A photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device

Abstract

The present invention provides a sensitizing or radiation-reducing resin composition that has excellent roughness performance and can suppress the occurrence of defects in the pattern when forming ultrafine patterns (e.g., line and space patterns of 30 nm or less, or hole patterns with a hole diameter of 30 nm or less). The sensitizing or radiation-reducing resin composition comprises (A) a resin having a repeating unit having an aromatic ring having a halogen atom or an organic group having a halogen atom and a halogen atom-free substituent, and (Y) an ionic compound (Y) having a halogen atom in a cationic portion, wherein the content of the ionic compound (Y) is 5.0 mass% or more with respect to the total solid content of the composition.

Description

Technology Field

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

[0002] In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large-Scale Integrated Circuits), microfabrication is performed using lithography with photosensitive compositions.

[0003] As a method of lithography, a resist film is formed using a photosensitive composition, the resulting film is exposed to light, and then developed. In particular, recently, in addition to the ArF excimer laser, the use of EB (Electron Beam) and EUV (Extreme Ultraviolet) light during exposure is being investigated, and the development of photosensitive or radiation-sensitive resin compositions suitable for EUV exposure is underway.

[0004] In the formation of resist patterns using EUV (wavelength 13.5 nm) or electron beams for the purpose of forming fine patterns, the requirements for various performances are becoming stricter than when using conventional ArF (wavelength 193 nm) light, etc.

[0005] For example, Patent Document 1 discloses a composition that is sensitized to light or radiation, comprising a resin and a compound that generates acid upon irradiation with active light or radiation, wherein the composition satisfies specific parameters and the compound is a specific compound.

[0006] Patent Document 2 discloses a resist material comprising an acid-generating agent comprising a sulfonium salt represented by a specific formula. Prior art literature

[0007] Patent Document 1: International Publication No. 2020 / 158417 Patent Document 2: Japanese Published Patent Application No. 2020-46661 The problem to be solved

[0008] Recently, the miniaturization of patterns formed using EUV light or electron beams is progressing, and further improvements are required in terms of pattern roughness performance and defect performance.

[0009] Therefore, the present invention aims to provide a light-sensitive or radiation-sensitive resin composition that has excellent roughness performance and can suppress the occurrence of defects in the pattern when forming ultrafine patterns (e.g., line and space patterns of 30 nm or less, or hole patterns with a hole diameter of 30 nm or less).

[0010] In addition, the present invention aims to provide a photosensitive or radiation-sensitive film using the above-mentioned photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device. means of solving the problem

[0011] The inventors have found that the above problem can be solved by the following configuration.

[0012] [1]

[0013] (A) A resin having repeating units having an aromatic ring having an organic group having a halogen atom or a halogen atom and a halogen-free substituent, and

[0014] (Y) A photosensitive or radiation-sensitive resin composition comprising an ionic compound having a halogen atom in the cation portion,

[0015] A light-sensitive or radiation-sensitive resin composition having a content of the above ionic compound (Y) of 5.0 mass% or more relative to the total solid content of the composition.

[0016] [2]

[0017] The above composition is a photosensitive or radiation-sensitive resin composition described in [1], containing an ionic compound having an acid-degradable group in the (Z) cation portion.

[0018] [3]

[0019] The above resin (A) is a photosensitive or radiation-sensitive resin composition described in [1] or [2], having repeating units having a lactone structure.

[0020] [4]

[0021] The above resin (A) is a desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [3], having repeating units having a polycyclic lactone structure.

[0022] [5]

[0023] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [4], wherein the above resin (A) has repeating units represented by the following formula (4).

[0024] [Chemical Formula 1]

[0025]

[0026] Among the formulas (4),

[0027] X 11 It represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group.

[0028] R 11 Each represents an alkyl group independently. Two Rs 11 It may combine to form a ring.

[0029] [6]

[0030] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [5], wherein the content of the above ionic compound (Y) is 10.0 mass% or more with respect to the total solid content of the composition.

[0031] [7]

[0032] A photosensitive or photosensitive film formed by a photosensitive or photosensitive resin composition as described in any one of [1] to [6].

[0033] [8]

[0034] A process of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of [1] to [6], and

[0035] A process for exposing the above-mentioned photosensitive or photosensitive film, and

[0036] A pattern forming method having a process of developing the exposed photosensitive or photosensitive film using a developer and forming a pattern.

[0037] [9]

[0038] A method for manufacturing an electronic device comprising the pattern forming method described in [8]. Effects of the invention

[0039] According to the present invention, a light-sensitive or radiation-sensitive resin composition can be provided that has excellent roughness performance in forming ultrafine patterns (e.g., line and space patterns of 30 nm or less, or hole patterns with a hole diameter of 30 nm or less, etc.) and can also suppress the occurrence of defects in the pattern.

[0040] In addition, according to the present invention, a photosensitive or radiation-sensitive film using the above-described photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device can be provided. Specific details for implementing the invention

[0041] Below, an example of a form for carrying out the present invention is described.

[0042] Additionally, in this specification, a numerical range indicated by "~" refers to a range that includes the values ​​listed before and after "~" as lower and upper limits.

[0043] The bonding direction of the divalent groups indicated in this specification is not limited unless specifically explained. For example, in a compound represented by the general formula "XYZ", if Y is -COO-, Y may be -CO-O- or -O-CO-. Also, the compound may be "X-CO-OZ" or "XO-CO-Z".

[0044] In this specification, "(meth)acrylic" is a general term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Likewise, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid."

[0045] In this specification, "active light" or "radiation" means, for example, emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. In this specification, "light" means active light or radiation.

[0046] Unless otherwise specifically explained, the term "exposure" in this specification includes not only exposure by emission spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, X-rays, and EUV light, but also drawing by particle beams such as electron beams and ion beams.

[0047] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also called molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene equivalent values ​​obtained by GPC measurement using a Gel Permeation Chromatography (GPC) device (Dosoh HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Dosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0048] 1 Å is 1 × 10⁻⁶ -10 It is m.

[0049] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, it is a value obtained by calculation based on the database of Hamette's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification represent values ​​obtained by calculation using this software package.

[0050] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0051] Meanwhile, pKa is also determined by molecular orbital calculations. Specifically, this method involves H₂ in the solvent based on thermodynamic cycles. + One method is to calculate the free energy of dissociation. (In addition, in this specification, water is typically used as the solvent, and DMSO (dimethyl sulfoxide) is used when the pKa cannot be determined with water.)

[0052] H +Regarding the method for calculating the dissociation free energy, it can be calculated, for example, by the Density Functional Path (DFT); however, various other methods have been reported in the literature and are not limited to this. Furthermore, while there are multiple software programs capable of performing DFT, Gaussian 16 can be cited as an example.

[0053] In this specification, pKa refers to a value obtained by calculation based on a database of Hammett's substituent constants and known literature values ​​using software package 1 as described above. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on the DFT (density functional method) is adopted.

[0054] In the notation of a group (atomic group) in this specification, a notation that does not specify substitution or non-substitution includes a group having a substituent along with a group not having a substituent. For example, the term "alkyl group" includes not only an alkyl group not having a substituent (non-substituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Furthermore, the term "organic group" in this specification refers to a group comprising at least one carbon atom.

[0055] In addition, in this specification, when it is said that "substituents may be present," the type of substituent, the position of the substituent, and the number of substituents are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetal atomic groups excluding hydrogen atoms, and may be selected from, for example, the following substituents T.

[0056] (Substituent T)

[0057] As substituent T, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acryl, methacryloyl, and methoxalyl groups; alkylsulfaneyl groups such as methylsulfaneyl and tert-butylsulfaneyl groups; arylsulfaneyl groups such as phenylsulfaneyl and p-tolylsulfaneyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formylic groups; Examples include sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; and combinations thereof.

[0058] [Resin composition of light-sensitive or radiation-sensitive resins]

[0059] The photosensitive or radiation-sensitive resin composition of the present invention is,

[0060] (A) A resin having repeating units having an aromatic ring having an organic group having a halogen atom or a halogen atom and a halogen-free substituent, and

[0061] (Y) A photosensitive or radiation-sensitive resin composition comprising an ionic compound having a halogen atom in the cation portion,

[0062] The above is a light-sensitive or radiation-sensitive resin composition in which the content of the above ionic compound (Y) is 5.0 mass% or more relative to the total solid content of the composition.

[0063] Although the mechanism by which the problem of the present invention is solved with such a configuration is not necessarily clear, the inventors consider it as follows.

[0064] That is, the inventors first investigated in detail a configuration in which a halogen atom, which has high absorption of EUV or electron beams and is expected to contribute to achieving the above objective, is introduced into an ionic compound in a photosensitive or radiation-sensitive resin composition (hereinafter also simply referred to as "composition") to achieve the objective of forming a good pattern of ultrafine size (e.g., line and space patterns of 30 nm or less, or hole patterns with a hole diameter of 30 nm or less), and in which this ionic compound is present at a high concentration (5.0 mass% or more relative to the total solid content of the composition). In order to form a good pattern, it was considered important that the resin and the ionic compound have high compatibility in the photosensitive or radiation-sensitive film (typically a resist film) formed by the composition.

[0065] Furthermore, the inventors estimated that when using a composition comprising a resin having an aromatic ring with a substituent and an ionic compound (especially an ionic compound at a high concentration), in order to achieve the objective of forming the ultrafine pattern, it is difficult to ensure sufficient compatibility between the resin having an aromatic ring with a substituent and the ionic compound, and the ionic compound tends to aggregate, making it prone to pattern defects. Additionally, they estimated that due to insufficient compatibility, it is difficult to achieve sufficient roughness performance in the exposure section, as the reaction of the resin controlled by the ionic compound (such as an acid-generating agent or an acid diffusion control agent) is difficult to carry out as intended.

[0066] Meanwhile, in the present invention, the objective of forming the ultrafine pattern can be achieved while introducing a halogen atom into the resin having an aromatic ring having a substituent and an ionic compound, and while the ionic compound is present in a predetermined amount, which is expected to contribute to the achievement of the objective, it is believed that this is because the compatibility between the resin and the ionic compound is increased by specifically determining the position of the introduction of the halogen atom in the ionic compound.

[0067] More specifically, first, by using an ionic compound (Y) having a halogen atom in the cation portion, the compatibility of the ionic compound (Y) with the resin becomes sufficient, so it is thought that the ionic compound (Y) is difficult to aggregate and pattern defects are less likely to occur.

[0068] In addition, by introducing an ionic compound (Y) at a high concentration (5.0 mass% or more relative to the total solid content of the composition), it is thought that in the exposure section, the reaction of the resin controlled by the action of the ionic compound (Y) (such as an acid generating agent or an acid diffusion control agent) is easily carried out as intended, and sufficient roughness performance is obtained.

[0069] In addition, when the ionic compound is less than 5.0 mass% relative to the total solid content, it is difficult to obtain sufficient roughness performance in forming the ultrafine pattern, possibly because the reaction of the resin in the exposure section is difficult to carry out.

[0070] [Components of a photosensitive or radiation-sensitive resin composition]

[0071] Below, the components that may be included in a photosensitive or radiation-sensitive resin composition are described in detail.

[0072] The photosensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and may be a positive-type resist composition or a negative-type resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention is typically a chemically amplified type resist composition.

[0073] <(A) Suzy>

[0074] A desensitizing photoreceptive or radiation-receptive resin composition (hereinafter also referred to as the "composition") comprises a resin (A).

[0075] Resin (A) is typically an acid-degradable resin, and is a resin in which polarity is increased by the action of acid, solubility in an alkaline developer is increased and solubility in an organic solvent is decreased.

[0076] Resin (A) has a group that decomposes upon the action of an acid to generate a polar group (in other words, a structure in which the polar group is protected by a detaching group that is detached upon the action of an acid). Such a group (structure) is also called an acid-degradable group. A resin having an acid-degradable group (i.e., a resin having repeating units having an acid-degradable group) has increased polarity upon the action of an acid, which increases solubility in an alkaline developer and decreases solubility in an organic solvent.

[0077] (Repeating unit having an aromatic ring having a halogen atom or an organic group having a halogen atom and a halogen-free substituent)

[0078] The resin (A) has a repeating unit (hereinafter also referred to as “repeating unit (a1”) having an organic group having a halogen atom or a halogen atom and an aromatic ring having a halogen-free substituent.

[0079] In addition, the above halogen atom-free substituent is a substituent that does not have a halogen atom, and is a group different from a halogen atom and an organic group having a halogen atom.

[0080] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0081] Examples of organic groups having a halogen atom include, but are not particularly limited, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, etc.

[0082] As for the alkyl group, although not particularly limited, examples include straight-chain or branched-chain alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0083] As for the alkeneyl group, although not particularly limited, examples include straight or branched alkeneyl groups having 2 to 12 carbon atoms, and vinyl groups are preferred.

[0084] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0085] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0086] As for the alkoxy group, although not particularly limited, examples include straight-chain or branched-chain alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 3 carbon atoms are more preferred.

[0087] The alkyl group, cycloalkyl group, aryl group, and alkoxy group may have additional substituents. As a preferred embodiment, the substituents are not particularly limited, but for example, halogen atoms and hydroxyl groups are preferred.

[0088] An organic group having a halogen atom has at least one halogen atom, and may have multiple halogen atoms.

[0089] As a preferred embodiment, the organic group having a halogen atom is preferably an alkyl group having a halogen atom. As for the alkyl group having a halogen atom, it is not particularly limited as long as it is an alkyl group having a halogen atom, but as a preferred embodiment, the alkyl group having a halogen atom is preferably a perhaloalkyl group.

[0090] Examples of alkyl groups having a halogen atom include trifluoromethyl groups, pentafluoroethyl groups, perfluorobutyl groups, etc.

[0091] Examples of halogen-free substituents include organic groups, hydroxyl groups, etc., although they are not particularly limited.

[0092] Examples of organic groups include, but are not particularly limited, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, etc.

[0093] As for the alkyl group, although not particularly limited, examples include straight-chain or branched-chain alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0094] As for the alkeneyl group, although not particularly limited, examples include straight or branched alkeneyl groups having 2 to 12 carbon atoms, and vinyl groups are preferred.

[0095] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0096] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0097] As for the alkoxy group, although not particularly limited, examples include straight-chain or branched-chain alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 3 carbon atoms are more preferred.

[0098] Alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and alkoxy groups may have substituents.

[0099] In addition, alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups may be bonded to an aromatic ring by interposing a heteroatom (e.g., an oxygen atom).

[0100] As a halogen-free substituent, a hydroxyl group and a group represented by OR4 (R4 is an organic group) described later are preferred.

[0101] As for the aromatic ring, it is not particularly limited, but an aromatic ring having 6 to 30 carbon atoms is preferred, and an aromatic ring having 6 to 14 carbon atoms is more preferred. Specifically, examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, etc.

[0102] The directional ring may have additional substituents.

[0103] The above repeating unit (a1) is preferably a repeating unit having a structure represented by the following formula (1).

[0104] [Chemical Formula 2]

[0105]

[0106] Among the formula (1),

[0107] R3 represents a halogen atom or an organic group having a halogen atom.

[0108] R4 represents a hydrogen atom or an organic group.

[0109] n represents an integer greater than or equal to 1. m represents an integer greater than or equal to 1. p represents an integer greater than or equal to 0. Provided that n, m, and p satisfy the relationship n+m≤5+2p.

[0110] If m represents an integer greater than or equal to 2, multiple R3s may be identical or different. If n represents an integer greater than or equal to 2, multiple R4s may be identical or different. * indicates a joining position.

[0111] Examples of halogen atoms of R3 include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0112] Examples of organic groups having a halogen atom include, but are not particularly limited, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, etc.

[0113] As for the alkyl group, although not particularly limited, examples include straight-chain or branched-chain alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0114] As for the alkeneyl group, although not particularly limited, examples include straight or branched alkeneyl groups having 2 to 12 carbon atoms, and vinyl groups are preferred.

[0115] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0116] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0117] As for the alkoxy group, although not particularly limited, examples include straight-chain or branched-chain alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 3 carbon atoms are more preferred.

[0118] The alkyl group, cycloalkyl group, aryl group, and alkoxy group may have additional substituents. As a preferred embodiment, the substituents are not particularly limited, but for example, halogen atoms, hydroxyl groups, etc. are preferred.

[0119] An organic group having a halogen atom has at least one halogen atom, and may have multiple halogen atoms.

[0120] As a preferred embodiment, the organic group having a halogen atom is preferably an alkyl group having a halogen atom. As for the alkyl group having a halogen atom, it is not particularly limited as long as it is an alkyl group having a halogen atom, but as a preferred embodiment, the alkyl group having a halogen atom is preferably a perhaloalkyl group.

[0121] Examples of alkyl groups having a halogen atom include trifluoromethyl groups, pentafluoroethyl groups, perfluorobutyl groups, etc.

