula (ALG1), R ＡＬ１ ~R ＡＬ２ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. * represents a bond.

[0026]

[0027] In formula (ALG2), R ＡＬ３ ~R ＡＬ５ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. ＡＬ３ ~R ＡＬ５ Two of the may be bonded to each other to form a ring. * represents a bond.

[0028] [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], further comprising a compound that generates an acid upon irradiation with actinic rays or radiation.

[10] 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 [9].

[0029]

[11] A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition according to any one of [1] to [9]; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

[12] A method for producing an electronic device, comprising the pattern forming method according to

[11] .

[0030] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can suppress pattern line width fluctuations that depend on PEB temperature when forming ultrafine patterns (e.g., line widths or space widths of 50 nm or less). The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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).

[0035] 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:

[0036] (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, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl 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 (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0037] 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".

[0038] 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).

[0039] 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.

[0040] 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.

[0041] 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.

[0042] <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") contains a resin (A) having the following repeating units (a-1) and (a-2), wherein the sum of the repeating units (a-1) and (a-2) accounts for 80 mol % or more of all repeating units, and the resin (A) has a weight-average molecular weight of 5,000 or less: (a-1) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a phenolic hydroxyl group; (a-2) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a structure in which the phenolic hydroxyl group or carboxyl group is protected by a group that is cleaved by the action of an acid.

[0043] According to the composition of the present invention, by adopting the above-described configuration, it is possible to obtain an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance in the formation of an ultrafine pattern (for example, a line width or space width of 50 nm or less), and that can suppress fluctuations in the line width of the pattern that depend on the PEB temperature, although the detailed reason is not clear.

[0044] The composition of the present invention is typically a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a 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 typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0045] [Resin (A)] The resin (A) contained in the composition of the present invention has the following repeating units (a-1) and (a-2), the sum of the repeating units (a-1) and (a-2) being 80 mol % or more of all repeating units, and the weight average molecular weight is 5,000 or less: (a-1) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a phenolic hydroxyl group; (a-2) a repeating unit containing at least an aromatic ring in which two or more aromatic rings are condensed or an aromatic ring in which two or more aromatic rings are linked by a single bond, and a structure in which the phenolic hydroxyl group or carboxyl group is protected by a group that is cleaved by the action of an acid.

[0046] The repeating unit (a-1) and the repeating unit (a-2) may be the same repeating unit. That is, a repeating unit containing at least an aromatic ring formed by condensing two or more aromatic rings or an aromatic ring formed by connecting two or more aromatic rings with a single bond, a phenolic hydroxyl group, and a structure in which the phenolic hydroxyl group or the carboxyl group is protected by a group that is cleaved by the action of an acid corresponds to the repeating unit (a-1) and also corresponds to the repeating unit (a-2).

[0047] Each repeating unit will be explained below. In this specification, the phenolic hydroxyl group refers to a hydroxyl group bonded to an aromatic hydrocarbon group.

[0048] (Repeating Unit (a-1)) The repeating unit (a-1) is a repeating unit containing at least an aromatic ring formed by condensing two or more aromatic rings or an aromatic ring formed by linking two or more aromatic rings with a single bond, and a phenolic hydroxyl group.

[0049] The aromatic ring formed by condensing two or more aromatic rings is preferably an aromatic hydrocarbon ring or aromatic heterocycle having 10 to 24 carbon atoms, and examples of the aromatic hydrocarbon ring include a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluoranthene ring. Examples of the aromatic heterocycle include a benzothiophene ring, a benzofuran ring, a benzoselenophene ring, a benzoxazole ring, a benzothiazole ring, a bithiophene ring, a dibenzothiophene ring, and a dibenzofuran ring. The aromatic ring formed by condensing two or more aromatic rings may further be condensed with a non-aromatic ring.

[0050] The aromatic ring in which two or more aromatic rings are linked by a single bond is preferably an aromatic ring having at least one structure in which a monocyclic or polycyclic aromatic hydrocarbon ring or aromatic heterocycle is linked by a single bond to another monocyclic or polycyclic aromatic hydrocarbon ring or aromatic heterocycle. Examples of the monocyclic or polycyclic aromatic hydrocarbon ring include aromatic hydrocarbon rings having 6 to 24 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring. Examples of the aromatic heterocycle include aromatic heterocycles having 5 to 24 carbon atoms, such as a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, an oxazole ring, a benzothiophene ring, a benzofuran ring, a benzoselenophene ring, a benzoxazole ring, a benzothiazole ring, a bithiophene ring, a dibenzothiophene ring, and a dibenzofuran ring.

[0051] The repeating unit (a-1) is preferably a repeating unit represented by the following general formula (b-1):

[0052]

[0053] In general formula (b-1), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ represents a single bond or —C(═O)O—. １ represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｂ４represents a substituent other than a hydroxyl group. p represents an integer of 1 or more. q represents an integer of 0 or more. When q is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ１ , R ｂ２ , or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ And, Ar １ may be bonded to each other to form a ring.

[0054] In general formula (b-1), R ｂ１ ~R ｂ３ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ ~R ｂ３ The alkyl group represented by 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. ｂ１ ~R ｂ３ The aryl group represented by is not particularly limited in the number of carbon atoms, but preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and is even more preferably a phenyl group.

[0055] R ｂ１ ~R ｂ３ preferably represents a hydrogen atom. ｂ１ , R ｂ２ represents a hydrogen atom, R ｂ３ Ar １ and a single bond to form a ring are also preferred.

[0056] In general formula (b-1), L ｂ１ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0057] In general formula (b-1), Ar １represents an aromatic ring group in which two or more aromatic rings are fused, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. Examples of the aromatic ring group in which two or more aromatic rings are fused and the aromatic ring group in which two or more aromatic rings are linked by a single bond include aromatic ring groups in which any (p+q+1) hydrogen atoms have been removed from the above-mentioned aromatic ring in which two or more aromatic rings are fused and the aromatic ring in which two or more aromatic rings are linked by a single bond.

[0058] In general formula (b-1), R ｂ４ represents a substituent other than a hydroxyl group, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, and a carboxy group.

[0059] R ｂ４ The alkyl group in R may be linear or branched. The alkyl group may have a substituent. ｂ４ The alkyl group of R is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. ｂ４ The alkyl group in the alkoxy group, alkylthio group, alkyloxycarbonyl group, and alkylcarbonyloxy group is R ｂ４ The preferred ranges are the same as those of the alkyl group.

[0060] R ｂ４ The aryl group in R may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may have a substituent. ｂ４ The aryl group in R is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. ｂ４ The aryl group in the aryloxycarbonyl group and arylcarbonyloxy group is R ｂ４ The preferred ranges are the same as those of the aryl group represented by the formula (I) and (II).

[0061] R ｂ４The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The heteroaryl group may have a substituent. ｂ４ The heteroaryl group of R is preferably a heteroaryl group having 5 to 9 carbon atoms, and examples thereof include a thiophenyl group, a furanyl group, a benzothiophenyl group, and a benzofuranyl group. ｂ４ The heteroaryl group in the heteroaryloxycarbonyl group and heteroarylcarbonyloxy group is R ｂ４ The preferred ranges are the same as those of the heteroaryl group represented by the formula (I) and (II), and the preferred ranges are also the same.

[0062] In general formula (b-1), p represents an integer of 1 or greater. The upper limit of p is not particularly limited, but is, for example, 20. p is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 or 2, and still more preferably 1. In general formula (b-1), q represents an integer of 0 or greater. The upper limit of q is not particularly limited, but is, for example, 20. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, preferably 0 or 1, and more preferably 0. p+q is preferably 20 or less, more preferably 15 or less, and more preferably 10 or less.

[0063] The repeating unit (a-1) is more preferably a repeating unit represented by the following general formula (b-1-1) or a repeating unit represented by the following general formula (b-1-2).

[0064]

[0065] In general formula (b-1-1), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ represents a single bond or —C(═O)O—. ｂ４ represents a substituent other than a hydroxyl group. t1 represents 1 or 2. p1 represents an integer of 1 to (5+2×t1). q1 represents an integer of 0 to (5+2×t1-p1). When q1 is 2 or more, multiple R ｂ４ may be the same or different and may be bonded to each other to form a ring.ｂ４ is R ｂ１ , R ｂ２ , or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ And L ｂ１ The aromatic rings to which are bonded may be bonded to each other to form a ring.

[0066] R in general formula (b-1-1) ｂ１ ~R ｂ３ , L ｂ１ and R ｂ４ represents R in the general formula (b-1) ｂ１ ~R ｂ３ , L ｂ１ and R ｂ４ The same applies to preferred examples.

[0067] In general formula (b-1-1), t1 represents 1 or 2, preferably 1. In general formula (b-1-1), p1 represents an integer of 1 to (5+2×t1), preferably 1 or 2, more preferably 1. In general formula (b-1-1), q1 represents an integer of 0 to (5+2×t1-p1), preferably 0 or 1, more preferably 0.

[0068]

[0069] In general formula (b-1-2), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ represents a single bond or —C(═O)O—. ｂ４ represents a substituent other than a hydroxyl group. t2 represents an integer of 1 to 3. p2 represents an integer of 1 to (4×t2+5). q2 represents an integer of 0 to (4×t2+5-p2). When q2 is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ２ , or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ And L ｂ１ The aromatic rings to which are bonded may be bonded to each other to form a ring.

[0070] R in general formula (b-1-2) ｂ１ ~R ｂ３ , L ｂ１ and R ｂ４ represents R in the general formula (b-1) ｂ１ ~R ｂ３ , L ｂ１ and R ｂ４ The same applies to preferred examples.

[0071] In general formula (b-1-2), t2 represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1. In general formula (b-1-2), p2 represents an integer of 1 to (4×t2+5), preferably 1 or 2, and more preferably 1. In general formula (b-1-2), q2 represents an integer of 0 to (4×t2+5-p2), preferably 0 or 1, and more preferably 0.

[0072] The repeating unit (a-1) is more preferably a repeating unit represented by the following general formula (b-11) or a repeating unit represented by the following general formula (b-12), and is particularly preferably a repeating unit represented by the following general formula (b-11):

[0073]

[0074] In general formula (b-11), R ｂ１ ~R ｂ３ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ４ represents a substituent other than a hydroxyl group. p11 represents an integer of 1 to 7. q11 represents an integer of 0 to (7-p11). When q11 is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ２ , or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ The naphthalene rings bonded to the main chain may be bonded to each other to form a ring.

[0075] R in general formula (b-11) ｂ１ ~R ｂ３ and R ｂ４represents R in the general formula (b-1) ｂ１ ~R ｂ３ and R ｂ４ The same applies to preferred examples.

[0076] In general formula (b-11), p11 represents an integer of 1 to 7, preferably 1 or 2, and more preferably 1. In general formula (b-11), q11 represents an integer of 0 to (7-p11), preferably 0 or 1, and more preferably 0.

[0077]

[0078] In general formula (b-12), R ｂ１ ~R ｂ３ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ４ represents a substituent other than a hydroxyl group. p21 represents an integer of 1 to 9. q21 represents an integer of 0 to 8. When q21 is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ２ or R ｂ３ may be linked to form a ring. ｂ２ or R ｂ３ The aromatic rings (biphenyl) bonded to the main chain may be bonded to each other to form a ring.

[0079] R in general formula (b-12) ｂ１ ~R ｂ３ and R ｂ４ represents R in the general formula (b-1) ｂ１ ~R ｂ３ and R ｂ４ The same applies to preferred examples.

[0080] In general formula (b-12), p21 represents an integer of 1 to 9, preferably 1 or 2, and more preferably 1. In general formula (b-12), q21 represents an integer of 0 to 8, preferably 0 or 1, and more preferably 0.

[0081] Specific examples of the repeating unit (a-1) are shown below, but the present invention is not limited to these.

[0082]

[0083]

[0084] Specific examples of the monomer corresponding to the repeating unit (a-1) are shown below, but the present invention is not limited to these.

[0085]

[0086]

[0087] The content of the repeating unit (a-1) is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 30 mol % or more, based on all repeating units in the resin (A), and the content of the repeating unit (a-1) is preferably 90 mol % or less, more preferably 80 mol % or less, based on all repeating units in the resin (A).

[0088] The repeating unit (a-1) contained in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0089] (Repeating Unit (a-2)) The repeating unit (a-2) is a repeating unit containing at least an aromatic ring formed by condensing two or more aromatic rings or an aromatic ring formed by linking two or more aromatic rings with a single bond, and a structure in which a phenolic hydroxyl group or a carboxyl group is protected with a group that is cleaved by the action of an acid.