[0122] The organic group of R4 is not particularly limited, but examples include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, etc.

[0123] As for the alkyl group, although not particularly limited, examples include straight-chain or branched-chain alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0124] As for the alkeneyl group, although not particularly limited, examples include straight or branched alkeneyl groups having 2 to 12 carbon atoms, and vinyl groups are preferred.

[0125] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0126] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0127] Alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups may have substituents.

[0128] It is preferable that R4 be a hydrogen atom.

[0129] The upper limit of n is not specifically limited, but is typically 5. n is preferably 1 to 3, and more preferably 1 to 2.

[0130] The upper limit of m is not specifically limited, but is typically 5. m is preferably 1 to 3, and more preferably 1 to 2.

[0131] The upper limit of p is not specifically limited, but is typically 3. p is preferably 0 to 3, and more preferably 0 to 2.

[0132] The direction ring in formula (1) may have additional substituents.

[0133] The above-mentioned repeating unit (a1) is preferably a repeating unit represented by the following formula (2).

[0134] [Chemical Formula 3]

[0135]

[0136] Among the (2) formulas,

[0137] X represents a hydrogen atom or an organic group.

[0138] L represents a single bond or a divalent linker.

[0139] R3, R4, n, m, and p each have the same meaning as R3, R4, n, m, and p in the above equation (1).

[0140] If m represents an integer greater than or equal to 2, multiple R3s may be the same or different. If n represents an integer greater than or equal to 2, multiple R4s may be the same or different.

[0141] The organic group of X is not particularly limited, but examples include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, etc.

[0142] As for the alkyl group, although not particularly limited, a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms may be used, and a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0143] As for the alkeneyl group, although not particularly limited, examples include straight or branched alkeneyl groups having 2 to 12 carbon atoms, and vinyl groups are preferred.

[0144] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0145] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0146] As for the alkoxy group, although not particularly limited, examples include straight-chain or branched-chain alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 3 carbon atoms are more preferred.

[0147] Alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and alkoxy groups may have substituents.

[0148] Examples of divalent linkers of L include -COO-, -CO-, -O-, alkylene groups, cycloalkylene groups, arylene groups, and linkers formed by connecting multiple of these.

[0149] The alkylene group is not particularly limited, but may be a straight chain or a branched chain.

[0150] The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred.

[0151] The cycloalkylene group is not particularly limited, but may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 6.

[0152] The arylene group is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is more preferred.

[0153] Alkylene groups, cycloalkylene groups, and arylene groups may have substituents.

[0154] As a preferred embodiment, the substituents are not particularly limited but may include alkyl groups, halogen atoms, etc. As the alkyl group, although not particularly limited, straight-chain or branched-chain alkyl groups having 1 to 12 carbon atoms may be used, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred. As for the halogen atoms, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0155] The alkyl group may have additional substituents. As for the substituents, they are not particularly limited, but, for example, halogen atoms are preferred.

[0156] As for L, a linker formed by a single bond, -COO-, an alkylene group, or a linker formed by connecting -COO- and an alkylene group is preferred, and a linker formed by connecting a single bond, -COO-, or a linker formed by connecting -COO- and an alkylene group is more preferred.

[0157] It is preferable that R4 be a hydrogen atom.

[0158] The following provides specific examples of monomers corresponding to the repeating unit (a1), but the present invention is not limited to these.

[0159] [Chemical Formula 4]

[0160]

[0161] [Chemical Formula 5]

[0162]

[0163] In resin (A), the repeating unit (a1) may be used as a single type or as two or more types.

[0164] In the resin (A), the content of the repeating unit (a1) is preferably 5 to 70 mol% with respect to the total repeating unit of the resin (A), more preferably 5 to 50 mol%, and more preferably 5 to 30 mol%.

[0165] (Repeating unit having an acid-degrading group (a2))

[0166] The resin (A) may further include a repeating unit having an acid-degradable group (also called a repeating unit (a2)).

[0167] It is desirable for the acid-degrading group to have a structure in which the polar group is protected by a group (detacher) that is detached by the action of acid.

[0168] Examples of polar groups include, for instance, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and acidic groups such as tris(alkylsulfonyl)methylene groups (typically groups that dissociate in an aqueous solution of 2.38 mass% tetramethylammonium hydroxide), and alcoholic hydroxyl groups.

[0169] In addition, an alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group, excluding a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and excludes aliphatic alcohol groups in which the α-position is substituted with an electron-reducing group such as a fluorine atom (e.g., hexafluoroisopropanol group, etc.). As for the alcoholic hydroxyl group, it is preferable that the hydroxyl group has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0170] Among these, as polar groups, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred.

[0171] As for the group that is removed by the action of acid (removal group), for example, the group represented by equations (Y1) to (Y4) can be cited.

[0172] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0173] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0174] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0175] Equation (Y4): -C(Rn)(H)(Ar)

[0176] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight or branched), an alkeneyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), or an aryl group (monocyclic or polycyclic).

[0177] Among these, it is preferable that Rx1 to Rx3 each independently represent a straight-chain or branched-chain alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a straight-chain alkyl group.

[0178] Two of Rx1 to Rx3 may combine to form a monocyclic or polycyclic ring.

[0179] As for the alkyl groups of Rx1 to Rx3, examples include alkyl groups having 1 to 20 carbon atoms, although they are not particularly limited; alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0180] As for the alkene groups of Rx1 to Rx3, examples include alkene groups having 2 to 20 carbon atoms, although they are not particularly limited, and alkene groups having 2 to 4 carbon atoms, such as vinyl groups, propene groups, and isopropene groups, are preferred.

[0181] As for the cycloalkyl groups of Rx1 to Rx3, examples include cycloalkyl groups having 3 to 20 carbon atoms, although they are not particularly limited. Single-ring cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0182] The aryl groups of Rx1 to Rx3 are preferably aryl groups having 6 to 14 carbon atoms, and examples include phenyl groups, naphthyl groups, and anthryl groups.

[0183] Alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups may have substituents.

[0184] As for the cycloalkyl group formed by combining two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group are preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0185] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0186] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may have a substituent.

[0187] In equation (Y3), R 36 ~R 38 Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 Silver may combine with one another to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R 36 It is also desirable that it be a hydrogen atom.

[0188] As for Equation (Y3), it is preferable to have a group represented by the following Equation (Y3-1).

[0189] [Chemical Formula 6]

[0190]

[0191] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (e.g., a combination of an alkyl group and an aryl group).

[0192] M represents a single bond or a divalent linker.

[0193] Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a combination of an alkyl group and a cycloalkyl group).

[0194] The alkyl group and the cycloalkyl group may be substituted, for example, with one of the methylene groups being a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0195] In addition, it is preferable that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group.

[0196] At least two of Q, M, and L1 may be combined to form a ring (preferably, a 5-membered or 6-membered ring).

[0197] In terms of pattern miniaturization, it is preferable that L2 be a secondary or tertiary alkyl group, and more preferable that it be a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl groups, cyclohexyl groups, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl groups or adamantane groups. In these embodiments, since the Tg (glass transition temperature) or activation energy is increased, in addition to ensuring film strength, fogging can be suppressed.

[0198] In formula (Y4), Ar represents an aromatic group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. More preferably, Ar is an aryl group.

[0199] It is desirable that the resin (A) has an acetal structure.

[0200] It is desirable for the acid-degradable group to have an acetal structure. The acetal structure is a structure in which polar groups, such as carboxyl groups, phenolic hydroxyl groups, and fluorinated alcohol groups, are protected by the group represented by the above formula (Y3).

[0201] As a repeating unit having an acid-degrading group, a repeating unit represented by formula (A) is preferred.

[0202] [Chemical Formula 7]

[0203]

[0204] L1 represents a divalent linker, R1 to R3 each independently represent a hydrogen atom or a monovalent substituent, and R4 represents a group that is decomposed and removed by the action of acid.

[0205] L1 represents a divalent linker. Examples of divalent linkers include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linkers formed by connecting multiple of these. Among these, -CO- and arylene groups are preferred as L1.

[0206] As for the arylene group, a phenylene group is preferred.

[0207] The alkylene group may be in a straight chain or a branched chain. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.

[0208] R1 to R3 each independently represent a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include alkyl groups, cycloalkyl groups, or halogen atoms.

[0209] The alkyl group may be in a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.

[0210] The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in this cycloalkyl group is preferably 3 to 8.

[0211] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0212] R4 represents the group that is removed by the action of acid (detachment).

[0213] Among them, as a degreasing agent, the group represented by the above formulas (Y1) to (Y4) can be cited, and the group represented by the above formula (Y3) is preferred.

[0214] When each of the above groups has a substituent, examples of the substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0215] As a repeating unit having an acid-degrading group, a repeating unit represented by the general formula (AI) is also desirable.

[0216] [Chemical Formula 8]

[0217]

[0218] In the general formula (AI),

[0219] Xa1 represents a hydrogen atom, or an alkyl group.

[0220] T represents a single bond, or a divalent linker.

[0221] Rx1 to Rx3 each independently represent an alkyl group (straight or branched), an alkeneyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), or an aryl group (monocyclic or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (straight or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0222] Two of Rx1 to Rx3 may be combined to form a cycloalkyl group (monocyclic or polycyclic).

[0223] As the alkyl group represented by Xa1, for example, a methyl group or -CH2-R 11 One example is the energy manifested as. R 11 It represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or fewer carbon atoms, and an acyl group having 5 or fewer carbon atoms, wherein an alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xa1, a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0224] Examples of the divalent linking groups of T include alkylene groups, aromatic groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0225] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0226] As for the alkyl groups of Rx1 to Rx3, examples include alkyl groups having 1 to 20 carbon atoms, although they are not particularly limited; alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0227] As for the alkene groups of Rx1 to Rx3, examples include alkene groups having 2 to 20 carbon atoms, although they are not particularly limited, and alkene groups having 2 to 4 carbon atoms, such as vinyl groups, propene groups, and isopropene groups, are preferred.

[0228] As for the cycloalkyl groups of Rx1 to Rx3, they are not particularly limited, but may include cycloalkyl groups having 3 to 20 carbon atoms, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0229] As for the aryl groups of Rx1 to Rx3, they are not particularly limited, but aryl groups having 6 to 14 carbon atoms, such as phenyl groups, naphthyl groups, and anthraceneyl groups, are preferred.

[0230] As for the cycloalkyl group formed by the combination of two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred, and additionally, a polycyclic cycloalkyl group such as a norvonyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0231] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0232] The repeating unit represented by the general formula (AI) is preferably, for example, in which Rx1 is a methyl or ethyl group and Rx2 and Rx3 are combined to form the cycloalkyl group described above.

[0233] When each of the above groups has a substituent, examples of the substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0234] The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

[0235] In a preferred embodiment, resin (A) contains a repeating unit represented by the following formula (4).

[0236] [Chemical Formula 9]

[0237]

[0238] Among the formulas (4),

[0239] X 11 It represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group.

[0240] R 11 Each represents an alkyl group independently. Two Rs 11 It may combine to form a ring.

[0241] X 11 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0242] X 11 Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, etc., although they are not particularly limited.

[0243] As for the alkyl group, although not particularly limited, a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms may be used, and a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0244] As for the cycloalkyl group, examples include cycloalkyl groups having 3 to 20 carbon atoms, although not particularly limited, and monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0245] As for the aryl group, it is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a naphthyl group, and anthryl group.

[0246] Alkyl groups, cycloalkyl groups, and aryl groups may include -O-, -COO-, and alkylene groups.

[0247] The alkyl group, cycloalkyl group, and aryl group may have additional substituents. The substituents are not particularly limited, but as a preferred embodiment, halogen atoms are preferred.

[0248] R 11 The alkyl group as is not particularly limited, but may be a straight-chain or branched-chain alkyl group, and the number of carbon atoms of the alkyl group is preferably 1 to 12, and more preferably 1 to 10.

[0249] The alkyl group may have additional substituents. The substituents are not particularly limited, but as a preferred embodiment, examples include alkoxy groups (1 to 4 carbon atoms), acyl groups (e.g., acetyl groups), hydroxyl groups, halogen atoms, etc.

[0250] 2 Rs 11 These may combine to form a ring. Specifically, 2 R 11 This bond may form a cycloalkyl group (monocyclic or polycyclic).

[0251] 2 Rs 11 As for the cycloalkyl group formed by this bond, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred, and additionally, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0252] 2 Rs 11The cycloalkyl group formed by this bond may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0253] Resin (A) may include a repeating unit having an acid-degradable group as a single type, or may include two or more types in combination.

[0254] The content of repeating units having acid-degradable groups included in the resin (A) (the total amount if there are multiple repeating units having acid-degradable groups) is preferably 10 to 90 mol% with respect to the total repeating units of the resin (A), more preferably 20 to 80 mol%, and more preferably 25 to 75 mol%.

[0255] The sum of the contents of repeating units (a1) and repeating units (a2) included in the resin (A) (the sum thereof in cases where there are multiple repeating units (a1) and repeating units (a2)) is preferably 60 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% with respect to the total repeating units of the resin (A).

[0256] In addition, if the resin (A) has only repeating units (a1) and repeating units (a2), the total amount of repeating units (a1) and repeating units (a2) included in the resin (A) is 100 mol%.

[0257] (Repetition unit (a3))

[0258] It is also preferable that the resin (A) has a repeating unit (a3) ​​having a different acid group from the repeating unit (a1).

[0259] The acid group having the repeating unit (a3) ​​is preferably at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a fluorinated alkyl alcohol group, and more preferably a phenolic hydroxyl group or a fluorinated alkyl alcohol group.

[0260] · Repeating unit having a phenolic hydroxyl group

[0261] As a repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (B2) is preferred.

[0262] [Chemical Formula 10]

[0263]

[0264] In general formula (B2), X represents a hydrogen atom, an alkyl group, or a halogen atom.

[0265] The above alkyl group may be in a straight chain or a branched chain. The number of carbon atoms in the above alkyl group is preferably 1 to 10.

[0266] The substituent of the alkyl group is preferably a hydroxyl group or a halogen atom. If the alkyl group has a substituent, it is preferable that the substituent has only a hydroxyl group and / or a halogen atom. The alkyl group is preferably -CH3.

[0267] In general formula (B2), X4 is a single bond, -COO-, or -CONR 64 - indicates, R 64 represents a hydrogen atom or an alkyl group (which may be straight or branched. Preferably, it has 1 to 5 carbon atoms). In -COO-, the carbonyl carbon is preferably directly bonded to the main chain of the repeating unit.

[0268] In general formula (B2), L4 represents a single bond or an alkylene group (it may be a straight chain or a branched chain. Preferably, it has 1 to 20 carbon atoms).

[0269] In general formula (B2), Ar4 represents an (n+1) valence aroma. The aroma is preferably an arylene group having 6 to 18 carbon atoms, such as a benzene group, a naphthalene group, and an anthracene group, or a heterocyclic group such as a thiophene group, a furan group, a pyrrole group, a benzothiophen group, a benzofuran group, a benzopyrrole group, a triazine group, an imidazole group, a benzimidazole group, a triazole group, a thiadiazole group, and a thiazole group, and a benzene group is more preferably an aroma.

[0270] In general formula (B2), n represents an integer from 1 to 5. The (n+1)-valence orientation group may have additional substituents that do not have halogen atoms.

[0271] The aforementioned R 64 Examples of substituents that the alkyl group, the L4 alkylene group, and the (n+1) valence aromatic group of Ar4 may have include alkoxy groups such as methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl groups; etc. In addition, examples of substituents that the (n+1) valence aromatic group of Ar4 may have include alkyl groups (which may be straight-chain or branched-chain; preferably, 1 to 20 carbon atoms).

[0272] Specific examples of repeating units having phenolic hydroxyl groups are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0273] [Chemical Formula 11]

[0274]

[0275] [Chemical Formula 12]

[0276]

[0277] [Chemical Formula 13]

[0278]

[0279] In addition, among the above repeating units, the repeating unit specifically described below is preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer from 1 to 3.

[0280] [Chemical Formula 14]

[0281]

[0282] · Repeating unit having a fluorinated alkyl alcohol group

[0283] As a repeating unit having a fluorinated alkyl alcohol group, a repeating unit having a hexafluoroisopropanol group is preferred.

[0284] The following are examples of repeating units corresponding to repeating units having a fluorinated alkyl alcohol group, but the present invention is not limited to these.

[0285] [Chemical Formula 15]

[0286]

[0287] [Chemical Formula 16]

[0288]

[0289] Specific examples of monomers corresponding to repeating units (a2) having acid groups other than phenolic hydroxyl groups and fluorinated alkyl alcohol groups are given, but the present invention is not limited thereto.

[0290] [Chemical Formula 17]

[0291]

[0292] When the resin (A) has repeating units (a3), the content is preferably 1 to 30 mol% with respect to the total repeating units of the resin (A), more preferably 5 to 25 mol%, and more preferably 5 to 20 mol%.