[0090] As for the aromatic ring formed by condensing two or more aromatic rings and the aromatic ring formed by linking two or more aromatic rings via a single bond, the same explanation as given above for the aromatic ring formed by condensing two or more aromatic rings and the aromatic ring formed by linking two or more aromatic rings via a single bond, which are contained in the repeating unit (a-1), can be directly applied.

[0091] The structure in which the phenolic hydroxyl group or carboxyl group in the repeating unit (a-2) is protected with a group that is cleaved by the action of an acid is a structure in which a phenolic hydroxyl group or carboxyl group as a polar group is protected with a group that is cleaved by the action of an acid, that is, a group that decomposes under the action of an acid and increases in polarity (also referred to as an "acid-decomposable group"). That is, the resin (A) is an acid-decomposable resin, and in a pattern formation method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is suitably formed. Typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.

[0092] Examples of the group that leaves when acted upon by an acid (leaving group) 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)

[0093] 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 ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of the Rx are preferably methyl groups. Each of the above groups may further have a substituent. １ ~Rx ３each 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 of Rx 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 tricyclodecanyl 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, such as a phenyl group or a naphthyl group. The aryl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl 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 ３The 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 tricyclodecanyl 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.

[0094] 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. ３８ The 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.

[0095] 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.

[0096] The repeating unit (a-2) preferably contains a structure in which a phenolic hydroxyl group is protected with a group that is cleaved by the action of an acid, and more preferably contains one structure in which a phenolic hydroxyl group is protected with a group that is cleaved by the action of an acid.

[0097] The repeating unit (a-2) is preferably a repeating unit represented by the following general formula (b-2) or (b-3), and more preferably a repeating unit represented by the following general formula (b-2).

[0098]

[0099] In general formula (b-2), R ｂ５ ~R ｂ７ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ２ represents a single bond or —C(═O)O—. ２ represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ is -OR Ｐ１ represents a substituent other than the group represented by the formula: r represents an integer of 1 or more; s represents an integer of 0 or more; when s is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ And, Ar ２ may be bonded to each other to form a ring.

[0100] In general formula (b-2), Rｂ５ ~R ｂ７ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ５ ~R ｂ７ The alkyl group and aryl group represented by R in general formula (b-1) ｂ１ ~R ｂ３ Examples of the alkyl group include alkyl groups and aryl groups, and preferred examples are also the same.

[0101] R ｂ５ ~R ｂ７ preferably represents a hydrogen atom. ｂ５ , R ｂ６ represents a hydrogen atom, R ｂ７ Ar ２ and a single bond to form a ring are also preferred.

[0102] In general formula (b-2), L ｂ２ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0103] In general formula (b-2), Ar ２ represents an aromatic ring group in which two or more aromatic rings are fused, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. Examples of the aromatic ring group in which two or more aromatic rings are fused and the aromatic ring group in which two or more aromatic rings are linked by a single bond include aromatic ring groups in which any (r+s+1) hydrogen atoms have been removed from the above-mentioned aromatic ring in which two or more aromatic rings are fused and the aromatic ring in which two or more aromatic rings are linked by a single bond.

[0104] In general formula (b-2), R ｐ１ represents a group which is eliminated by the action of an acid. Examples of the group which is eliminated by the action of an acid 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.

[0105] R ｐ１ is preferably a group represented by the following formula (ALG1) or formula (ALG2).

[0106]

[0107] In formula (ALG1), RＡＬ１ ~R ＡＬ２ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. * represents a bond.

[0108] R ＡＬ１ ~R ＡＬ２ The alkyl group in R may be linear or branched. The alkyl group may have a substituent. ＡＬ１ ~R ＡＬ２ The alkyl group of R is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. ＡＬ１ ~R ＡＬ２ The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The cycloalkyl group may have a substituent. ＡＬ１ ~R ＡＬ２ The cycloalkyl group 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 tricyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have, for example, one methylene group constituting the ring substituted with a heteroatom such as an oxygen atom or a sulfur atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0109] R ＡＬ１ ~R ＡＬ２ The aryl group in R may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may have a substituent. ＡＬ１ ~R ＡＬ２ The aryl group in R is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. ＡＬ１ ~R ＡＬ２The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The heteroaryl group may have a substituent. ＡＬ１ ~R ＡＬ２ The heteroaryl group is preferably a heteroaryl group having 5 to 9 carbon atoms, and examples thereof include a thiophenyl group, a furanyl group, a benzothiophenyl group, and a benzofuranyl group.

[0110]

[0111] In formula (ALG2), R ＡＬ３ ~R ＡＬ５ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. ＡＬ３ ~R ＡＬ５ Two of the may be bonded to each other to form a ring. * represents a bond.

[0112] R ＡＬ３ ~R ＡＬ５ The alkyl group, cycloalkyl group, aryl group, and heteroaryl group of R ＡＬ１ ~R ＡＬ２ Examples of the alkyl group, cycloalkyl group, aryl group, and heteroaryl group are the same as those of the alkyl group, cycloalkyl group, aryl group, and heteroaryl group, and the preferred ranges are also the same.

[0113] R ＡＬ３ ~R ＡＬ５ Two of R may be bonded to each other to form a ring. ＡＬ３ ~R ＡＬ５ When two of R are bonded to each other to form a ring, the formed ring may be a monocyclic ring or a polycyclic ring. The formed ring is preferably a cycloalkane ring. ＡＬ３ ~R ＡＬ５ The ring formed by bonding two of R ＡＬ３ ~R ＡＬ５The cycloalkane ring formed by bonding two of these is preferably a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring. Polycyclic cycloalkane rings such as a norbornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring are also preferred. Of these, a monocyclic cycloalkane ring having 5 to 6 carbon atoms is preferred. ＡＬ３ ~R ＡＬ５ In the cycloalkane ring formed by bonding two of the above, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group, and one or more of the ethylene groups constituting the ring may be replaced with a vinylene group.

[0114] In general formula (b-2), R ｂ８ is -OR Ｐ１ R represents a substituent other than the group represented by ｂ８ represents -OR Ｐ１ Examples of the substituent other than the group represented by the formula (I) include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, and a carboxy group.

[0115] R ｂ８ The alkyl group in R may be linear or branched. The alkyl group may have a substituent. ｂ８ The alkyl group of R is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. ｂ８ The alkyl group in the alkoxy group, alkylthio group, alkyloxycarbonyl group, and alkylcarbonyloxy group is R ｂ８ The preferred ranges are the same as those of the alkyl group.

[0116] R ｂ８The aryl group in R may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may have a substituent. ｂ８ The aryl group in R is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. ｂ８ The aryl group in the aryloxycarbonyl group and arylcarbonyloxy group is R ｂ８ The preferred ranges are the same as those of the aryl group represented by the formula (I) and (II).

[0117] R ｂ８ The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The heteroaryl group may have a substituent. ｂ８ The heteroaryl group of R is preferably a heteroaryl group having 5 to 9 carbon atoms, and examples thereof include a thiophenyl group, a furanyl group, a benzothiophenyl group, and a benzofuranyl group. ｂ８ The heteroaryl group in the heteroaryloxycarbonyl group and heteroarylcarbonyloxy group is R ｂ４ As described above, the preferred ranges of the heteroaryl group R ｂ８ is -OR Ｐ１ represents a substituent other than the group represented by -OR Ｐ１ It does not include a group represented by the following formula:

[0118] In general formula (b-2), r represents an integer of 1 or greater. The upper limit of r is not particularly limited, but is, for example, 20. r is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 or 2, and still more preferably 1. In general formula (b-2), s represents an integer of 0 or greater. The upper limit of s is not particularly limited, but is, for example, 20. s is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, preferably 0 or 1, and more preferably 0. r+s is preferably 20 or less, more preferably 15 or less, and more preferably 10 or less.

[0119]

[0120] In general formula (b-3), R ｂ９ ~R ｂ１１ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ３ represents a single bond or —C(═O)O—. ３ represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｂ４ represents a single bond or a divalent linking group. ｐ２ represents a group that is eliminated by the action of an acid. ｂ１２ Is, -L ｂ４ -C(=O)OR Ｐ２ v represents an integer of 1 or more. w represents an integer of 0 or more. When w is 2 or more, a plurality of R ｂ１２ may be the same or different and may be bonded to each other to form a ring. ｂ１２ is R ｂ１０ , R ｂ１１ , and R ｐ２ may be linked to any one of R to form a ring. ｂ１０ or R ｂ１１ And, Ar ３ may be bonded to each other to form a ring.

[0121] In general formula (b-3), R ｂ９ ~R ｂ１１ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ９ ~R ｂ１１ The alkyl group and aryl group represented by R in general formula (b-1) ｂ１ ~R ｂ３ Examples of the alkyl group include alkyl groups and aryl groups, and preferred examples are also the same.

[0122] In general formula (b-3), L ｂ３ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0123] In general formula (b-3), Ar ３represents an aromatic ring group in which two or more aromatic rings are fused, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. Examples of the aromatic ring group in which two or more aromatic rings are fused and the aromatic ring group in which two or more aromatic rings are linked by a single bond include aromatic ring groups in which any (v+w+1) hydrogen atoms have been removed from the above-mentioned aromatic ring in which two or more aromatic rings are fused and the aromatic ring in which two or more aromatic rings are linked by a single bond.

[0124] In general formula (b-3), L ｂ４ represents a single bond or a divalent linking group. ｂ４ Examples of the divalent linking group represented by the formula include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. ｂ４ is preferably a single bond.

[0125] In general formula (b-3), R ｐ２ represents a group which is eliminated by the action of an acid. Examples of the group which is eliminated by the action of an acid include the groups represented by the above formulae (Y1) to (Y4), and the group represented by the above formula (ALG2) is preferred. -C(=O)OR in general formula (b-3) ｐ２ is converted to R by the action of an acid. ｐ２ is eliminated to produce a carboxyl group.

[0126] In general formula (b-3), R ｂ１２ Is, -L ｂ４ -C(=O)OR Ｐ２ R represents a substituent other than the group represented by ｂ１２ represents -L ｂ４ -C(=O)OR Ｐ２ Examples of the substituent other than the group represented by R include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, and a carboxy group. ｂ１２The alkyl group, alkoxy group, alkylthio group, aryl group, heteroaryl group, alkyloxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, and heteroarylcarbonyloxy group are R ｂ８ Examples of the alkyl group, alkoxy group, alkylthio group, aryl group, heteroaryl group, alkyloxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, and heteroarylcarbonyloxy group mentioned above can be mentioned, and the preferred ranges are also the same.

[0127] In general formula (b-3), v represents an integer of 1 or greater. The upper limit of v is not particularly limited, but is, for example, 20. v is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 or 2, and still more preferably 1. In general formula (b-3), w represents an integer of 0 or greater. The upper limit of w is not particularly limited, but is, for example, 20. w is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, preferably 0 or 1, and more preferably 0. v+w is preferably 20 or less, more preferably 15 or less, and more preferably 10 or less.

[0128] The repeating unit (a-2) is more preferably a repeating unit represented by the following general formula (b-2-1) or a repeating unit represented by the following general formula (b-2-2).

[0129]

[0130] In general formula (b-2-1), R ｂ５ ~R ｂ７ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ２ represents a single bond or —C(═O)O—. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ is -OR Ｐ１represents a substituent other than the group represented by the formula: u1 represents 1 or 2. r1 represents an integer of 1 to (5+2×u1). s1 represents an integer of 0 to (5+2×u1-r1). When s1 is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ And L ｂ２ The aromatic rings to which are bonded may be bonded to each other to form a ring.

[0131] R in general formula (b-2-1) ｂ５ ~R ｂ７ , L ｂ２ , R ｐ１ , and R ｂ８ represents R in the general formula (b-2) ｂ５ ~R ｂ７ , L ｂ２ , R ｐ１ , and R ｂ８ The same applies to preferred examples.

[0132] In general formula (b-2-1), u1 represents 1 or 2, preferably 1. In general formula (b-2-1), r1 represents an integer of 1 to (5+2×u1), preferably 1 or 2, more preferably 1. In general formula (b-2-1), s1 represents an integer of 0 to (5+2×u1-r1), preferably 0 or 1, more preferably 0.

[0133]

[0134] In general formula (b-2-2), R ｂ５ ~R ｂ７ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ２ represents a single bond or —C(═O)O—. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ is -OR Ｐ１u2 represents an integer of 1 to 3. r2 represents an integer of 1 to (u2×4+5). s2 represents an integer of 0 to (u2×4+5−r2). When s2 is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ And L ｂ２ The aromatic rings to which are bonded may be bonded to each other to form a ring.

[0135] R in general formula (b-2-2) ｂ５ ~R ｂ７ , L ｂ２ , R ｐ１ , and R ｂ８ represents R in the general formula (b-2) ｂ５ ~R ｂ７ , L ｂ２ , R ｐ１ , and R ｂ８ The same applies to preferred examples.