[0293] The repeating unit (a3) ​​may be used as a single unit or as two or more units.

[0294] (Repeating unit with polarity (a4))

[0295] The resin (A) may further include a repeating unit having a polarity different from that of the repeating unit (a1) (also called a repeating unit (a4)).

[0296] The polar group having the repeating unit (a4) is preferably at least one group selected from the group consisting of an ester group, a sulfonate group, a sulfonamide group, a carbonate group, a carbamate group, an alcoholic hydroxyl group (excluding the fluorinated alkyl alcohol group in the repeating unit (a2) described above), a sulfoxide group, a sulfonyl group, a ketone group, an imide group, an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group; more preferably at least one group selected from the group consisting of a lactone group, a sulfon group, a sulfam group, an alcoholic hydroxyl group (excluding the fluorinated alkyl alcohol group in the repeating unit (a2) described above), and a cyclic carbonate group; more preferably a lactone group or a sulfon group; and particularly preferably a lactone group.

[0297] That is, the repeating unit (a4) is preferably to have a lactone structure or a sulfone structure, and is particularly preferably to have a lactone structure.

[0298] It is preferable that the resin (A) has repeating units having a lactone structure.

[0299] In addition, it is desirable that the resin (A) has repeating units having a polycyclic lactone structure.

[0300] As for the lactone structure or sulfon structure, it is sufficient to have a lactone ring or a sulfon ring, and a lactone structure having a 5 to 7-membered lactone ring or a sulfon structure having a 5 to 7-membered sulfon ring is preferred.

[0301] A lactone structure in which another ring is condensed onto a 5- to 7-membered lactone ring in a manner forming a bicyclo structure or a spiro structure (i.e., a polycyclic lactone structure) is also desirable. A sulfon structure in which another ring is condensed onto a 5- to 7-membered sulfon ring in a manner forming a bicyclo structure or a spiro structure is also desirable.

[0302] Among these, resin (A) preferably comprises a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-22) or a sulfone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). In addition, the lactone structure or the sulfone structure may be directly bonded to the main chain.

[0303] Among them, a lactone structure represented by general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), or general formula (LC1-22), or a sulfone structure represented by general formula (SL1-1) is preferred.

[0304] [Chemical Formula 18]

[0305]

[0306] The lactone structure or sulfone structure may or may not have a substituent (Rb2). As for the substituent (Rb2), 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 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, or a cyano group is preferred, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferred. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different. In addition, the multiple substituents (Rb2) may bond with each other to form a ring.

[0307] As a repeating unit having a lactone structure or a sulfone structure, a repeating unit represented by the following general formula (LS1) is preferred.

[0308] [Chemical Formula 19]

[0309]

[0310] Among the above general formula (LS1),

[0311] A LS represents an ester bond (a group represented as -COO-) or an amide bond (a group represented as -CONH-).

[0312] t is, -R LS2 -R LS3 It is the number of repetitions of the structure represented by -, representing an integer from 0 to 5, preferably 0 or 1, and more preferably 0. When t is 0, (-R LS2 -R LS3 -)t becomes a single bond.

[0313] R LS2 represents an alkylene group, a cycloalkylene group, or a combination thereof. R LS2 If there are multiple instances of , the multiple Rs that exist LS2 Each can be the same or different.

[0314] R LS2 The alkylene group or cycloalkylene group of may have a substituent.

[0315] R LS3 R represents a single bond, ether bond, ester bond, amide bond, urethane bond, or urea bond. LS3 In cases where multiple exist, R where multiple exist LS3 Each may be the same or different.

[0316] Among them, R LS3 Silver, ether bonds or ester bonds are preferred, and ester bonds are more preferred.

[0317] R LS4 represents a monovalent organic group having a lactone structure or a sulfone structure.

[0318] Among these, in any one of the structures represented by the general formulas (LC1-1) to (LC1-22) and the general formulas (SL1-1) to (SL1-3) described above, it is preferable that the structure is formed by removing one hydrogen atom from one carbon atom constituting the lactone structure or sulfone structure. Furthermore, it is preferable that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting the substituent (Rb2).

[0319] R LS1 It represents silver, hydrogen atoms, halogen atoms, or monovalent organic groups (preferably methyl groups).

[0320] The following are examples of monomers corresponding to repeating units having at least one selected from the group consisting of lactone structures and sulfone structures.

[0321] In the following examples, the methyl group bonded to the vinyl group may be substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[0322] [Chemical Formula 20]

[0323]

[0324] [Chemical Formula 21]

[0325]

[0326] [Chemical Formula 22]

[0327]

[0328] As a repeating unit (a4), it is also preferable to have a repeating unit having a carbonate group.

[0329] In a repeating unit having a carbonate group, it is preferable that the carbonate group be included in a cyclic carbonate ester group.

[0330] A repeating unit having a carbonate group is preferably a repeating unit represented by the general formula (A4).

[0331] [Chemical Formula 23]

[0332]

[0333] Among the general formulas (A4),

[0334] R A 1 It represents silver, a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

[0335] n represents an integer greater than or equal to 0 (preferably 0 to 3).

[0336] R A 2 represents a substituent. If n is 2 or greater, there are multiple Rs. A 2 Each can be the same or different.

[0337] A represents a single bond or a divalent linker. The divalent linker is preferably an alkylene group (preferably having 1 to 4 carbon atoms), a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxylic acid group, or a combination thereof.

[0338] Z represents an atomic group that forms a single or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0339] The single or polycyclic group formed by Z together with the group represented as -O-CO-O- in the formula is preferably a 5-membered cyclic carbonate ester group, and a cyclic carbonate ester structure represented by the following general formula (CC1-1) is more preferable.

[0340] That is, A in general formula (A4) is preferably bonded to a group formed by removing one hydrogen atom from a reducing atom of a cyclic carbonate ester structure represented by the following general formula (CC1-1).

[0341] [Chemical Formula 24]

[0342]

[0343] The cyclic carbonate ester structural portion of the general formula (CC1-1) may have a substituent (Rb2). Preferred substituents (Rb2) include, for example, 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 carboxylic acid group, a halogen atom (preferably a fluorine atom), a hydroxyl group, and a cyano group. n3 represents an integer of 0 or 1.

[0344] The resin (A) may have repeating units having polar groups other than the above-mentioned lactone, sulfonate, or carbonate groups. As repeating units having polar groups other than the above-mentioned lactone, sulfonate, or carbonate groups, repeating units having a cyclocyclic hydrocarbon structure substituted with said polar groups are preferred. In the cyclocyclic hydrocarbon structure substituted with polar groups, cyclohexyl groups, adamantyl groups, or norbornene groups are preferred as the cyclocyclic hydrocarbon structure.

[0345] Specific examples of monomers corresponding to repeating units having the above-mentioned polar groups are provided below, but the present invention is not limited to these specific examples.

[0346] [Chemical Formula 25]

[0347]

[0348] It is also preferable that the resin (A) has a repeating unit (a4) as a repeating unit described in paragraphs

[0370] to

[0433] of U.S. Patent Application Publication 2016 / 0070167A1.

[0349] When the resin (A) includes a repeating unit (a4), the type of repeating unit (a4) included in the resin (A) may be one type or two or more types.

[0350] When the resin (A) includes repeating units (a4), the content of the repeating units (a4) included in the resin (A) (the total content if there are multiple repeating units (a4)) is preferably 5 to 50 mol% with respect to the total repeating units in the resin (A), more preferably 10 to 45 mol%, and even more preferably 10 to 30 mol%.

[0351] (Other repeating units)

[0352] In addition, the number (A) may further include a repeating unit (a5) represented by the following formula (D).

[0353] [Chemical Formula 26]

[0354]

[0355] In formula (D), "cylclic" represents a group forming a main chain in a cyclic structure. The number of constituent atoms of the ring is not particularly limited.

[0356] As for the repetition unit represented by Equation (D), for example, the following repetition unit can be cited.

[0357] [Chemical Formula 27]

[0358]

[0359] In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl 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 having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxylic acid group. Additionally, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. In the above formula, R' each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl 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 having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxylic acid group. Additionally, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.

[0360] m represents an integer greater than or equal to 0. The upper limit of m is not specifically restricted, but it is often 2 or less, and more often 1 or less.

[0361] When the resin (A) includes a repeating unit (repeating unit (a5)) represented by formula (D), the content thereof is preferably 1 to 50 mol% with respect to the total repeating unit of the resin (A), more preferably 3 to 40 mol%, and more preferably 5 to 30 mol%.

[0362] In addition, the number (A) may further include a repeating unit (a6) represented by the following formula (E).

[0363] [Chemical Formula 28]

[0364]

[0365] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of organic groups that may have substituents include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

[0366] "Cylclic" is a cyclic group containing carbon atoms of the main chain. The number of atoms included in the cyclic group is not particularly limited.

[0367] As for the repetition unit represented by Equation (E), for example, the following repetition unit can be cited.

[0368] [Chemical Formula 29]

[0369]

[0370] In the above formulas, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl 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 having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxylic acid group. Additionally, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.

[0371] R' each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl 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 20 carbon atoms), or a carboxylic acid group. Additionally, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.

[0372] m represents an integer greater than or equal to 0. The upper limit of m is not specifically restricted, but it is often 2 or less, and more often 1 or less.

[0373] Also, among Equation (E-2), Equation (E-4), Equation (E-6), Equation (E-8), and Equation (E-12), two Rs may be combined to form a ring.

[0374] When the resin (A) includes a repeating unit (a6) represented by formula (E), the content is preferably 1 to 50 mol% with respect to the total repeating unit of the resin (A), more preferably 3 to 40 mol%, and more preferably 5 to 30 mol%.

[0375] The resin (A) may include other repeating units different from the repeating unit (a1) to the extent that it does not impede the effects of the present invention, and may include, for example, a repeating unit having a light generator.

[0376] The repeating unit having the mine generator is not particularly limited, but is preferably a repeating unit (repeating unit (a7)) represented by the general formula (A7).

[0377] [Chemical Formula 30]

[0378]

[0379] In general formula (A7), the two Xfs each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (preferably CF3) substituted with at least one fluorine atom. Of the two Xfs, at least one is preferably something other than a hydrogen atom.

[0380] The above alkyl group may be in a straight chain or a branched chain. The number of carbon atoms in the above alkyl group is preferably 1 to 10. The above alkyl group preferably has only fluorine atoms as substituents.

[0381] Among the general formula (A7), R 1 and R 2 represents, respectively, a hydrogen atom, a fluorine atom, or an alkyl group, and R in the case where multiple are present. 1 and R 2 Each can be the same or different.

[0382] The above alkyl group may be in a straight chain or a branched chain. The number of carbon atoms in the above alkyl group is preferably 1 to 10. The substituent of the above alkyl group is preferably a fluorine atom. When the above alkyl group has a substituent, it is preferable that the substituent has only a fluorine atom.

[0383] In general formula (A7), L represents a 2-valent linker, and in the case of multiple links, L may be the same or different.

[0384] Examples of the divalent linkers of L include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, and linkers in which a plurality of these are connected, and linkers with a total carbon number of 12 or fewer are preferred.

[0385] In general formula (A7), x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0386] Among general formulas (A7), X 7It represents silver, hydrogen atoms, alkyl groups, or halogen atoms.

[0387] X 7 As for the alkyl group representing this alkyl group, a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms may be used, and a methyl group, an ethyl group, an i-propyl group, or an n-propyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0388] As substituents for cases where the above alkyl group has a substituent, the substituents listed in the above substituent T may be used.

[0389] X 7 Examples of halogen atoms representing this halogen atom include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, and it is preferable that it be a fluorine atom.

[0390] Among general formula (A7), M + It represents a cation. M + Details of, for example, M in the general formula (PA-1) described later + The same cation can be used.

[0391] When the resin (A) has repeating units (a7), the content is preferably 1 to 40 mol% with respect to the total repeating units of the resin (A), more preferably 1 to 25 mol%, and more preferably 1 to 15 mol%.

[0392] The repeating unit (a7) may be used as a single unit or as two or more units.

[0393] As described above, the resin (A) has halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0394] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization).

[0395] As a polystyrene equivalent value by the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and more preferably 4,500 to 15,000. If the weight average molecular weight of the resin (A) is set to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and also deterioration of developability and deterioration of film-forming ability due to increased viscosity can be prevented.

[0396] The degree of dispersion (molecular weight distribution) of the resin (A) is typically 1 to 5, 1 to 3 is preferred, 1.2 to 3.0 is more preferred, and 1.2 to 2.0 is more preferred. The smaller the degree of dispersion, the better the resolution and resist shape, and the sidewalls of the resist pattern are smooth, resulting in excellent roughness.

[0397] In the composition of the present invention, the content of resin (A) is preferably 30.0 to 99.9 mass% of the total solid content, and more preferably 60.0 to 99.0 mass%. In addition, the resin (A) may be used as one type or as two or more types.

[0398] The composition of the present invention may contain, in addition to the resin (A), a resin (also called resin (A')) that does not have repeating units (a1) to a extent that does not impede the effects of the present invention.

[0399] As for the resin (A'), it is not particularly limited to a resin that does not have a repeating unit (a1), but for example, a resin that does not have a repeating unit (a1) can be cited.

[0400] When the composition of the present invention contains resin (A'), the ratio of the content of resin (A) to the content of resin (A') in the composition of the present invention is preferably 9:1 to 8:2 in mass ratio.

[0401] <(Y) Ionic compounds having a halogen atom in the cation part>

[0402] The composition of the present invention contains an ionic compound (Y) having a halogen atom in a cation portion (hereinafter also referred to as "ionic compound (Y)" or "compound (Y)").

[0403] The ionic compound (Y) is a compound having an anionic part and a cation part, and is a compound having a halogen atom in the cation part. The ionic compound (Y) is typically an onium salt, and examples include sulfonium salts, iodonium salts, etc.

[0404] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0405] The iodine atom in the cation portion may be an iodine cation in an iodium salt.

[0406] The above ionic compound (Y) is preferably an ionic compound having an acid-degrading group in the (Y') cation portion.

[0407] The acid-degradable group is a group that is decomposed by the action of acid to generate a polar group. The acid-degradable group is the same as the acid-degradable group described in the resin (A) above.

[0408] In a preferred embodiment, the ionic compound (Y) is a compound having a halogen atom in the cation portion of the photogenerator (B) described below.

[0409] In a preferred embodiment, the ionic compound (Y) is a compound having a halogen atom in the cation portion of the ionic compound (C) described below.

[0410] In a preferred embodiment, the ionic compound (Y) is a compound having a halogen atom in the cation portion of the ionic compound (D) described below.

[0411] The content of the above ionic compound (Y) is 5.0 mass% or more with respect to the total solid content of the composition, but is preferably 10.0 mass% or more, and more preferably 15.0 mass% or more.

[0412] The upper limit of the content of the above ionic compound (Y) is not particularly limited, but with respect to the total solid content of the above composition, it is typically 70.0 mass% or less, preferably 60.0 mass% or less, and more preferably 50.0 mass% or less.

[0413] <(Z) Ionic compound having an acid-degrading group in the cation portion>

[0414] The composition of the present invention contains an ionic compound (Z) having an acid-degrading group in a cation portion (hereinafter also referred to as "ionic compound (Z)" or "compound (Z)").

[0415] The ionic compound (Z) is a compound having an anionic part and a cation part, and has an acid-degradable group in the cation part. The acid-degradable group is a group that decomposes by the action of an acid to generate a polar group. The acid-degradable group property is the same as the acid-degradable group described in the resin (A) above.

[0416] The ionic compound (Y) is typically an onium salt, examples of which include sulfonium salts, iodine salts, etc.

[0417] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0418] In a preferred embodiment, the ionic compound (Z) is the ionic compound (Y').

[0419] In a preferred embodiment, the ionic compound (Z) is a compound having an acid-degrading group in the cation portion of the photogenerator (B) described below.

[0420] In a preferred embodiment, the ionic compound (Z) is a compound having an acid-degrading group in the cation portion of the ionic compound (C) described below.

[0421] In a preferred embodiment, the ionic compound (Z) is a compound having an acid-degrading group in the cation portion of the ionic compound (D) described below.

[0422] The content of the above ionic compound (Z) is 1.0 mass% or more with respect to the total solid content of the composition, but is preferably 5.0 mass% or more, and more preferably 10.0 mass% or more.

[0423] The upper limit of the content of the above ionic compound (Y) is not particularly limited, but with respect to the total solid content of the above composition, it is typically 70.0 mass% or less, preferably 60.0 mass% or less, and more preferably 50.0 mass% or less.

[0424] <(B) Compounds that generate acid upon irradiation with active light or radiation>

[0425] The composition of the present invention preferably comprises a compound that generates acid upon irradiation with active light or radiation (also referred to as a photoacid generator or photoacid generator (B)). The photoacid generator is a compound that generates acid upon exposure to light (preferably exposure to EUV light).