[0136] In general formula (b-2-2), u2 represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1. In general formula (b-2-2), r2 represents an integer of 1 to (u2×4+5), preferably 1 or 2, and more preferably 1. In general formula (b-2-2), s2 represents an integer of 0 to (u2×4+5−r2), preferably 0 or 1, and more preferably 0.

[0137] The repeating unit (a-2) is more preferably a repeating unit represented by the following general formula (b-21) or a repeating unit represented by the following general formula (b-22), and is particularly preferably a repeating unit represented by the above general formula (b-21).

[0138]

[0139] In general formula (b-21), R ｂ５ ~R ｂ７R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ Ha-OR ｐ１ represents a substituent other than the group represented by the formula: r11 represents an integer of 1 to 7. s11 represents an integer of 0 to (7-r11). When s11 is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ The naphthalene rings bonded to the main chain may be bonded to each other to form a ring.

[0140] R in general formula (b-21) ｂ５ ~R ｂ７ , R ｐ１ , and R ｂ８ represents R in the general formula (b-2) ｂ５ ~R ｂ７ , R ｐ１ , and R ｂ８ The same applies to preferred examples.

[0141] In general formula (b-21), r11 represents an integer of 1 to 7, preferably 1 or 2, and more preferably 1. In general formula (b-21), s11 represents an integer of 0 to (7-r11), preferably 0 or 1, and more preferably 0.

[0142]

[0143] In general formula (b-22), R ｂ５ ~R ｂ７ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｐ１ represents a group that is eliminated by the action of an acid. ｂ８ represents a substituent other than a hydroxyl group. r21 represents an integer of 1 to 9. s21 represents an integer of 0 to 8. When s21 is 2 or more, a plurality of R ｂ８may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of R to form a ring. ｂ６ or R ｂ７ The aromatic rings bonded to the main chain may be bonded to each other to form a ring.

[0144] R in general formula (b-22) ｂ５ ~R ｂ７ , R ｐ１ , and R ｂ８ represents R in the general formula (b-2) ｂ５ ~R ｂ７ , R ｐ１ , and R ｂ８ The same applies to preferred examples.

[0145] In general formula (b-22), r21 represents an integer of 1 to 9, preferably 1 or 2, and more preferably 1. In general formula (b-22), s21 represents an integer of 0 to 8, preferably 0 or 1, and more preferably 0.

[0146] Specific examples of the repeating unit (a-2) are shown below, but the present invention is not limited to these. In the formula, 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. Z represents a substituent, and when a plurality of Zs are present, each Z is independent. p represents 0 or a positive integer.

[0147]

[0148]

[0149]

[0150] The content of the repeating unit (a-2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all repeating units in the resin (A), and the content of the repeating unit (a-2) is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on all repeating units in the resin (A).

[0151] The repeating unit (a-2) contained in the resin (A) may be one type or two or more types. When two or more types are contained, the total content thereof is preferably within the above-mentioned suitable content range.

[0152] In the resin (A), the sum of the repeating units (a-1) and (a-2) is 80 mol % or more of all repeating units, and from the viewpoint of improving roughness performance, it is preferably 90 mol % or more, and the resin (A) is more preferably composed only of the repeating units (a-1) and (a-2).

[0153] The repeating unit (a-2) is preferably a repeating unit having a structure in which the phenolic hydroxyl group in the repeating unit (a-1) is protected with a group that is cleaved by the action of an acid.

[0154] It is also preferred that the repeating unit (a-1) is a repeating unit represented by the general formula (b-1) and the repeating unit (a-2) is a repeating unit represented by the general formula (b-2), and it is more preferred that the repeating unit (a-1) is a repeating unit represented by the general formula (b-11) and the repeating unit (a-2) is a repeating unit represented by the general formula (b-21).

[0155] (Other Repeating Units) The resin (A) may contain other repeating units in addition to the repeating units (a-1) and (a-2), as long as the effects of the present invention are not impaired. The other repeating units are described below.

[0156] (Repeating unit having a polar group) The repeating unit having a polar group is a repeating unit different from the repeating unit (a-1) and the repeating unit (a-2). Examples of the polar group of the repeating unit having a polar group include a hydroxyl group, a lactone group, a sultone group, a lactam group, an imide group, an amide group, a sulfonamide group, a carbonate group, a urethane group, a urea group, a nitrile group, a sulfoxide group, and a sulfonyl group. The polar group may be an acid group. The polar group is preferably a hydroxyl group or a lactone group, more preferably an aromatic hydroxyl group, and even more preferably a phenolic hydroxyl group. The repeating unit containing a polar group is preferably a repeating unit represented by the following general formula (S3):

[0157] The repeating unit having a polar group is preferably a repeating unit represented by the following general formula (S3).

[0158]

[0159] In general formula (S3), 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.

[0160] R in general formula (S3) １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0161] R １０１ , R １０２ and R １０３The alkyl group represented by is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0162] R １０１ , R １０２ and R １０３ The cycloalkyl group represented by may be a monocyclic or polycyclic group. Among them, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is preferred. １０１ , R １０２ and R １０３ 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 is preferred. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group represented by R １０１ , R １０２ and R １０３ The same alkyl groups as those in the above are preferred.

[0163] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

[0164] Ar in general formula (S3) 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, for example, a phenylene group or a divalent monocyclic aromatic ring group containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a triazine ring, an imidazole 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 hydroxyl groups. Multiple substituents may be bonded to form a ring. Ar Ａ More preferably, represents a benzene ring group.

[0165] L in general formula (S3) 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 ６４ -, an alkylene group, or a group formed by combining two or more of these groups. ６４ 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 ６４ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0166] The repeating unit represented by general formula (S3) 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.

[0167] Specific examples of repeating units having a polar group are shown below, but are not limited to these.

[0168]

[0169] (Repeating Unit Having an Acid-Decomposable Group) The resin (A) may contain a repeating unit having an acid-decomposable group as another repeating unit. The repeating unit having an acid-decomposable group is a repeating unit different from the repeating unit (a-1) and the repeating unit (a-2).

[0170] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferable that unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0171] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused in the form of a bicyclo structure or a spiro structure, is more preferred. Regarding resin (A), the descriptions of paragraphs

[0120] to

[0134] of WO 2022 / 024928 can be incorporated by reference.

[0172] (Repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the repeating units described above, the resin (A) may have a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). The <repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is preferably different from the above-mentioned <repeating unit having a lactone group, a sultone group, or a carbonate group> and the below-described <repeating unit having a photoacid-generating group>.