[0426] In addition, in the light-sensitive or radiation-sensitive resin composition of the present invention, the compound (B) that generates acid upon irradiation with active light or radiation and the compound (C) described below may be the same compound.

[0427] The photogenerator may be in the form of a low-molecular-weight compound or incorporated into a part of a polymer. Additionally, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.

[0428] When the photogenerator is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and more preferably 1000 or less.

[0429] In the case where the photogenerator is introduced into a part of the polymer, it may be introduced into a part of the resin (A) or into a resin different from the resin (A).

[0430] In the present invention, it is preferable that the photogenerator be in the form of a low-molecular-weight compound.

[0431] The photogenerator is not particularly limited, but among them, a compound that generates an organic acid upon irradiation with EUV light is preferred, and a photogenerator having a fluorine atom or an iodine atom in its molecule is more preferred.

[0432] Examples of the above organic acids include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, and camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, and aralkylcarboxylic acid, etc.), carbonylsulfonylimide, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0433] In the present invention, the strength of the acid generated from the photogenerative agent (B) is not particularly limited, but for example, the pKa of the generated acid is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and more preferably -5.00 to 0.00.

[0434] Although the volume of acid generated from the photogenerative agent is not particularly limited, 240 Å is used in terms of suppressing the diffusion of acid generated by exposure to the unexposed area to improve resolution. 3 The above is desirable, and 305Å 3 The above is more preferable, and 350Å 3 The above is more desirable, and 400Å 3 The above is particularly desirable.

[0435] In addition, in terms of sensitivity or solubility as a coating solvent, the volume of acid generated from the photogenerator is 1500 Å. 3 The following is preferable, and 1000 Å 3 The following is more preferable, and 700Å 3 The following is more desirable.

[0436] The above volume values ​​are obtained using "WinMOPAC" manufactured by Fujitsu Corporation. In calculating the above volume values, first, the chemical structure of the acid for each example is input, and next, the most stable stereochemical position of each acid is determined by calculating the molecular force field using the MM (Molecular Mechanics) 3 method with this structure as the initial structure, and then, the "accessible volume" of each acid can be calculated by performing molecular orbital calculations using the PM (Parameterized Model Number) 3 method for these most stable stereochemical positions.

[0437] The structure of the acid generated from the photogenerator is not particularly limited, but it is desirable that the interaction between the acid generated from the photogenerator and the resin (A) be strong in order to suppress the diffusion of the acid and improve resolution. In this regard, when the acid generated from the photogenerator is an organic acid, for example, it is desirable to have additional polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonylsulfonylimide groups, bissulfonylimide groups, and trissulfonylmedide groups.

[0438] Examples of polar groups include, for instance, ether groups, ester groups, amide groups, acyl groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, carbamate groups, hydroxyl groups, and mercapto groups.

[0439] The number of polar groups of the acid generated is not particularly limited, but it is preferable to have one or more, and more preferable to have two or more. However, in order to suppress the phenomenon of excess, it is preferable that the number of polar groups be less than 6, and more preferable to have less than 4.

[0440] The photocatalyst is preferably an acid-generating photocatalyst exemplified below. In addition, for some of the examples, calculated volume values ​​are noted (unit Å). 3 ).

[0441] [Chemical Formula 31]

[0442]

[0443] [Chemical Formula 32]

[0444]

[0445] [Chemical Formula 33]

[0446]

[0447] As for the photogenerator, it is not particularly limited, but may be a photogenerator with a non-anionic structure that does not have anions and cations, or a photogenerator that has anions and cations, so-called onium salts.

[0448] In terms of superior effects of the present invention, it is preferable that the photogener be an onium salt.

[0449] The photogenerator may have a halogen atom in its cation portion, or it may not have a halogen atom in its cation portion. In a preferred embodiment, it is preferable that the photogenerator has a halogen atom in its cation portion.

[0450] A photogenerator having a halogen atom in the cation portion (hereinafter also referred to as "photogenerator B1") is included in the above ionic compound (Y).

[0451] The photogenerator may be a photogenerator that does not have a halogen atom in the cation portion (hereinafter also referred to as "photogenerator B2").

[0452] (Compounds represented by the general formula (PA-1))

[0453] It is preferable that the photogenerator include a compound represented by the general formula (PA-1).

[0454] [Chemical Formula 34]

[0455]

[0456] Among the general formula (PA-1), A 1 and A 2 -SO2-R, each independently P , or, -CO-R P It represents. R P represents an organic group.

[0457] Among the general formula (PA-1), there are 2 R's. P It may be the same or different.

[0458] Among the general formula (PA-1), there are 2 R's. P The number of carbon atoms is, independently, preferably 1 to 25, and more preferably 1 to 15.

[0459] Among the general formula (PA-1), there are 2 R's. P The number of atoms excluding hydrogen atoms is, independently, preferably 2 to 30, and more preferably 4 to 20.

[0460] R P It is desirable to have a device represented by the general formula (RF).

[0461] -L RF -R RF (RF)

[0462] Among the general formula (RF), L RF represents a single link or a divalent link.

[0463] Examples of the above divalent linkers include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (may be straight or branched; preferably 1 to 6 carbon atoms), cycloalkylene groups (preferably 3 to 15 carbon atoms), alkenylene groups (may be straight or branched; preferably 2 to 6 carbon atoms), and divalent linkers formed by combining a plurality of these.

[0464] In addition, the substituents that can be provided for these divalent linkers are preferably halogen atoms, and more preferably fluorine atoms. For example, it is also preferable that the alkylene group (including alkylene groups that can be included in a divalent linker formed by combining multiple groups) be a perfluoroalkylene group.

[0465] The above divalent linker is preferably -alkylene group-COO- or -alkylene group-SO2-. For -alkylene group-COO- and -alkylene group-SO2-, it is preferable that the alkylene group be located on the N- side.

[0466] Among the general formula (RF), R RF represents a cycloalkyl group or an alkyl group.

[0467] R RF In the case where α is a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic.

[0468] The number of carbon atoms in the cycloalkyl group is preferably 3 to 15, and more preferably 5 to 10.

[0469] Examples of the above cycloalkyl groups include a norbonyl group, a decalinyl group, and an adamantyl group.

[0470] The substituent that the above cycloalkyl group may have is preferably an alkyl group (which may be straight-chain or branched-chain; preferably, having 1 to 5 carbon atoms). It is also preferable that the above cycloalkyl group does not have any other substituents.

[0471] One or more of the carbon atoms that are the reducing atoms of the above cycloalkyl group may be substituted with carbonyl carbon atoms and / or heteroatoms. For example, L in the cycloalkyl group RF The carbon atom (-CH<) bonded to it may be replaced with a nitrogen atom (-N<).

[0472] R RF In the case where the alkyl group is an alkyl group, the alkyl group may be a straight chain or a branched chain.

[0473] The number of carbon atoms in the above alkyl group is preferably 1 to 10, and more preferably 1 to 5.

[0474] The substituents that the above alkyl group may have are preferably cycloalkyl groups, fluorine atoms, or cyano groups. It is also preferable that the above alkyl group does not have substituents other than these.

[0475] Examples of cycloalkyl groups as the above substituents include, for example, R RF In the case where is a cycloalkyl group, the cycloalkyl group described above can be cited in the same way.

[0476] When the above alkyl group has a fluorine atom as a substituent, the alkyl group may or may not be a perfluoroalkyl group. When the above alkyl group has a fluorine atom as a substituent, it is also preferable that part or all of the alkyl group is a perfluoromethyl group.

[0477] Among the general formula (PA-1), "A 1 -N - -A 2 2 Rs included in " P They may combine with each other to form a ring.

[0478] Among the general formula (PA-1), M + Silver represents a cation.

[0479] M + The cation is preferably an organic cation, and an organic cation having a halogen atom is more preferable.

[0480] The above organic cations are preferably, respectively, a cation represented by the general formula (ZaI) or a cation represented by the general formula (ZaII) (cation (ZaII)).

[0481] [Chemical Formula 35]

[0482]

[0483] In the above general formula (ZaI),

[0484] R 201 , R 202 , and R 203 Each represents an organic group independently. R 201 , R 202 , and R 203 It is preferable that at least one of them is an organic group having a halogen atom.

[0485] R 201 , R 202 , and R 203 The number of carbon atoms in the organic group as is typically 1 to 30, and preferably 1 to 20. Also, R 201 ~R 203 Two of them may combine 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. R 201 ~R 203 Examples of groups formed by the combination of two of them include, for instance, alkylene groups (e.g., butylene groups, pentylene groups), and -CH2-CH2-O-CH2-CH2-.

[0486] Examples of cations in the general formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), cation represented by the general formula (ZaI-3b) (cation (ZaI-3b)), and cation represented by the general formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0487] First, we will explain the cation (ZaI-1).

[0488] The cation (ZaI-1) is R of the above general formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group. R of the above general formula (ZaI). 201 ~R 203 It is preferable that at least one of them is an aryl group having a halogen atom.

[0489] The arylsulfonium cation is, R 201 ~R 203 It is okay if everything is Arilgi, R 201 ~R 203 A portion of it may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.

[0490] Also, R 201 ~R 203 One of them is an aryl group, and R 201 ~R 203 The remaining two may combine 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. R 201 ~R 203 Examples of groups formed by the combination of two of them include alkylene groups (e.g., butylene group, pentylene group, or -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups are substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and / or carbonyl groups.

[0491] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0492] The aryl group included 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 having an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.

[0493] The alkyl group or cycloalkyl group that the arylsulfonium cation has as needed is preferably a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples include 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, and a cyclohexyl group.

[0494] R 201 ~R 203 The aryl group, alkyl group, and cycloalkyl group may have substituents.

[0495] R 201 ~R 203 The substituents that may be present in the aryl group, alkyl group, and cycloalkyl group are not particularly limited, but each independently preferably are an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 14 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group.

[0496] The above substituent may have additional substituents if possible, for example, the above alkyl group may have a halogen atom as a substituent and may be an alkyl halide group such as a trifluoromethyl group.

[0497] Next, the cation (ZaI-2) will be described.

[0498] The cation (ZaI-2) is R in the formula (ZaI). 201 ~R 203 These are cations that each independently represent an organic group that does not possess an aromatic ring. Here, the term "aromatic ring" includes aromatic rings containing heteroatoms. R in formula (ZaI) 201 ~R 203 This is a cation representing an organic group that does not have an aromatic ring, and it is preferable that at least one of the organic groups has a halogen atom.

[0499] R 201 ~R 203 The organic group that does not have an aromatic ring generally has 1 to 30 carbon atoms, and 1 to 20 carbon atoms is preferred.

[0500] R 201 ~R 203 Each independently, an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group is preferred, a straight-chain or branched-chain 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group is more preferred, and a straight-chain or branched-chain 2-oxoalkyl group is even more preferred.

[0501] R 201 ~R 203 Examples of alkyl groups and cycloalkyl groups include straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and novonyl group).

[0502] R 201 ~R 203 It may be further substituted by silver, halogen atoms, alkoxy groups (e.g., carbon atoms 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0503] Next, the cation (ZaI-3b) is described.

[0504] The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

[0505] [Chemical Formula 36]

[0506]

[0507] Among the general formula (ZaI-3b),

[0508] R 1c ~R 5c Each represents, independently, 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.

[0509] R 6c and R 7c Each represents, independently, a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0510] R x and R y Each represents an alkyl group, cycloalkyl group, 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxycarbonylalkyl group, allyl group, or vinyl group, which may independently have a halogen atom.

[0511] R 1c ~R 5c Any 2 or more of, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y Each may combine to form a ring, and each ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

[0512] Examples of the above rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. The rings may be 3 to 10-membered rings, 4 to 8-membered rings are preferred, and 5 or 6-membered rings are more preferred.

[0513] R 1c ~R 5c Any 2 or more of, R 6c and R 7c , and, R x and R y Examples of groups formed by bonding include alkylene groups such as butylene groups and pentylene groups. The methylene group in these alkylene groups may be substituted with a heteroatom such as an oxygen atom.

[0514] R 5c and R 6c , and, R 5c and R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene groups and ethylene groups.

[0515] Next, the cation (ZaI-4b) is described. The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

[0516] [Chemical Formula 37]

[0517]

[0518] Among the general formula (ZaI-4b),

[0519] l represents an integer from 0 to 2.

[0520] r represents an integer from 0 to 8.

[0521] R 13It represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be the cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents.

[0522] R 14 R represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (it may be the cycloalkyl group itself or a group comprising a cycloalkyl group in part). These groups may have substituents. R 14 In cases where multiple groups exist, each independently represents the above groups, such as hydroxyl groups.

[0523] R 15 represents, respectively, an alkyl group, a cycloalkyl group, or a naphthyl group that may have a halogen atom. These groups may have substituents. Two Rs 15 They may combine to form a ring. Two R 15 When they combine with each other to form a ring, heteroatoms such as oxygen atoms or nitrogen atoms may be included within the ring framework. In one embodiment, two R 15 It is desirable that the groups be alkylene groups and bond with each other to form a ring structure.

[0524] In the general formula (ZaI-4b), R 13 , R 14 , and, R 15 The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

[0525] Next, the general formula (ZaII) is explained. Among the general formula (ZaII), R 204 and R 205Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group that may have a halogen atom.

[0526] R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. R 204 and R 205 The aryl group may be an aryl group having a heterocyclic group having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the backbone of an aryl group having a heterocyclic group include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0527] R 204 and R 205 The alkyl group and cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0528] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of may each independently have a substituent. R 204 and R 205 Examples of substituents that may be present in the aryl group, alkyl group, and cycloalkyl group include, for example, an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 15 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthione group.

[0529] As a preferred embodiment, the cation represented by the general formula (ZaI) and the cation represented by the general formula (ZaII) may or may not have an acid-degrading group, and it is preferable that they have an acid-degrading group.

[0530] The acid-degradable group is a group that is decomposed by the action of acid to generate a polar group. The acid-degradable group is the same as the acid-degradable group described in the resin (A) above.

[0531] (Other mine-generating agents)

[0532] The composition of the present invention may use other photocatalytic agents other than those described above.

[0533] Other mine-generating agents include, for example, "M + Z - (M + Silver represents a cation and Z - Examples include compounds (onium salts) that appear as "represents an anion".

[0534] "M + Z - In compounds represented as ", M + Silver represents a cation, and examples of cations identical to the cation in the general formula (PA-1) can be given.

[0535] "M + Z - In compounds represented as ", Z - It is desirable to have an anion that exhibits an anion and has a significantly low ability to cause a nucleus reaction.

[0536] Examples of the above anions include sulfonic acid anions (aliphatic sulfonic acid anions such as fluoroalkylsulfonic acid anions, aromatic sulfonic acid anions, and camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkylcarboxylic acid anions, etc.), and tris(alkylsulfonyl)methide anions.

[0537] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and is preferably a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

[0538] The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples include a phenyl group, a tolyl group, and a naphthyl group.

[0539] As substituents that the alkyl group, cycloalkyl group, and aryl group described above may have, for example, a nitro group, a halogen atom such as a fluorine atom, a carboxylic acid group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably 6 to 20 carbon atoms). Examples include an alkylaryl oxysulfonyl group (preferably 7 to 20 carbon atoms), a cycloalkylaryl oxysulfonyl group (preferably 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferably 8 to 20 carbon atoms).

[0540] The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0541] In the tris(alkylsulfonyl)methide anion, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

[0542] A plurality of sulfonate anions may be bonded to each other via a linker. A plurality of sulfonate anions may be bonded to each other via a linker. Also, a plurality of tris(alkylsulfonyl)methide anions may be bonded to each other via a linker.

[0543] Other non-nucleated anions include, for example, phosphorus fluoride (e.g., PF6) - ), boron fluoride (e.g., BF4 - ), and, antimony fluoride (e.g., SbF6 - ...can be cited.

[0544] The non-nucleated anion is preferably an aliphatic sulfonate anion in which at least the α-site of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom. Among these, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferred, and a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.

[0545] In terms of acid strength, it is desirable for the pKa of the generated acid to be -1 or lower to improve sensitivity.

[0546] In addition, non-nucleated anions are also preferred as anions represented by the following general formula (AN1).

[0547] [Chemical Formula 38]

[0548]

[0549] In the formula, Xf represents, respectively, a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0550] R 1 and R 2represents, respectively, a hydrogen atom, a fluorine atom, or an alkyl group, and R in the case where multiple are present. 1 and R 2 Each can be the same or different.

[0551] L represents a 2-valent linker, and in the case of multiple links, L may be the same or different.

[0552] A represents an illusory organic device.

[0553] x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0554] The general formula (AN1) is explained in more detail.

[0555] The number of carbon atoms in the alkyl group substituted with a fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4. In addition, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

[0556] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of Xf include a fluorine atom, CF3, C2F5, C3F7, C4F9, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, among which a fluorine atom or CF3 is preferred. In particular, it is preferred that both Xf are fluorine atoms.

[0557] R 1 and R 2 The alkyl group may have a substituent (preferably a fluorine atom), and the number of carbon atoms in the substituent is preferably 1 to 4. The substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R 1 and R 2 Alkyl groups having substituents are, for example, CF3, C2F5, C3F7, C4F9, C5F 11 , C6F13 , C7F 15 , C8F 17 Examples include CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, among which CF3 is preferred.

[0558] R 1 and R 2 Fluorine atoms or CF3 are preferred.

[0559] x is preferably an integer from 1 to 10, and more preferably from 1 to 5.

[0560] y is preferably an integer between 0 and 4, and 0 is more preferable.

[0561] z is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0562] Examples of divalent linkers of L include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, and linkers formed by connecting multiple of these, and linkers with a total carbon number of 12 or fewer are preferred. Among these, -COO-, -CO-, or -O- are preferred, and -COO- is more preferred.

[0563] The cyclic organic groups of A are not particularly limited as long as they have a cyclic structure, and examples include radicular groups, directional groups, and complex groups (including those that are aromatic as well as those that are not aromatic).

[0564] The alicyclic group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups are preferred, and additionally polycyclic cycloalkyl groups such as norbornyl groups, tricyclodecaneyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl groups, tricyclodecaneyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups, are preferred in terms of improving MEEF (Mask Error Enhancement Factor) because they can suppress diffusivity within the film during the heating process after exposure.

[0565] Examples of directional radiators include the benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring.

[0566] Examples of complex ring groups include groups derived from furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Among these, groups derived from furan rings, thiophene rings, or pyridine rings are preferred.

[0567] In addition, as a cyclic organic group, a lactone structure can be cited, and as a specific example, a lactone structure represented by the general formulas (LC1-1) to (LC1-22) described above can be cited.

[0568] The above-mentioned cyclic organic group may have a substituent. Examples of the substituents include an alkyl group (which may be straight-chain or branched and may include a cyclic structure; preferably, the number of carbon atoms is 1 to 12), a cycloalkyl group (which may be either monocyclic or polycyclic, and in the case of polycyclic, may be a spirocyclic group; preferably, the number of carbon atoms is 3 to 20), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a uretane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. Additionally, the carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0569] In addition, the photogenerator may be a beta compound having a cationic part and an anionic part, and the two parts connected by a covalent bond.

[0570] As for photocatalytic agents, reference may be made to paragraphs

[0368] to

[0377] of Japanese Patent Publication No. 2014-41328 and paragraphs

[0240] to

[0262] of Japanese Patent Publication No. 2013-228681 (corresponding U.S. Patent Application Publication No. 2015 / 004533

[0339] ), and the contents thereof are incorporated into the present specification.

[0571] In addition, the following compounds may be cited as preferred embodiments. In the following compounds, the anion and the cation may be optionally interchangeable.

[0572] [Chemical Formula 39]

[0573]

[0574] [Chemical Formula 40]

[0575]

[0576] [Chemical Formula 41]

[0577]

[0578] [Chemical Formula 42]

[0579]

[0580] [Chemical Formula 43]

[0581]

[0582] [Chemical Formula 44]

[0583]

[0584] [Chemical Formula 45]

[0585]

[0586] [Chemical Formula 46]

[0587]

[0588] The content of the photogenerator in the composition of the present invention is not particularly limited, but for superior effects of the present invention, it is preferable to have 5.0 mass% or more, 9.0 mass% or more, and 15.0 mass% or more with respect to the total solid content of the composition. In addition, the content is preferably 70 mass% or less, more preferably 60 mass% or less, and more preferably 50 mass% or less.

[0589] The photocatalytic agent may be used as a single type or as two or more types.

[0590] <(C) Ionic compounds that decompose upon irradiation with active light or radiation, thereby reducing their scattering ability>

[0591] The composition of the present invention may include, as an acid diffusion control agent, (C) an ionic compound that decomposes upon irradiation with active light or radiation and reduces acid capture ability (also referred to as compound (C), ionic compound (C), photodegradable quencher, or photodegradable quencher (C)).

[0592] The ionic compound (C) acts as a quencher that traps the acid generated from the photogenerative agent (B) during exposure and suppresses the reaction of the resin (A) in the unexposed area caused by the excess generated acid.

[0593] The ionic compound (C) is a compound that generates an acid that is relatively weak compared to the acid generated from the photogenerator (B). That is, the ionic compound (C) is a compound that generates an acid with a pKa greater than that of the acid generated from the photogenerator (B).

[0594] The difference between the pKa of the acid generated from the ionic compound (C) and the pKa of the acid generated from the photogenerator (B) (the value obtained by subtracting the pKa of the acid generated from the photogenerator (B) from the pKa of the acid generated from the ionic compound (C)) is preferably 1.00 or more, preferably 1.00 to 10.00, more preferably 1.00 to 5.00, and more preferably 1.00 to 3.00.

[0595] In addition, the pKa of the acid generated from the ionic compound (C) varies depending on the type of photogenerator (B) used, but, for example, -4.00 to 14.00 is preferred, -2.00 to 12.00 is more preferred, and -1.00 to 5.00 is more preferred.

[0596] In a preferred embodiment, the ionic compound (C) contains a halogen atom in the anionic portion. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred.

[0597] In addition, the acid-capturing group of the ionic compound (C) is preferably anionic.

[0598] As the ionic compound (C), the compound used as the photogenerator (B) (preferably, the compound represented by the general formula (PA-1), M + Z - Among the onium salts that appear as such, a compound that generates an acid that is relatively weak compared to the acid generated from the photogenerative agent (B) used can be selected and used.

[0599] The ionic compound (C) may have a halogen atom in its cation portion, or it may not have a halogen atom in its cation portion. As a preferred embodiment, the ionic compound (C) preferably has a halogen atom in its cation portion.

[0600] An ionic compound (C) having a halogen atom in the cation portion (hereinafter also referred to as "ionic compound C1" or "photodecaying quencher C1") is included in the above ionic compound (Y).

[0601] The ionic compound (C) may be an ionic compound that does not have a halogen atom in the cation portion (hereinafter also referred to as "ionic compound C2" or "photodecaying quencher C2").

[0602] The ionic compound (C) is preferably a compound represented by the following general formulas (C1) to (C3).

[0603] (Compounds represented by the general formula (C1))

[0604] [Chemical Formula 47]

[0605]

[0606] Among the general formula (C1),

[0607] R C1 It represents a cycloalkyl group or an aryl group.

[0608] L C1 It represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linker formed by a combination thereof.

[0609] M C + represents an organic cation.

[0610] Among the general formula (C1),

[0611] R C1 It represents a cycloalkyl group or an aryl group.

[0612] R C1As for the cycloalkyl group representing this cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic.

[0613] Examples of cycloalkyl groups include norbonyl groups, decalinyl groups, and adamantyl groups, and it is preferable that the adamantyl group be one.

[0614] R C1 As for the aryl group representing this aryl group, an aryl group having 6 to 15 carbon atoms is preferred.

[0615] Examples of aryl groups include phenyl groups and naphthyl groups, and it is preferable that it be a phenyl group.

[0616] R C1 It may have substituents.

[0617] As a desirable mode of work, R C1 Examples of substituents that have this substituent include fluorine atoms, groups having fluorine atoms, hydroxyl groups, alkyl groups, halogen atoms other than fluorine atoms, etc.

[0618] As for the group having a fluorine atom, a fluorine-substituted alkyl group or a fluorine-substituted cycloalkyl group is preferred.

[0619] As for the fluorine-substituted alkyl group, a fluorinated alkyl group having 1 to 5 carbon atoms is preferred. Specifically, examples include a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, etc., and it is preferred to be a trifluoromethyl group.

[0620] As a fluorine-substituted cycloalkyl group, a fluorinated cycloalkyl group having 3 to 15 carbon atoms is preferred. Specifically, examples include a fluorinated cyclohexyl group, a fluorinated cyclopentyl group, a fluorinated adamantyl group, etc., and it is preferred to be a fluorinated cyclohexyl group.

[0621] Examples of alkyl groups include chain-like or branched alkyl groups having 1 to 5 carbon atoms.

[0622] Halogen atoms other than fluorine atoms include chlorine, bromine, and iodine atoms.

[0623] As a desirable mode of work, R C1 , and L C1 At least one of them is substituted with a fluorine atom or a group having a fluorine atom.

[0624] As a desirable mode of work, R C1 It is preferable that it be a polycyclic cycloalkyl group or an aryl group substituted with a fluorine atom or a group having a fluorine atom.

[0625] Among the general formula (C1),

[0626] L C1 It represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a divalent linker formed by a combination thereof.

[0627] L C1 Examples of alkylene groups that represent this alkylene group include chain-like or branched alkylene groups having 1 to 20 carbon atoms.

[0628] Examples of chain-like or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, n-pentylene groups, etc., and methylene groups, ethylene groups, n-propylene groups, or n-butylene groups are preferred.

[0629] L C1 Examples of cycloalkylene groups that represent this cycloalkylene group include monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms.

[0630] Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene groups, cyclohexylene groups, cyclopentylene groups, cycloheptylene groups, norbornylene groups, and adamantylene groups, cyclohexylene groups, and norbornylene groups are preferred.

[0631] L C1 It may have substituents.

[0632] As a desirable mode of work, L C1 As a substituent in the case having this substituent, the above R C1 Examples of substituents that have this substituent can be given.

[0633] L C1 It is preferable that the bond be a single bond or an alkylene group, and more preferable that the bond be a single bond or an n-butylene group.

[0634] Among the general formula (C1),

[0635] M C + represents an organic cation.

[0636] M C + It is preferable that it be a cation represented by the following general formula (ZcI) or general formula (ZcII).

[0637] [Chemical Formula 48]

[0638]

[0639] Among the general formula (ZcI),

[0640] R C01 , R C02 , and R C03 Each independently represents an organic group.

[0641] [Chemical Formula 49]

[0642]

[0643] Among the general formula (ZcII),

[0644] R C04 , and R C05 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0645] In the above general formula (ZcI),

[0646] R C01 , R C02 , and R C03 Each independently represents an organic group.

[0647] R C01 , R C02 , and R C03 The number of carbon atoms in the organic group as is typically 1 to 30, and preferably 1 to 20. Also, R C01 ~R C03 Two of them may combine 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. R C01 ~R C03 Examples of groups formed by the combination of two of them include, for instance, alkylene groups (e.g., butylene groups, pentylene groups), and -CH2-CH2-O-CH2-CH2-.

[0648] Examples of cations in the general formula (ZcI) include the cation (ZaI-1), cation (ZaI-2), cation represented by the general formula (ZaI-3b) and cation represented by the general formula (ZaI-4b) in the photogenerator (B) described above.

[0649] In the general formula (ZcII),

[0650] R C04 , and R C05 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0651] R C04 , and R C05 The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. R C04 , and R C05 The aryl group may be an aryl group having a heterocyclic group having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the backbone of an aryl group having a heterocyclic group include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0652] R C04 , and R C05The alkyl group and cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0653] R C04 , and R C05 The aryl group, alkyl group, and cycloalkyl group of may each independently have a substituent. R C04 , and R C05 Examples of substituents that may be present in the aryl group, alkyl group, and cycloalkyl group include, for example, an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 15 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthione group.

[0654] In a preferred embodiment, the cation represented by the general formula (ZcI) and the cation represented by the general formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes by the action of an acid to generate a polar group. The acid-degradable group property is the same as the acid-degradable group described in the resin (A) above.

[0655] The compound represented by the general formula (C1) may have a halogen atom in the cation portion, or it may not have a halogen atom in the cation portion.

[0656] (Compounds represented by the general formula (C2))

[0657] [Chemical Formula 50]

[0658]

[0659] Among the general formula (C2),

[0660] R C2 represents a cycloalkyl group or an aryl group.

[0661] L C2 represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a combination thereof.

[0662] M C + represents an organic cation.

[0663] Among the general formula (C2),

[0664] R C2 represents a cycloalkyl group or an aryl group.

[0665] R C2 When the cycloalkyl group is represented, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic.

[0666] Examples of cycloalkyl groups include norbonyl groups, decalinyl groups, and adamantyl groups, and it is preferable that the adamantyl group be one.

[0667] R C2 When ga represents an aryl group, an aryl group having 6 to 15 carbon atoms is preferred as the aryl group.

[0668] Examples of aryl groups include phenyl groups and naphthyl groups, and it is preferable that it be a phenyl group.

[0669] R C2 It may have substituents.

[0670] As a desirable mode of work, R C2 As a substituent in the case where ga has a substituent, R in the general formula (C1) as a preferred embodiment above is C1 Examples of substituents that have this substituent can be given.

[0671] R C2It is preferable that the group is a polycyclic cycloalkyl group, a polycyclic cycloalkyl group substituted with a fluorine atom or a group having a fluorine atom, or an aryl group substituted with a fluorine atom or a group having a fluorine atom, and more preferable that the group is an adamantyl group or a phenyl group substituted with a fluorine atom or a group having a fluorine atom.

[0672] Among the general formula (C2),

[0673] L C2 represents a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a combination thereof.

[0674] L C2 Examples of alkylene groups that represent alkylene groups include chain-like or branched alkylene groups having 1 to 20 carbon atoms.

[0675] Examples of chain-like or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, n-pentylene groups, etc., and methylene groups, ethylene groups, n-propylene groups, or n-butylene groups are preferred.

[0676] L C2 Examples of cycloalkylene groups that represent a cycloalkylene group include a monocyclic or polycyclic cycloalkylene group having 3 to 20 carbon atoms.

[0677] Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene groups, cyclohexylene groups, cyclopentylene groups, cycloheptylene groups, norbornylene groups, and adamantylene groups, cyclohexylene groups, and norbornylene groups are preferred.

[0678] L C2 It may have substituents.

[0679] As a desirable mode of work, L C2 As a substituent in the case where ga has a substituent, R as in the above-mentioned preferred embodiment C2 Examples of substituents that have a substituent can be given.

[0680] The above R C2 If ga represents an aryl group, L C2 It is preferable that it be a single bond.

[0681] The above R C2 If represents a cycloalkyl group, L C2 It is preferable that the linker is a divalent linker formed by an alkylene group, -O-, -C(=O)-, or a combination thereof, and it is preferable that the linker is a divalent linker formed by an alkylene group, -O-, -C(=O)-, or a combination thereof substituted with a fluorine atom or a group having a fluorine atom.

[0682] As a desirable mode of work, R C2 , and L C2 At least one of them is substituted with a fluorine atom or a group having a fluorine atom. The group having a fluorine atom is as described above.

[0683] M C + represents an organic cation.

[0684] M C + It is preferable that it be a cation represented by the above general formula (ZcI) or the above general formula (ZcII).

[0685] In a preferred embodiment, the cation represented by the general formula (ZcI) and the cation represented by the general formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes by the action of an acid to generate a polar group. The acid-degradable group property is the same as the acid-degradable group described in the resin (A) above.

[0686] The compound represented by the general formula (C2) may have a halogen atom in the cation portion, or it may not have a halogen atom in the cation portion.

[0687] (Compounds represented by the general formula (C3))

[0688] [Chemical Formula 51]

[0689]

[0690] Among the general formula (C3),

[0691] A C31 , and A C32 -SO2-R, each independently PC1 , or -CO-R PC2 It represents.

[0692] R PC1 , and R PC2 represents an organic group.

[0693] M C + represents an organic cation.

[0694] Among the general formula (C3), A C31 and A C32 -SO2-R, each independently PC1 , or -CO-R PC2 It represents.

[0695] R PC1 , and R PC2 represents an organic group.

[0696] R PC1 , and R PC2 is, respectively, -L C31 -R C31 , and -L C32 -R C32 It is desirable that it be expressed as such.

[0697] R C31 , and R C32 Each represents, independently, an alkyl group or a cycloalkyl group.

[0698] R C31 , or R C32 As for the alkyl group in which α represents an alkyl group, a chain-like or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0699] Examples of alkyl groups include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, etc., and methyl groups or ethyl groups are preferred, and methyl groups are more preferred.

[0700] R C31 , or R C32 When the cycloalkyl group is represented, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic.

[0701] Examples of cycloalkyl groups include cyclohexyl groups, norbornyl groups, decalinyl groups, and adamantyl groups, and it is preferable that the cyclohexyl group or the adamantyl group be a cyclohexyl group or an adamantyl group.

[0702] One or more of the carbon atoms that are the reducing atoms of the above cycloalkyl group may be substituted with carbonyl carbon atoms.

[0703] R C31 , or R C32 It may have substituents.

[0704] As a desirable mode of work, R C31 , or R C32 As a substituent in the case where ga has a substituent, R in the general formula (C1) as a preferred embodiment above is C1 Examples of substituents that have this substituent can be given.