[0173] The unit X is preferably a repeating unit represented by formula (C).

[0174]

[0175] L ５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0176] (Repeating unit having a photoacid generating group) The resin (A) may have, as a repeating unit other than those described above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (preferably electron beams or extreme ultraviolet rays) (hereinafter also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0177]

[0178] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain. Examples of repeating units having a photoacid generating group are shown below, but are not limited to these.

[0179] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of WO 2018 / 193954 A.

[0180] (Repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formula (V-1) and formula (V-2) are different from the repeating unit (a-1) and the repeating unit (a-2).

[0181]

[0182] In the formula, R ６ and R ７ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0183] (Repeating Unit Having At Least One Type of Group Selected from a Hydroxyl Group, a Cyano Group, and an Alkali-Soluble Group) The resin (A) may have a repeating unit having at least one type of group selected from a hydroxyl group, a cyano group, and an alkali-soluble group.

[0184] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0185] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0186] (Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability) Resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[0187] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0188]

[0189] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP 2014-098921 A.

[0190] In addition to the repeating structural units described above, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0191] The content of other repeating units relative to the total repeating units is 20 mol % or less, preferably 10 mol % or less, more preferably 5 mol % or less, and even more preferably no other repeating units are contained.

[0192] As the resin (A), particularly when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferred that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond.

[0193] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as a polystyrene equivalent value measured by GPC, is 5,000 or less, and from the viewpoint of improving roughness performance, it is preferably 4,500 or less, more preferably 4,000 or less. The lower limit is not particularly limited, but is, for example, 1,000 or more, preferably 1,500 or more. The dispersity (molecular weight distribution, Pd, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 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 properties.

[0194] In the composition of the present invention, the content of resin (A) 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 (A) may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0195] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention preferably contains a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Furthermore, both the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferred. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of -2.0 or more upon irradiation with actinic rays or radiation, and more preferably a compound that generates an acid having a pKa of -2.0 or more and 1.0 or less.

[0196] Examples of the photoacid generator 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, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0197] "M ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation. The organic cation is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. Among them, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0198]

[0199] In the above 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 represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0200] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0201] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0202] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0203] R ２０１ ~R ２０３ Preferred 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 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents if possible, and it is also preferred that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents form an acid-decomposable group in any combination. Note that the acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and is preferably a structure in which the polar group is protected with a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0204] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0205] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0206] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0207]

[0208] In formula (ZaI-3b), R １ｃ ~R ５ｃR each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0209] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0210] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙExamples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0211] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0212] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0213]

[0214] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４represents a hydroxyl group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0215] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0216] Next, formula (ZaII) will be described. 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 ２０５The 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 ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0217] 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.

[0218] "M ＋ X － In the compound represented by the formula "X － represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0219] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0220] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0221] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0222] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0223] 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.

[0224] An example of the sulfonylimide anion is a saccharin anion.

[0225] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0226] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0227] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0228] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0229]

[0230] In formula (AN1), R １ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0231] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0232] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0233] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0234] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-*Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0235] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0236] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by the following formulae (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) is preferred.

[0237]

[0238] The lactone structure or sultone structure may be formed by the substituent (Rb ２ ) may have a preferable substituent (Rb ２ ) includes an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ２ may be different, and a plurality of Rb ２ They may be bonded to each other to form a ring.

[0239] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0240] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0241]

[0242] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0243] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0244] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0245] L represents a divalent linking group. The definition of L is the same as that of L in formula (AN1). When a plurality of L's are present, they may be the same or different.

[0246] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0247] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0248] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0249] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0250] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0251]

[0252] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0253] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0254] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0255] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0256] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0257]

[0258]

[0259] In formula (d1-1), R ５１represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0260] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃ The hydrocarbon group in the formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. ２ｃ -SO ３ － " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z ２ｃ is preferably other than an aryl group. For example, Z ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ － The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0261] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0262] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４may be bonded to each other to form a ring.

[0263] The organic anions may be used singly or in combination of two or more. Preferred examples are shown below.

[0264]

[0265] From the viewpoint of suppressing development defects, the composition of the present invention preferably contains a salt (C) having a group that is decomposed by the action of an acid, and more preferably contains a compound represented by the following general formula (c1) as a photoacid generator:

[0266]

[0267] In general formula (c1), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. A represents a group that decomposes under the action of an acid. When there are multiple As, the multiple As may be the same or different. nc represents an integer of 1 to 5. Xc represents an nc+1-valent linking group. Mc ＋ represents a sulfonium ion or an iodonium ion.

[0268] In formula (c1), L represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L include -CO-, -O-, -S-, -SO-, and -SO ２ Examples of L include -, hydrocarbon groups (for example, alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups), and linking groups in which a plurality of these groups are linked together. Among these, L is preferably an alkylene group, an arylene group, -arylene group-alkylene group having a fluorine atom or an iodine atom-, a -COO-Rt- group, or a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0269] The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ - group, -(CH ２ ) ２ - group, or -(CH ２ ) ３ The - group is more preferred.

[0270] L is particularly preferably an arylene group, an alkylene group, or a single bond, and most preferably a phenylene group or a single bond.

[0271] In general formula (c1), A represents a group that decomposes under the action of an acid. The group that decomposes under the action of an acid preferably has a structure in which a polar group is protected with a group that leaves under the action of an acid (leaving group).

[0272] As the polar group, an alkali-soluble group is preferred, for example, 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 an acidic group such as a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group. Among these, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred, and a carboxyl group or a phenolic hydroxyl group is more preferred. Examples of groups that are released by the action of an acid include groups represented by formulas (Y1) to (Y4) described in the above-mentioned resin (A).

[0273] In formula (c1), nc represents an integer of 1 to 5. nc is preferably an integer of 1 to 3.

[0274] In general formula (c1), Xc represents a linking group having a valence of (nc+1). Xc is preferably an aromatic ring group, more preferably an aromatic ring group having 6 to 20 carbon atoms, and even more preferably a benzene ring group.

[0275] In general formula (c1), Mc ＋ represents a sulfonium ion or an iodonium ion. Examples of the sulfonium ion and the iodonium ion include the cations represented by the above formula (ZaI) and formula (ZaII), and among these, the above cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) are preferred.

[0276] The compound represented by the above general formula (c1) is more preferably a compound represented by the following general formula (c2).