[0705] R C31 , and R C32 It is preferable that each is independently an alkyl group, an alkyl group substituted with a fluorine atom or a group having a fluorine atom, or a cycloalkyl group, and more preferable that it is a methyl group, a trifluoromethyl group, a cyclohexyl group, or an adamantyl group.

[0706] L C31 , and L C32 Each represents, independently, a single bond or a divalent linker.

[0707] LC31 , and L C32 It is preferable that each represent a divalent linker formed independently of a single bond, an alkylene group, a cycloalkylene group, -O-, -C(=O)-, or a combination thereof.

[0708] L C31 or L C32 Examples of alkylene groups that represent alkylene groups include chain-like or branched alkylene groups having 1 to 20 carbon atoms.

[0709] Examples of chain-like or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, n-pentylene groups, etc., and methylene groups, ethylene groups, n-propylene groups, or n-butylene groups are preferred.

[0710] L C31 or L C32 Examples of cycloalkylene groups that represent a cycloalkylene group include a monocyclic or polycyclic cycloalkylene group having 3 to 20 carbon atoms.

[0711] Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene groups, cyclohexylene groups, cyclopentylene groups, cycloheptylene groups, norbornylene groups, and adamantylene groups, cyclohexylene groups, and norbornylene groups are preferred.

[0712] L C31 , or L C32 It may have substituents.

[0713] As a desirable mode of work, L C31 , or L C32 As a substituent in the case where ga has a substituent, the above R as in the above preferred embodiment C31 , or R C32 Examples of substituents that have a substituent can be given.

[0714] L C31 , and L C32It is preferable that each is independently a single bond, an alkylene group, or a fluorine-substituted alkylene group.

[0715] As a desirable mode of work, A C31 , and A C32 At least one of them is substituted with a fluorine atom or a group having a fluorine atom.

[0716] Among the general formula (C3), M C + represents an organic cation.

[0717] M C + It is preferable that the cation is represented by the above general formula (ZcI) or general formula (ZcII).

[0718] In a preferred embodiment, the cation represented by the general formula (ZcI) and the cation represented by the general formula (ZcII) may or may not have an acid-degradable group, but it is preferable that they have an acid-degradable group. An acid-degradable group is a group that decomposes by the action of an acid to generate a polar group. The acid-degradable group property is the same as the acid-degradable group described in the resin (A) above.

[0719] A compound represented by the general formula (C3) may have a halogen atom in the cation portion, or it may not have a halogen atom in the cation portion.

[0720] As preferred embodiments of the above ionic compound (C), the following compounds may be cited. In the following compounds, the anion and the cation may be optionally interchangeable.

[0721] [Chemical Formula 52]

[0722]

[0723] [Chemical Formula 53]

[0724]

[0725] [Chemical Formula 54]

[0726]

[0727] [Chemical Formula 55]

[0728]

[0729] [Chemical Formula 56]

[0730]

[0731] [Chemical Formula 57]

[0732]

[0733] [Chemical Formula 58]

[0734]

[0735] The content of the ionic compound (C) in the composition of the present invention is not particularly limited, but for superior effects of the present invention, it is preferable to have 1.0 mass% or more, 2.0 mass% or more, and 5.0 mass% or more with respect to the total solid content of the composition. In addition, the content is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, and more preferably 50.0 mass% or less.

[0736] The ionic compound (C) may be used as a single type or as two or more types.

[0737] <Ionic compound (D) that generates acid upon irradiation with active light or radiation and decomposes upon irradiation with active light or radiation, thereby reducing acid capture ability>

[0738] The composition of the present invention may contain a compound that is both a photogenerator (B) and an ionic compound (C), that is, an ionic compound (D) that generates acid upon irradiation with active light or radiation and decomposes upon irradiation with active light or radiation, thereby reducing acid capture ability (also referred to as ionic compound (D), photogenerator-linked quencher, or photogenerator-linked quencher (D)). In other words, the ionic compound (D) is a compound having a structure having a function equivalent to that of the photogenerator (B) and a structure having a function equivalent to that of the ionic compound (C).

[0739] The ionic compound (D) is a preferred embodiment of the photogenerator (B) and is also a preferred embodiment of the ionic compound (C).

[0740] In addition, as described above, in the present invention, the ionic compound (C) is a compound that generates an acid that is relatively weak compared to the acid generated from the photogenerator (B). That is, the ionic compound (C) is a compound that generates an acid with a pKa greater than that of the acid generated from the photogenerator (B). In the case where the photogenerator (B) and the ionic compound (C) are the same ionic compound (D), the pKa of the acid generated from the structure having a function equivalent to that of the ionic compound (C) in the ionic compound (D) is made greater than the pKa of the acid generated from the structure having a function equivalent to that of the photogenerator (B).

[0741] (Compounds represented by the general formula (PD))

[0742] The ionic compound (D) is not particularly limited, but is preferably a compound represented by the following general formula (PD).

[0743] [Chemical Formula 59]

[0744]

[0745] Among the general formula (PD),

[0746] M D1 + , and M D2 + Each independently represents an organic cation.

[0747] L D represents a divalent organic group.

[0748] A D1 - , and B D1 - Each independently represents an acid anion group.

[0749] However, M of the compound represented by the general formula (PD) D1 + and M D2 + HA in which each is substituted with a hydrogen atom D1 -L D -B D1 In compounds represented by H, HA D1 The pKa of the group represented as is B D1 It is lower than the pKa of the group represented by H.

[0750] The compound represented by the general formula (PD) is a structure ("M) having a function equivalent to a photogenerator (B). D1 + A D1 - - (part corresponding to -) and a structure having a function corresponding to an ionic compound (C) ("-B D1 - M D2 + Because both sides of the "part corresponding to" are included in one molecule, the respective existence ratios of the above structure can be kept constant within the resist film.

[0751] For this reason, the inventors speculate that even when the resist film is exposed to light, the amount and diffusion of acid generated within the resist film tend to become uniform, and the width of the pattern obtained after development becomes stable.

[0752] Among the general formula (PD), M D1 + and MD2 + Each independently represents an organic cation.

[0753] M D1 + and M D2 + It is preferable that the organic cations are each independently cations represented by the general formula (ZcI) or the general formula (ZcII).

[0754] Among the general formula (PD), L D represents a divalent organic group.

[0755] Examples of the above divalent organic groups include -COO-, -CONH-, -CO-, alkylene groups (preferably having 1 to 6 carbon atoms; they may be straight or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linkers formed by combining a plurality of these.

[0756] One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and / or oxygen atom.

[0757] It is also desirable that the divalent linkers of these have a group selected from the group consisting of -O-, -S-, -SO-, and -SO2-.

[0758] Among them, L D It is preferable that it be represented by the following general formula (LD).

[0759] *A D -L D AL D BL D CL D DL D E-*B D (LD)

[0760] Among the general formula (LD), *A D is A in the general formula (PD). D1 - Indicates the connection location with.

[0761] Among the general formula (LD), *B D is B in the general formula (PD). D1 - Indicates the connection location with.

[0762] Among the general formula (LD), L D A is, -(C(R D LA1 )(R D LA2 )) XA D -, or represents an arylene group.

[0763] The above XA D represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3.

[0764] R D LA1 and R D LA2 Each represents, independently, a hydrogen atom or a substituent.

[0765] R D LA1 and R D LA2 The substituents are each independently preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and more preferably a fluorine atom or a perfluoromethyl group.

[0766] XA D If is 2 or more, XA D R that exists D LA1 Each may be the same or different.

[0767] XA D If is 2 or more, XA D R that exists D LA2 Each can be the same or different.

[0768] -(C(R D LA1 )(R D LA2))- is preferably -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0769] Among them, A in the general formula (PD) D1 - -(C(R that directly combines with D LA1 )(R D LA2 ))- is preferably -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0770] A in the general formula (PD) D1 - -(C(R that directly combines with D LA1 )(R D LA2 ))- other than -(C(R D LA1 )(R D LA2 ))- is, independently, -CH2-, -CHF-, or -CF2- is preferred.

[0771] L D As for the arylene group of A, it is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred.

[0772] The arylene group may have a substituent. As for the substituent, it is not particularly limited, but a halogen atom is preferred, and a fluorine atom is more preferred.

[0773] Among the general formula (LD), L D B represents a single bond, an ether group (-O-), an ester group (-COO-), or a sulfonyl group (-SO2-).

[0774] Among the general formula (LD), L D C represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, or a group formed by a combination thereof ("-alkylene group-cycloalkylene group-" etc.).

[0775] The above alkylene group may be in a straight chain or a branched chain.

[0776] The number of carbon atoms in the above alkylene group is preferably 1 to 5, more preferably 1 to 2, and more preferably 1. The number of carbon atoms in the above cycloalkylene group is preferably 3 to 15, and more preferably 5 to 10.

[0777] The above cycloalkylene group may be monocyclic or polycyclic.

[0778] Examples of the above cycloalkylene groups include the norbornendiyl group and the adamantendiyl group.

[0779] The substituent that the above cycloalkylene group may have is preferably an alkyl group (which may be straight-chain or branched-chain. Preferably, it has 1 to 5 carbon atoms).

[0780] One or more of the methylene groups constituting the cycloalkane ring of the above cycloalkylene group may be substituted with a carbonyl carbon and / or a heteroatom (nitrogen atom, oxygen atom, etc.).

[0781] L D If C is "-alkylene group-cycloalkylene group-", the alkylene group portion is L D It is desirable for it to exist on side B.

[0782] L D As for the arylene group of C, it is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred.

[0783] The arylene group may have a substituent.

[0784] L D If B is a single bond, L D C is preferably a single bond or a cycloalkylene group.

[0785] Among the general formula (LD), L D D represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

[0786] Among the general formula (LD), L D E is a single bond or -(C(R D LE1 )(R D LE2 )) XE D - represents.

[0787] Above -(C(R D LE1 )(R D LE2 )) XE D XE in - D represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3.

[0788] R D LE1 and R D LE2 Each represents, independently, a hydrogen atom or a substituent.

[0789] XE D If ga is 2 or more, XE D R that exists D LE1 Each may be the same or different.

[0790] XE D If ga is 2 or more, XE D R that exists D LE2 Each can be the same or different.

[0791] Among them, -(C(R D LE1 )(R D LE2 ))- is, -CH2- is preferred. General formula (L D ) Among, L D B, L D C, and L D If D is a single bond, L D It is also desirable that E be a single bond.

[0792] Among the general formula (PD), A D1 -Silver represents an acid anion group.

[0793] Acid anion groups are groups that have anion atoms.

[0794] A D1 - Specifically, it is preferable that it be represented by the general formula (AD-1) or (AD-2).

[0795] [Chemical Formula 60]

[0796]

[0797] In general formulas (AD-1) to (AD-2), * indicates the bonding position.

[0798] Among the general formula (AD-2), R AD represents an organic group.

[0799] R AD The alkyl group is not particularly limited, but is preferred.

[0800] The above alkyl group may be in a straight chain or a branched chain.

[0801] The number of carbon atoms in the above alkyl group is preferably 1 to 10, and more preferably 1 to 5.

[0802] The substituent that the above alkyl group may have is preferably a fluorine atom.

[0803] The alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.

[0804] Among the general formula (PD), B D1 - Silver represents an acid anion group.

[0805] B D1 - Specifically, it is desirable that it be represented by any one of general formulas (B-1) to (B-6).

[0806] B D1 -A group represented by any one of general formulas (BD-1) to (BD-3) is preferable, and a group represented by any one of general formulas (BD-1) to (BD-2) is more preferable.

[0807] [Chemical Formula 61]

[0808]

[0809] Among general formulas (BD-1) to (BD-6),

[0810] R BD Each independently represents an organic group.

[0811] L BD Each represents, independently, a single bond, an alkylene group, a cycloalkylene group, an arylene group, -O-, -C(=O)-, -SO2-, or a combination thereof.

[0812] * indicates the connection position.

[0813] R BD represents an alkyl group, a cycloalkyl group, or an aryl group.

[0814] R BD As for the alkyl group in which α represents an alkyl group, a chain-like or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0815] Examples of alkyl groups include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, etc., and methyl groups or ethyl groups are preferred, and methyl groups are more preferred.

[0816] R BD When the cycloalkyl group is represented, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 5 to 10 carbon atoms is more preferred. The cycloalkyl group may be monocyclic or polycyclic.

[0817] Examples of cycloalkyl groups include cyclopentyl groups, norbornyl groups, decalinyl groups, and adamantyl groups.

[0818] R BD When ga represents an aryl group, an aryl group having 6 to 15 carbon atoms is preferred as the aryl group.

[0819] Examples of aryl groups include phenyl groups and naphthyl groups, and it is preferable that it be a phenyl group.

[0820] R BD It may have substituents.

[0821] As a desirable mode of work, R BD As a substituent in the case where ga has a substituent, R in the general formula (C1) as a preferred embodiment above is C1 Examples of substituents that have this substituent can be given.

[0822] As a desirable mode of work, R BD As substituents in the case where ga has a substituent, the substituents include an alkoxycarbonyl group, SO3 - Examples include the alkyl group in the alkoxycarbonyl group. Although not particularly limited, a chain-like or branched alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

[0823] R BD As a substituent in the case where has a substituent, R in the above general formula (C1) C1 Examples of substituents that have this substituent can be given.

[0824] L BD represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, -O-, -C(=O)-, -SO2-, or a divalent linker formed by a combination thereof.

[0825] L BD Examples of alkylene groups that represent alkylene groups include chain-like or branched alkylene groups having 1 to 20 carbon atoms.

[0826] Examples of chain-like or branched alkylene groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, n-propylene groups, i-propylene groups, n-butylene groups, n-pentylene groups, etc., and methylene groups, ethylene groups, n-propylene groups, or n-butylene groups are preferred.

[0827] L BD Examples of cycloalkylene groups that represent a cycloalkylene group include a monocyclic or polycyclic cycloalkylene group having 3 to 20 carbon atoms.

[0828] Examples of monocyclic or polycyclic cycloalkylene groups having 3 to 20 carbon atoms include adamantylene groups, cyclohexylene groups, cyclopentylene groups, cycloheptylene groups, norbornylene groups, and adamantylene groups, cyclohexylene groups, and norbornylene groups are preferred.

[0829] L BD When the arylene group is represented, the arylene group is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is particularly preferred.

[0830] L BD It may have a substituent.

[0831] As a desirable mode of work, L BD As a substituent in the case where ga has a substituent, the above R as in the above preferred embodiment BD Examples of substituents that have a substituent can be given.

[0832] L BD It is preferable that the linker be a single bond, a methylene group, -O-, -C(=O)-, or a combination thereof, and more preferable that the linker be a single bond or a methylene group.

[0833] M of a compound represented by the general formula (PD) D1 + and M D2 + HA in which each is substituted with a hydrogen atom D1 -L D -BD1 In compounds represented by H, HA D1 The pKa of the group represented as is B D1 It is lower than the pKa of the group represented by H.

[0834] More specifically, HA D1 -L D -B D1 In the case where the acid dissociation constant is calculated for a compound represented by H, "HA D1 -L D -B D1 H" is "A D1 - -L D -B D1 The pKa when it becomes "HA" D1 Let the pKa of the group represented by be "", and also "A D1 - -L D -B D1 H" is "A D1 - -L D -B D1 - "The pKa when this happens is "B D1 Let pKa be the group represented by H.

[0835] "HA D1 The pKa of the group represented by "" and "B D1 The pKa of the group represented by H is obtained using "Software Package 1" or "Gaussian 16", respectively, as described above.

[0836] Among them, HA D1 The pKa of the group represented by is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and more preferably -5.00 to 0.00.

[0837] B D1 The pKa of the group represented by H is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and more preferably -1.00 to 5.00.

[0838] B D1pKa of the group represented by H and HA D1 The difference in pKa of the group represented by ("B D1 pKa"-"HA of the energy represented by H D1 The pKa of the group represented by is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, and more preferably 2.00 to 15.00.

[0839] The following are preferred embodiments of a compound corresponding to an ionic compound (D).

[0840] [Chemical Formula 62]

[0841]

[0842] [Chemical Formula 63]

[0843]

[0844] [Chemical Formula 64]

[0845]

[0846] [Chemical Formula 65]

[0847]

[0848] The content of the ionic compound (D) in the composition of the present invention is not particularly limited, but for superior effects of the present invention, it is preferable to have 5.0 mass% or more, 9.0 mass% or more, and 15.0 mass% or more with respect to the total solid content of the composition. In addition, the content is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, and more preferably 50.0 mass% or less.

[0849] The ionic compound (D) may be used as a single type or as two or more types.

[0850] In addition to the ionic compound (D), the composition of the present invention may also contain at least one of a photogenerator (B) and an ionic compound (C).