[0277]

[0278] In the general formula (c2), L, A, nc, and Mc ＋ represents L, A, nc, and Mc in the general formula (c1) above. ＋ The same applies to preferred examples.

[0279] Specific examples of the compound represented by general formula (c1) are shown below, but the compound is not limited to these.

[0280]

[0281]

[0282]

[0283] As the photoacid generator, for example, compounds B-1 to B-5 used in the examples can be used.

[0284] The content of the photoacid generator is not particularly limited, but is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention, in order to form a more rectangular cross-sectional pattern. The content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention. The photoacid generator may be used alone or in combination of two or more types.

[0285] [Acid Diffusion Controller] The composition of the present invention may further contain an acid diffusion controller. The acid diffusion controller traps the acid generated from the photoacid generator or the like upon exposure and acts as a quencher to suppress the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller is not particularly limited, and examples include a basic compound (DA), a low-molecular-weight compound (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (DC) whose acid diffusion control ability is reduced or eliminated upon irradiation with actinic rays or radiation. Examples of the compound (DC) include an onium salt compound (DD) of an acid that is weaker than the acid generated from the photoacid generator (e.g., salt (C)), and a basic compound (DE) whose basicity is reduced or eliminated upon irradiation with actinic rays or radiation. Specific examples of the basic compound (DA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

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

[0164] of WO 2020 / 066824, and specific examples of the low molecular weight compound (DB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of the onium salt compound (DD) that is a weaker acid than the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0286] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller.

[0287] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.1 to 15.0 mass %, more preferably 0.5 to 15.0 mass %, based on the total solid content of the composition of the present invention. One type of acid diffusion controller 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.

[0288] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed 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 polar and non-polar substances. The effects of adding a hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with water, and suppressing outgassing.

[0289] 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.

[0290] 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.

[0291] [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.

[0292] 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.

[0293] [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).

[0294] 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.

[0295] 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.

[0296] 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.

[0297] [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).

[0298] 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.

[0299] The composition of the present invention is suitable for use as a photosensitive composition for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, and therefore the number of incident photons is smaller when exposed at the same sensitivity. As a result, the effect of "photon shot noise," in which the number of photons varies stochastically, is significant, leading to deterioration of line edge roughness (LER) and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at a trade-off with the demand for higher sensitivity.

[0300] When the value A calculated by the following formula (1) is high, the resist film formed from the resist composition has a high absorption efficiency of EUV light and electron beams, which is effective in reducing photon shot noise. The value A represents the absorption efficiency of EUV light and electron beams by mass of the resist film. Formula (1): A = ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] x 39.5) / ([H] x 1 + [C] x 12 + [N] x 14 + [O] x 16 + [F] x 19 + [S] x 32 + [I] x 127). The value A is preferably 0.120 or greater. There is no particular upper limit to the A value, but if the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. Therefore, the A value is preferably 0.240 or less, and more preferably 0.220 or less.

[0301] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from all solids to all atoms in all solids, [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition. For example, when a resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent, the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solids. In other words, the total atoms in all solids correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion controller. For example, [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids. Explaining based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the acid-decomposable resin, the photoacid generator, and the acid diffusion controller to the sum of all atoms derived from the acid-decomposable resin, the photoacid generator, and the acid diffusion controller.

[0302] The A value can be calculated by calculating the atomic ratio of the components contained in the resist composition when the structures and contents of the components of the total solid content of the resist composition are known. Even when the components are unknown, the atomic ratio of the components can be calculated by analytical techniques such as elemental analysis of a resist film obtained by evaporating the solvent component of the resist composition.

[0303] <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 procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention; Step 2: exposing the actinic ray- or radiation-sensitive film; Step 3: developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of each of the above steps will be described in detail below.

[0304] (Step 1: Actinic Ray- or Radiation-Sensitive Film Forming Step) Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention.

[0305] An example of a method for forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention is to coat the composition of the present invention on the substrate. It is preferable to filter the composition of the present invention before coating, 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.

[0306] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed 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 an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

[0307] 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.

[0308] The thickness of the actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0309] A top coat may be formed on the actinic ray- or radiation-sensitive film using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray- or radiation-sensitive 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 actinic ray- or radiation-sensitive 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.

[0310] (Step 2: Exposure Step) Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film. Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film 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 include far ultraviolet light with a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and 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.

[0311] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction in 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 carried out using a means provided in a typical exposure machine and / or developer, and may also be carried out using a hot plate or the like. This step is also called post-exposure baking. The composition of the present invention can suppress fluctuations in the line width of the pattern that depend on the heating temperature during this process.

[0312] (Step 3: Development Step) Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive 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).

[0313] 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.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0318] 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.

[0319] 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.

[0320] 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).

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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).

[0325] 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.

[0326] 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.

[0327] <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).

[0328] 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.

[0329] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0330] <Resin (A)> P-1 to P-20 were used as resin (A). RP-1 to RP-4 were also used as resins other than resin (A). For convenience, RP-1 to RP-4 are also listed in the resin (A) column in Table 2 below.

[0331] Table 1 shows the composition ratio (mol %), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown below. The weight average molecular weight (Mw) and dispersity (Pd=Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of the repeating unit is １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0332]

[0333] The structures of the repeating units MA-1 to MA-4, MP-1 to MP-10, and MC-1 to MC-4 shown in Table 1 are shown below.

[0334]

[0335] <Photoacid Generator (B)> The structure of the photoacid generator (B) used is shown below.

[0336]

[0337] <Acid Diffusion Controller> The structure of the acid diffusion controller used is shown below.

[0338]

[0339] <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.

[0340]

[0341] <Surfactant> The surfactants used are as follows: W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)

[0342] <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

[0343] <Preparation of Resist Composition> The components shown in Table 2 were dissolved in the solvents shown in Table 2 to prepare solutions with the solid content concentrations shown in Table 2. These solutions were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions. The solid content refers to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. The "mass %" column in the table indicates the content (mass %) of each component relative to the total solid content in the resist composition. The table also lists the amount (parts by mass) of the solvent used.

[0344]

[0345] <Pattern Forming Method (1): EB Exposure, Alkali Development (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. Here, 1 inch is 0.0254 m. 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). The lithography was performed so as to form a 1:1 line and space. After electron beam writing, post-exposure baking (PEB) was performed by heating the wafer on a hot plate at 110° C. for 60 seconds, developing it with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsing it with pure water, rotating the wafer at 4000 rpm for 30 seconds, and then heating it at 95° C. for 60 seconds to obtain a resist pattern with a 1:1 line and space pattern and a line width of 50 nm. The PEB temperature dependency was evaluated for patterns formed under the conditions described below.

[0346] <Performance Evaluation> [Evaluation of LWR] A line and space pattern (line / space = 1 / 1) with a line width of 50 nm resolved by the above-described method was observed from above the pattern using a critical dimension scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)). The line width of the pattern was observed at arbitrary points (160 points), and the measurement variation 3σ (nm) was evaluated as the LWR value. A smaller value indicates better performance.

[0347] [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.

[0348] [PEB Temperature Dependence] The optimal exposure dose was defined as the exposure dose that reproduced a 1:1 line and space pattern with a width of 50 nm when post-exposure baking (PEB) was performed at 110°C for 90 seconds. Next, after irradiation at the optimal exposure dose, post-baking was performed at two temperatures, +5°C and -5°C relative to the post-baking temperature (i.e., 115°C and 105°C), and the resulting line and space patterns were measured to determine their line widths L1 and L2. PEB temperature dependency was defined as the change in line width per 1°C change in PEB temperature and calculated using the following formula: PEB temperature dependency (nm / °C) = |L1 - L2| / 10. A smaller value of PEB temperature dependency indicates a smaller change in performance with temperature change and is therefore more favorable.

[0349] Table 3 below shows the resist compositions used in each of the Examples and Comparative Examples, and the results of each of the Examples and Comparative Examples.

[0350]

[0351] <Pattern Forming Method (2): EUV Exposure, Alkali Development (Positive)> An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick underlayer film. A resist composition shown in Table 2 was applied thereon and baked at 100°C for 60 seconds to form a 50 nm thick resist film. Using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation. A mask with a line size of 50 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 100° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[0352] <Performance Evaluation> The resists obtained were evaluated in the same manner as above. The evaluation results are shown in Table 4.

[0353]

[0354] The results in Tables 3 and 4 show that the resist compositions used in the examples have excellent resolution and LWR performance in the formation of ultrafine patterns, and can suppress pattern line width fluctuations that depend on the PEB temperature.

[0355] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and LWR performance and can suppress pattern line width fluctuations that depend on PEB temperature when forming ultrafine patterns (e.g., line widths or space widths of 50 nm or less). The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0356] 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. 2023-143240) filed on September 4, 2023, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) having the following repeating units (a-1) and (a-2), the sum of the repeating units (a-1) and (a-2) being 80 mol % or more of the total repeating units, and the weight average molecular weight being 5000 or less: (a-1) a repeating unit containing at least an aromatic ring having two or more aromatic rings condensed thereto or an aromatic ring having two or more aromatic rings linked by a single bond, and a phenolic hydroxyl group; (a-2) a repeating unit containing at least an aromatic ring having two or more aromatic rings condensed thereto or an aromatic ring having two or more aromatic rings linked by a single bond, and a structure in which the phenolic hydroxyl group or carboxyl group is protected by a group which is cleaved by the action of an acid.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a-2) is a repeating unit having a structure in which a phenolic hydroxyl group in the repeating unit (a-1) is protected with a group that is eliminated by the action of an acid.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a-1) is a repeating unit represented by the following general formula (b-1), and the repeating unit (a-2) is a repeating unit represented by the following general formula (b-2): In general formula (b-1), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ１ represents a single bond or -C(=O)O-. １ R represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｂ４ represents a substituent other than a hydroxyl group. p represents an integer of 1 or more. q represents an integer of 0 or more. When q is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ１ , R ｂ２ , or R ｂ３ may be linked to form a ring. ｂ２ Or R ｂ３ And, Ar １ may be bonded to each other to form a ring. In general formula (b-2), R ｂ５ ~R ｂ７ each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ２ represents a single bond or -C(=O)O-. ２ R represents an aromatic ring group in which two or more aromatic rings are condensed, or an aromatic ring group in which two or more aromatic rings are linked by a single bond. ｐ１ represents a group which is eliminated by the action of an acid. ｂ８ is -OR Ｐ１ R represents an integer of 1 or more. s represents an integer of 0 or more. When s is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , and R ｂ７ may be linked to any one of the groups to form a ring. ｂ６ Or R ｂ７ And, Ar ２ may be bonded to each other to form a ring.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the sum of the repeating units (a-1) and (a-2) is 90 mol % or more of all repeating units.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) is a resin constituted only of the repeating unit (a-1) and the repeating unit (a-2).

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a-1) is a repeating unit represented by the following general formula (b-11), and the repeating unit (a-2) is a repeating unit represented by the following general formula (b-21): In general formula (b-11), R ｂ１ ~R ｂ３ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｂ４ represents a substituent other than a hydroxyl group. p11 represents an integer of 1 to 7. q11 represents an integer of 0 to (7-p11). When q11 is 2 or more, a plurality of R ｂ４ may be the same or different and may be bonded to each other to form a ring. ｂ４ is R ｂ２ Or R ｂ３ may be linked to form a ring. ｂ２ Or R ｂ３ The naphthalene rings bonded to the main chain may be bonded to each other to form a ring. In general formula (b-21), R ｂ５ ~R ｂ７ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. ｐ１ represents a group which is eliminated by the action of an acid. ｂ８ Yes - OR ｐ１ represents a substituent other than the group represented by the formula: r11 represents an integer of 1 to 7. s11 represents an integer of 0 to (7-r11). When s11 is 2 or more, a plurality of R ｂ８ may be the same or different and may be bonded to each other to form a ring. ｂ８ is R ｂ５ , R ｂ６ , R ｂ７ , and R ｐ１ may be linked to any one of the groups to form a ring. ｂ６ Or R ｂ７ The naphthalene rings bonded to the main chain may be bonded to each other to form a ring.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a-2) contains one structure in which a phenolic hydroxyl group is protected by a group that is eliminated by the action of an acid.

8. R in the general formula (b-2) ｐ１ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3 , wherein is a group represented by the following formula (ALG1) or formula (ALG2): In formula (ALG1), R ＡＬ１ ~R ＡＬ２ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. * represents a bond. In formula (ALG2), R ＡＬ３ ~R ＡＬ５ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. ＡＬ３ ~R ＡＬ５ Two of may be bonded to each other to form a ring. * represents a bond.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a compound which generates an acid upon exposure to actinic rays or radiation.

10. 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 9.

11. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition according to any one of claims 1 to 9; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

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

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