[0851] Specifically, the following embodiments may be cited as the forms in which a compound corresponding to a photogenerator (B) or an ionic compound (C) is contained in the composition of the present invention.

[0852] (i) Photogenerator other than ionic compound (D) (B) + ionic compound other than ionic compound (D) (C)

[0853] (ii) Ionic compound (D)

[0854] (iii) Ionic compound (D) + photogenerator other than ionic compound (D) (B)

[0855] (iv) Ionic compound (D) + ionic compound other than ionic compound (D) (C)

[0856] (v) Ionic compound (D) + Photogenerator other than ionic compound (D) (B) + Ionic compound other than ionic compound (D) (C)

[0857] In the above (iii), the ionic compound (D) needs to function as an ionic compound (C), and in this case, the pKa of the acid generated from the structure having a function equivalent to that of the ionic compound (C) in the ionic compound (D) is greater than the pKa of the acid generated from the photogenerator (B).

[0858] In the above (iv), the ionic compound (D) needs to function as a photogenerator (B), and in this case, the pKa of the acid generated from the ionic compound (C) is greater than the pKa of the acid generated from the structure having a function equivalent to the photogenerator (B) in the ionic compound (D).

[0859] In the above (v), the ionic compound (D) may function as a photogenerator (B) or as an ionic compound (C). When it functions as a photogenerator (B), the pKa of the acid generated from the ionic compound (C) becomes greater than the pKa of the acid generated from the structure of the ionic compound (D) that has a function equivalent to that of the photogenerator (B). When it functions as an ionic compound (C), the pKa of the acid generated from the structure of the ionic compound (D) that has a function equivalent to that of the ionic compound (C) becomes greater than the pKa of the acid generated from the photogenerator (B).

[0860] The composition of the present invention comprises at least one ionic compound (Y).

[0861] In a preferred embodiment, when the composition of the present invention contains a photogenerator (B), the photogenerator (B) is an ionic compound (Y). In this case, the composition of the present invention may contain a photogenerator (B) other than the ionic compound (Y).

[0862] In a preferred embodiment, when the composition of the present invention contains an ionic compound (C), the ionic compound (C) is an ionic compound (Y). In this case, the composition of the present invention may contain an ionic compound (C) other than the ionic compound (Y).

[0863] In a preferred embodiment, when the composition of the present invention contains an ionic compound (D), the ionic compound (D) is an ionic compound (Y). In this case, the composition of the present invention may contain an ionic compound (D) other than the ionic compound (Y).

[0864] <Other acid diffusion control agents (E)>

[0865] The composition of the present invention may further include an acid diffusion control agent other than the ionic compound (C) and the ionic compound (D) (also referred to as other acid diffusion control agent (E) or acid diffusion control agent (E)) to the extent that it does not impede the effects of the present invention. The acid diffusion control agent acts as a quencher that traps acid generated from the photogenerative agent and plays a role in controlling the diffusion phenomenon of acid in the resist film.

[0866] The acid diffusion control agent (E) may be, for example, a basic compound.

[0867] The basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).

[0868] [Chemical Formula 66]

[0869]

[0870] Among general formulas (A) and (E), R 200 , R 201 and R 202 may be the same or different and represents a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), or an aryl group (preferably 6 to 20 carbon atoms), wherein R 201 and R 202 They may combine with each other to form a ring.

[0871] Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[0872] R 203 , R 204 , R 205 and R 206 It may be the same or different and represents an alkyl group having 1 to 20 carbon atoms.

[0873] It is more preferable that the alkyl group in these general formulas (A) and (E) be unsubstituted.

[0874] As a basic compound, guanidine, aminopyrrolidine, pyrazol, pyrazolin, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl group portion may be straight or branched, and a portion may be substituted with ether and / or ester groups. The sum of the total number of atoms other than hydrogen atoms in the alkyl group portion is preferably 1 to 17), or piperidine, etc. are preferred. Among these, compounds having an imidazole structure, a diazobicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having hydroxyl groups and / or ether bonds, or aniline derivatives having hydroxyl groups and / or ether bonds, etc. are more preferred.

[0875] Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of compounds having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undes-7-ene. Examples of compounds having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Compounds having an onium carboxylate structure are those in which the anionic portion of a compound having an onium hydroxide structure becomes a carboxylate; examples include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Compounds having a trialkylamine structure include examples such as tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include examples such as 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of alkylamine derivatives having hydroxyl groups and / or ether bonds include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and (HO-C2H4-O-C2H4)2N(-C3H6-O-CH3). Examples of aniline derivatives having hydroxyl groups and / or ether bonds include N,N-bis(hydroxyethyl)aniline.

[0876] As basic compounds, amine compounds having a phenoxy group and ammonium salt compounds having a phenoxy group are preferably cited.

[0877] As for the amine compound, for example, primary, secondary, and tertiary amine compounds may be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. It is more preferable that the amine compound be a tertiary amine compound. In the amine compound, if at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.

[0878] In addition, it is preferable that the amine compound has oxyalkylene groups. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CH2O- or CH2CH2CH2O-) is preferred, and an oxyethylene group is more preferred.

[0879] Examples of ammonium salt compounds include primary, secondary, tertiary, and quaternary ammonium salt compounds, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. In the ammonium salt compound, if at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.

[0880] It is preferable that the ammonium salt compound has oxyalkylene groups. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CH2O-, or -CH2CH2CH2O-) is preferred, and an oxyethylene group is more preferred.

[0881] Examples of anions of ammonium salt compounds include halogen atoms, sulfonates, borates, and phosphates, among which halogen atoms or sulfonates are preferred. The halogen atoms are preferably chlorine atoms, bromine atoms, or iodine atoms. The sulfonates are preferably organic sulfonates having 1 to 20 carbon atoms. Examples of organic sulfonates include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituents include fluorine atoms, chlorine atoms, bromine atoms, alkoxy groups, acyl groups, and aromatic groups. Examples of alkyl sulfonates include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of aryl groups of aryl sulfonates include benzene groups, naphthalene groups, and anthracene groups. The substituents that the benzene groups, naphthalene groups, and anthracene groups may have are preferably straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms, or cycloalkyl groups having 3 to 6 carbon atoms. Examples of straight-chain or branched-chain alkyl groups and cycloalkyl groups include, for instance, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, i-butyl groups, t-butyl groups, n-hexyl groups, and cyclohexyl groups. Other substituents include, for instance, alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, acyl groups, and acyloxy groups.

[0882] An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the end opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.

[0883] Examples of substituents for the phenoxy group include alkyl groups, alkoxy groups, halogen atoms, cyano groups, nitro groups, carboxylic acid groups, carboxylic acid ester groups, sulfonic acid ester groups, aryl groups, aralkyl groups, acyloxy groups, and aryloxy groups. The substituent positions may be any of positions 2 to 6. The number of substituents may be any of positions 1 to 5.

[0884] It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CH2O- or -CH2CH2CH2O-) is preferred, and an oxyethylene group is more preferred.

[0885] An amine compound having a phenoxy group is obtained by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, adding an aqueous solution of a strong base (e.g., sodium hydroxide, potassium hydroxide, and tetraalkylammonium, etc.) to the reaction system, and further extracting the reaction product with an organic solvent (e.g., ethyl acetate and chloroform, etc.). Alternatively, it is obtained by heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal end, adding an aqueous solution of a strong base to the reaction system, and further extracting the reaction product with an organic solvent.

[0886] A low-molecular-weight compound having a nitrogen atom and a group that is detached by the action of an acid can also be used as an acid diffusion control agent. The low-molecular-weight compound is preferably an amine derivative having a group that is detached by the action of an acid on the nitrogen atom.

[0887] As for the group that is removed by the action of acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferred, and a carbamate group or a hemiaminal ether group is more preferred.

[0888] The molecular weight of the low molecular weight compound is preferably 100 to 1000, more preferably 100 to 700, and more preferably 100 to 500.

[0889] Low molecular weight compounds may have a carbamate group having a protecting group on the nitrogen atom.

[0890] Specific examples of acid diffusion control agents (E) are shown below, but the present invention is not limited thereto.

[0891] [Chemical Formula 67]

[0892]

[0893] [Chemical Formula 68]

[0894]

[0895] When the composition of the present invention includes an acid diffusion control agent (E), the content of the acid diffusion control agent (E) is preferably 0.001 to 20.0 mass% with respect to the total solid content of the composition, more preferably 0.01 to 5.0 mass%, and more preferably not include the acid diffusion control agent (E).

[0896] Acid diffusion control agent (E) may be used as a single type or as two or more types.

[0897] As for acid diffusion control agents (E), examples include compounds described in paragraphs

[0140] to

[0144] of Japanese Patent Publication No. 2013-11833 (amine compounds, compounds containing amide groups, urea compounds, and nitrogen-containing heterocyclic compounds, etc.).

[0898] <hydrophobic resin (F)>

[0899] The composition of the present invention may include a hydrophobic resin different from the resin (A), separately from the resin (A).

[0900] It is desirable for hydrophobic resins to be designed to be localized on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and non-polar substances.

[0901] Effects of adding hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.

[0902] In terms of localization to the film surface layer, it is preferable for the hydrophobic resin to have one or more of "fluorine atoms," "silicon atoms," and "CH3 substructures included in the side chain portion of the resin," and it is more preferable for it to have two or more. In addition, it is preferable for the hydrophobic resin to have hydrocarbon groups having five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0903] When a hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be included in the main chain of the resin or in the side chain.

[0904] When a hydrophobic resin contains fluorine atoms, the partial structure having fluorine atoms is preferably an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms.

[0905] The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight-chain or branched-chain alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may additionally have substituents other than fluorine atoms.

[0906] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may additionally have substituents other than the fluorine atom.

[0907] As for the aryl group having a fluorine atom, examples include aryl groups such as phenyl groups and naphthyl groups in which at least one hydrogen atom is substituted with a fluorine atom, and it may also have additional substituents other than fluorine atoms.

[0908] As repeating units having fluorine atoms or silicon atoms, for example, the repeating unit exemplified in paragraph

[0519] of US2012 / 0251948A1 can be cited.

[0909] In addition, as mentioned above, it is also desirable for the hydrophobic resin to include a CH3 portion structure in the side chain portion.

[0910] Here, the CH3 part structure of the side chain portion in the hydrophobic resin includes the CH3 part structure of the ethyl group and the propyl group.

[0911] Meanwhile, methyl groups directly bonded to the main chain of the hydrophobic resin (e.g., α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 substructure of the present invention because their contribution to the surface localization of the hydrophobic resin due to the influence of the main chain is small.

[0912] Regarding hydrophobic resins, reference may be made to paragraphs

[0348] to

[0415] of Japanese Patent Publication No. 2014-010245, and the contents thereof are incorporated into the present specification.

[0913] In addition, hydrophobic resins described in Japanese Published Patent Application No. 2011-248019, Japanese Published Patent Application No. 2010-175859, and Japanese Published Patent Application No. 2012-032544 may also be preferably used.

[0914] When the composition of the present invention includes a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20 mass% with respect to the total solid content of the composition, and more preferably 0.1 to 15 mass%.

[0915] Solvent

[0916] The composition of the present invention may include a solvent.

[0917] The solvent preferably comprises at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Additionally, the solvent may further comprise components other than components (M1) and (M2).

[0918] The inventors have discovered that by using a combination of such a solvent and the resin described above, the coating properties of the composition are improved, and a pattern with a low number of development defects can be formed. Although the reason is not necessarily clear, the inventors believe that this is due to the fact that these solvents provide a good balance of the solubility, boiling point, and viscosity of the resin described above, which enables the suppression of variations in the film thickness of the composition film and the occurrence of precipitates during spin coating.

[0919] The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate (PGMEA) is more preferred.

[0920] The component (M2) is preferably the following solvent.

[0921] Propylene glycol monoalkyl ethers preferably include propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE).

[0922] Lactic acid esters are preferably ethyl lactate, butyl lactate, or propyl lactate.

[0923] Acetic acid esters are preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate.

[0924] In addition, butyl butyl butyric acid is also desirable.

[0925] The alkoxypropionic acid ester is preferably methyl methoxypropionic acid (MMP) or ethyl ethoxypropionic acid (EEP).

[0926] Chain ketones are preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetoneylacetone, ionone, diacetoneyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, or methylamyl ketone.

[0927] The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.

[0928] The lactone is preferably γ-butylolactone.

[0929] The alkylene carbonate is preferably propylene carbonate.

[0930] Component (M2) is preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methylamyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone, or propylene carbonate.

[0931] In addition to the above components, it is preferable to use an ester-based solvent having 7 or more carbon atoms (7 to 14 is preferred, 7 to 12 is more preferred, and 7 to 10 is more preferred) and 2 or fewer heteroatoms.

[0932] Examples of ester-based solvents having 7 or more carbon atoms and 2 or fewer heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and isoamyl acetate is preferred.

[0933] The component (M2) is preferably a solvent having a flash point (hereinafter also referred to as fp) of 37°C or higher.

[0934] Such a component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methylamyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), pentyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C). Among these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is even more preferred.

[0935] In addition, the term "flash point" here refers to the value listed in the reagent catalogs of Tokyo Kasei High School Co., Ltd. or Sigma Aldrich.

[0936] It is preferable that the solvent contains component (M1). It is more preferable that the solvent consists substantially of component (M1) alone, or is a mixed solvent of component (M1) and other components. In the latter case, it is more preferable that the solvent contains both component (M1) and component (M2).

[0937] The mass ratio (M1 / M2) of component (M1) and component (M2) is preferably "100 / 0" to "0 / 10", more preferably "100 / 0" to "15 / 85", even more preferably "100 / 0" to "40 / 60", and particularly preferably "100 / 0" to "60 / 40".

[0938] That is, when the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is preferably 15 / 85 or higher, more preferably 40 / 60 or higher, and more preferably 60 / 40 or higher. By adopting such a composition, the number of developed defects can be further reduced.

[0939] In addition, if the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is, for example, 99 / 1 or less.

[0940] As described above, the solvent may further include components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably 5 to 30 mass% with respect to the total amount of the solvent.

[0941] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30 mass%, and more preferably set so that it is 1 to 20 mass%. By doing so, the coating properties of the composition of the present invention can be further improved.

[0942] In addition, solid content refers to all components other than the solvent.

[0943] Solid content concentration is the mass percentage of the mass of the components other than the solvent, excluding the solvent, relative to the total mass of the composition of the present invention.

[0944] "Total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition of the present invention. Also, "solid content" refers to the components excluding the solvent as described above, and may be, for example, solid or liquid at 25°C.

[0945] Surfactants

[0946] The composition of the present invention may include a surfactant. If a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.

[0947] The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include, for instance, the surfactant described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Also, F-Top EF301, or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431, and 4430 (manufactured by Sumitomo 3M Corporation); MegaPac F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC Corporation); Surfron S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by Asahi Glass Co., Ltd.); Troizol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Doa Kosei Kagaku Co., Ltd.), Surfron S-393 (manufactured by Seimi Chemical Co., Ltd.); F-Top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos Co., Ltd.) may also be used. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) may also be used as a silicone-based surfactant.

[0948] In addition, the surfactant may be synthesized using a fluoroaliphatic compound prepared by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method), in addition to the known surfactants described above. Specifically, a polymer having fluoroaliphatic groups derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in Japanese Patent Publication No. 2002-90991.

[0949] In addition, surfactants other than fluorine-based and / or silicone-based ones described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may be used.

[0950] These surfactants may be used as a single type or as two or more types.

[0951] When the composition of the present invention includes a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass% with respect to the total solid content of the composition, and more preferably 0.0005 to 1 mass%.

[0952] Other Additives

[0953] The composition of the present invention may further include a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (e.g., a phenol compound with a molecular weight of 1000 or less, or a cycloaliphatic or aliphatic compound containing a carboxylic acid group).

[0954] The composition of the present invention may further include a dissolution-inhibiting compound. Herein, "dissolution-inhibiting compound" is a compound with a molecular weight of 3,000 or less that decomposes upon the action of an acid and reduces its solubility in an organic developer.

[0955] [use]

[0956] The composition of the present invention relates to a photosensitive or radiation-sensitive resin composition that changes its properties by reacting to irradiation with active light or radiation. More specifically, the composition of the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, fabrication of mold structures for imprinting, other photofabrication processes, or manufacturing of flat printing plates or acid-curable compositions. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, redistribution formation processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0957] [Desensitizing photoreactive or radioactive membrane]

[0958] The present invention also relates to a light-sensitive or radiation-sensitive film (typically a "resist film") formed by the light-sensitive or radiation-sensitive composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm.

[0959] As a method of coating on a substrate, the coating is applied to the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, but spin coating is preferred, and the rotation speed is preferably 1000 to 3000 rpm (rotations per minute). The coating film is pre-baked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes to form a thin film.

[0960] The material constituting the substrate to be processed and the outermost layer thereof may, for example, use a silicon wafer in the case of a semiconductor wafer, and examples of the material that becomes the outermost layer include Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.

[0961] [Pattern Formation Method]

[0962] The steps of the pattern formation method using the above-mentioned photosensitive or radiation-sensitive resin composition are not particularly limited, but it is preferable to have the following process.

[0963] Process 1: A process of forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition.

[0964] Process 2: A process of exposing a desensitizing photopolymer or radiation-reducing film (preferably with EUV light).

[0965] Process 3: A process of developing an exposed photosensitive or radiation-sensitive film using a developer and forming a pattern.

[0966] Below, the sequence of each of the above processes will be explained in detail.

[0967] <Process 1: Desensitizing Light or Desensitizing Radiation Film Formation Process>

[0968] Process 1 is a process of forming a desensitizing light or a desensitizing film on a substrate using a desensitizing light or a desensitizing resin composition.

[0969] As a method for forming a resist film on a substrate using a desensitizing light or a radiation-sensitive resin composition, for example, a method of applying the desensitizing light or a radiation-sensitive resin composition on the substrate may be used.

[0970] In addition, it is preferable to filter the desensitizing light or radiation-sensitive resin composition as needed before application. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. Furthermore, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0971] A desensitizing light or radiation-sensitive resin composition can be applied to a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or a coater. Spin coating using a spinner is preferred as the application method. When performing spin coating using a spinner, the rotation speed is preferably 1,000 to 3,000 rpm.

[0972] After applying a desensitizing light or a radiation-sensitive resin composition, the substrate may be dried to form a resist film. Additionally, if necessary, various underlayers (inorganic films, organic films, anti-reflective films) may be formed on the underside of the resist film.

[0973] As a drying method, for example, a method of drying by heating may be used. Heating can be performed using means equipped in a conventional exposure machine and / or a developer, or it may be performed using a hot plate, etc. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0974] The film thickness of the desensitizing light or desensitizing radiation film is not particularly limited, but 10 to 65 nm is preferred and 15 to 50 nm is more preferred in that it can form a fine pattern with higher precision.

[0975] In addition, a top coat may be formed on the upper layer of the desensitizing light or radiation-sensitive film using a top coat composition.

[0976] It is preferable that the top coat composition be uniformly applied to the upper layer of the desensitizing light or desensitizing radiation film without mixing with the desensitizing light or desensitizing radiation film.

[0977] In addition, it is preferable to dry the desensitizing light or radiation-sensitive film before forming the top coat. Subsequently, a top coat composition may be applied to the obtained resist film by means identical to the method of forming the desensitizing light or radiation-sensitive film, and then dried again to form the top coat.

[0978] The film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and more preferably 40 to 80 nm.

[0979] Regarding the top coat, it is not particularly limited and can be formed by conventionally known top coats using conventionally known methods, for example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Publication No. 2014-059543.

[0980] For example, it is preferable to form a top coat containing a basic compound as described in Japanese Patent Publication No. 2013-61648 on a desensitizing light or radiation-sensitive film. Specific examples of basic compounds that the top coat may contain include basic compounds that may be included in the desensitizing light or radiation-sensitive resin composition described above.

[0981] In addition, the top coat preferably comprises a compound having at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0982] <Process 2: Photolithography Process>

[0983] Process 2 is a process of exposing a desensitizing light or a radiation-reducing film (preferably with EUV light).

[0984] As a method of exposure, for example, a method of irradiating EUV light through a predetermined mask onto a formed desensitizing light or desensitizing radiation film may be used.

[0985] It is desirable to perform baking (heating) after exposure and before developing. Baking promotes the reaction of the exposed area, and improves sensitivity and pattern shape.

[0986] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0987] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0988] Heating can be performed using means provided in a conventional exposure machine and / or developer, or by using a hot plate, etc.

[0989] This process is also called post-exposure baking.

[0990] <Process 3: Development Process>

[0991] Process 3 is a process of developing an exposed desensitized light or desensitized radiation film using a developer and forming a pattern.

[0992] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0993] Examples of development methods include a method of immersing a substrate in a tank filled with a developer solution for a certain period of time (dip method), a method of developing by raising the developer solution on the surface of the substrate by surface tension and letting it stand for a certain period of time (puddle method), a method of spraying the developer solution onto the surface of the substrate (spray method), and a method of continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a certain speed onto a substrate rotating at a certain speed (dynamic dispensing method).

[0994] In addition, after the process of performing the development, a process of stopping the development may be carried out while replacing it with another solvent.

[0995] There is no particular limit to the development time as long as it is the time for the resin in the unexposed area to sufficiently dissolve, and 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred.

[0996] The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0997] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include an alkaline aqueous solution containing a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, or a cyclic amine. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1 to 20 mass%. In addition, the pH of the alkaline developer is typically 10.0 to 15.0.

[0998] 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.

[0999] Examples of ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone monoacetone, ionone, diacetone monoalcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[1000] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[1001] As for alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, for example, solvents disclosed in paragraphs

[0715] –

[0718] of U.S. Patent Application Publication 2016 / 0070167A1 may be used.

[1002] The above solvents may be mixed in multiple quantities, or mixed with solvents other than those mentioned above or with water. The water content of the entire developer solution is preferably less than 50 mass%, more preferably less than 20 mass%, more preferably less than 10 mass%, and is particularly preferably not substantially water-free.

[1003] The content of the organic solvent in the organic developer is preferably 50 mass% or more and 100 mass% or less with respect to the total amount of the developer, more preferably 80 mass% or more and 100 mass% or less, more preferably 90 mass% or more and 100 mass% or less, and particularly preferably 95 mass% or more and 100 mass% or less.

[1004] Other processes

[1005] The above pattern forming method preferably includes a process of cleaning using a rinse solution after process 3.

[1006] As a rinsing solution used in the rinsing process after the development process using an alkaline developer, pure water may be used, for example. In addition, an appropriate amount of surfactant may be added to the pure water. An appropriate amount of surfactant may be added to the rinsing solution.

[1007] The rinsing solution used in the rinsing process after the development process using an organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent may be used. It is preferable to use a rinsing solution 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.

[1008] Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include those described in relation to developers containing organic solvents.

[1009] The method of the rinsing process is not particularly limited, and examples include a method of continuously dispensing a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with rinsing liquid for a certain period of time (dip method), and a method of spraying a rinsing liquid onto the surface of the substrate (spray method).

[1010] In addition, the pattern forming method of the present invention may include a heating process (Post Bake) after the rinsing process. Through this process, the developer and rinsing liquid remaining between and inside the patterns are removed by baking. In addition, through this process, the resist pattern is annealed, and the surface roughness of the pattern is improved. The heating process after the rinsing process is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[1011] In addition, the formed pattern may be used as a mask to perform an etching treatment on the substrate. That is, the substrate (or the lower layer and the substrate) may be processed using the pattern formed in process 3 as a mask, and a pattern may be formed on the substrate.

[1012] The processing method of the substrate (or the lower layer and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the lower layer and the substrate) using the pattern formed in process 3 as a mask is preferred.

[1013] Dry etching may be a single-stage etching or a multi-stage etching. In the case of a multi-stage etching, each stage of etching may be the same treatment or a different treatment.

[1014] All known methods can be used for etching, and various conditions are appropriately determined according to the type or application of the substrate. For example, etching can be performed in accordance with the International Society for Photonics and Optics (Proc. of SPIE) Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. In addition, the method described in "Chapter 4 Etching" of the "Semiconductor Process Manual, 4th Edition, 2007, Publisher: SEMI Japan" may also be used.

[1015] Among them, oxygen plasma etching is preferred for dry etching.

[1016] It is preferable that the composition of the present invention and the various materials used in the pattern forming method of the present invention (e.g., solvent, developer, rinse solution, composition for forming an anti-reflective film, composition for forming a top coat, etc.) do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. 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.

[1017] As a method for removing impurities such as metals from various materials, filtration using a filter may be cited, for example. The filter pore diameter is preferably less than 100 nm, more preferably 10 nm or less, and more preferably 5 nm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. The filter may be composed of a composite material combining the above filter material and an ion exchange medium. The filter may be a filter that has been pre-cleaned with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore diameters and / or materials may be combined. In addition, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulating filtration process.

[1018] In the preparation of the composition of the present invention, it is preferable to dissolve each component, such as a resin and a photocatalytic agent, in a solvent and then perform circulation filtration using a plurality of filters made of different materials. For example, it is preferable to perform circulation filtration at least 10 times by connecting a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and a polyethylene filter with a pore diameter of 3 nm in a permutation. The pressure difference between filters is preferably smaller; generally, it is 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The pressure difference between the filter and the filling nozzle is also preferably smaller; generally, it is 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less.

[1019] It is preferable to perform gas exchange with an inert gas, such as nitrogen, inside the manufacturing apparatus of the composition of the present invention. By doing so, the dissolution of active gases, such as oxygen, into the composition of the present invention can be suppressed.

[1020] The composition of the present invention is filtered by a filter and then filled into a clean container. It is preferable that the composition of the present invention filled into the container be refrigerated. This suppresses performance deterioration over time. The time from the completion of filling the composition into the container until the start of refrigerated storage is preferably shorter; generally, it is within 24 hours, within 16 hours is preferable, within 12 hours is more preferable, and within 10 hours is more preferable. The storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and more preferably 0 to 5°C.

[1021] In addition, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as the raw materials constituting various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as lining the inside of the device with Teflon (registered trademark).

[1022] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used. In order to reduce impurities such as metals contained in the various materials mentioned above, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be verified by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing apparatus. The content of metal components contained in the cleaning solution after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.

[1023] In organic treatment solutions such as rinse solutions, a conductive compound may be added to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and continuous electrostatic discharge. The conductive compound is not particularly limited, but methanol may be cited as an example. The amount added is not particularly limited, but in order to maintain desirable developing characteristics or rinsing characteristics, it is preferable to have 10 mass% or less, and more preferable to have 5 mass% or less.

[1024] As for the chemical piping, various types of piping can be used, for example, made of SUS (stainless steel), or coated with antistatic-treated polyethylene, polypropylene, or fluoropolymer (polytetrafluoroethylene, or perfluoroalkoxy resin, etc.). Likewise, regarding the filter and O-ring, antistatic-treated polyethylene, polypropylene, or fluoropolymer (polytetrafluoroethylene, or perfluoroalkoxy resin, etc.) can be used.

[1025] For a pattern formed by the method of the present invention, a method for improving the surface roughness of the pattern may be applied. As a method for improving the surface roughness of the pattern, for example, a method of treating the pattern with a plasma of a hydrogen-containing gas disclosed in International Patent Publication No. 2014 / 002808 may be cited. In addition, known methods such as those described in Japanese Patent Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, Japanese Patent Publication No. 2008-83384, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" may be cited.

[1026] When the pattern formed is on a line, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and more preferably 1.7 or less.

[1027] When the pattern formed is a trench (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the trench width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and more preferably 3.0 or less.

[1028] The pattern forming method of the present invention can also be used for guide pattern forming in Directed Self-Assembly (DSA) (e.g., see ACS Nano Vol. 4 No. 8 Page 4815-4823).

[1029] In addition, the pattern formed by the above method can be used as a core for a spacer process disclosed, for example, in Japanese Patent Publication No. Hei 3-270227 and Japanese Patent Publication No. 2013-164509.

[1030] In addition, the present invention relates to a method for manufacturing an electronic device comprising the above-described pattern forming method, and to an electronic device manufactured by the method.

[1031] The electronic device of the present invention is suitablely mounted in electrical and electronic devices (home appliances, OA (Office Automation), media-related devices, optical devices and communication devices, etc.).

[1032] Examples

[1033] The present invention will be described in more detail below based on the examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[1034] [Various components of light-sensitive or radiation-sensitive resin compositions]

[1035] [Suzy (A)]

[1036] Resin A (resins A-1 to A-67, A'-1 to A'-3) shown in Table 3 is shown below.

[1037] Resins A-1 to A-65 and A'-1 to A'-3 were used after being synthesized according to the synthesis method of resin A-1 (Synthesis Example 1) described below. Table 1 shows the composition ratio (mol% ratio; corresponding in order from left), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit as described below.

[1038] In addition, the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resins A-1 to A-67 and A'-1 to A'-3 were measured by GPC (solvent: tetrahydrofuran (THF)). Furthermore, the compositional ratio (molar % ratio) of the resins was, 13 It was measured by C-NMR (nuclear magnetic resonance).

[1039] In addition, resins A'-2 and A'-3 are not resins (A), but for convenience, they are listed as resins (A) in Table 1.

[1040] [Table 1-1]

[1041]

[1042] [Table 1-2]

[1043]

[1044] The structures of monomers M-1 to M-93 corresponding to each repeating unit constituting resins A-1 to A-67 and A'-1 to A'-3 shown in Table 1 are shown below.

[1045] [Chemical Formula 69]

[1046]

[1047] [Chemical Formula 70]

[1048]

[1049] [Chemical Formula 71]

[1050]

[1051] [Chemical Formula 72]

[1052]

[1053] [Chemical Formula 73]

[1054]

[1055] <Synthetic Example 1: Synthesis of Resin A-1>

[1056] Cyclohexanone (226 g) was heated to 80°C under a nitrogen stream. While stirring the liquid, a mixed solution of a monomer (53 g) represented by the formula M-75 below, a monomer (47 g) represented by the formula M-31 below, cyclohexanone (420 g), and 2,2'-azobisisobutyrate dimethyl [V-601, manufactured by Wako Junyaku Kogyo Co., Ltd.] (12.42 g) was added dropwise over 6 hours to obtain a reaction solution. After the dropwise addition was finished, the reaction solution was stirred again at 80°C for 2 hours. After cooling the obtained reaction solution, it was reprecipitated with a large amount of methanol / water (mass ratio 6:4), filtered, and the obtained solid was vacuum dried to obtain 83 g of resin A-1.

[1057] [Chemical Formula 74]

[1058]

[1059] The weight average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-1 obtained from GPC (solvent: tetrahydrofuran (THF)) was 10,000, and the degree of dispersion (Mw / Mn) was 1.60. 13 The composition ratio measured by C-NMR (nuclear magnetic resonance) was 50 / 50 in molar ratio.

[1060] The other resins were also synthesized in the same way.

[1061] [Ore-generating agent]

[1062] <Mining Agent (B)>

[1063] The structures of photogenerators (photogenerator B1) (compounds B-1 to B-24) having a halogen atom in the cation portion, as shown in Table 3, are shown below.

[1064] [Chemical Formula 75]

[1065]

[1066] [Chemical Formula 76]

[1067]

[1068] [Chemical Formula 77]

[1069]

[1070] The structure of a photogenerator (photogenerator B2) (compounds C-1 to C-14) that does not have a halogen atom in the cation portion, as shown in Table 3, is shown below.

[1071] [Chemical Formula 78]

[1072]

[1073] [Optical Collapse Quencher]

[1074] <Optical Collapse Quencher (C)>

[1075] The structures of photodecaying quenchers (C) (photodecaying quencher C1) (compounds D-1 to D-7) having a halogen atom in the cation portion, as shown in Table 3, are shown below.

[1076] [Chemical Formula 79]

[1077]

[1078] The structures of photodecaying quenchers (photodecaying quencher C2) (compounds E-1 to E-9) that do not have a halogen atom in the cation portion, as shown in Table 3, are shown below.

[1079] [Chemical Formula 80]

[1080]

[1081] [Ore-generating linked ore-disintegrating quencher]

[1082] <Mining Agent Linked Ore-Disintegrating Quencher (D)>

[1083] The specific compound of the photocatalytic linked photocatalytic quencher (D) is described in the column of the photocatalytic (B) above.

[1084] [Acid Diffusion Control Agent]

[1085] The structures of acid diffusion control agents (E) (compounds G-1 to G-5) shown in Table 3 are shown below.

[1086] [Chemical Formula 81]

[1087]

[1088] [Suzy F]

[1089] The resins (F) (resins I-1 to I-7) shown in Table 3 are shown below.

[1090] Resins I-1 to I-7 were used by synthesizing them in accordance with the synthesis method of resin A-1 described above (Synthesization Example 1). Table 2 shows the composition ratio (mass % ratio; corresponding in order from left), weight average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit as described below.

[1091] In addition, the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resins I-1 to I-7 were measured by GPC (solvent carrier: tetrahydrofuran (THF)) (polystyrene equivalent). Furthermore, the compositional ratio (mass % ratio) of the resins is, 13 It was measured by C-NMR (nuclear magnetic resonance).

[1092] [Table 2]

[1093]

[1094] The structural formulas of resins I-1 to I-7 shown in Table 2 are shown below.

[1095] [Chemical Formula 82]

[1096]

[1097] [Surfactant]

[1098] The surfactants shown in Table 3 are shown below.

[1099] H-1: MegaPac F176 (Manufactured by DIC Co., Ltd., fluorinated surfactant)

[1100] H-2: Megapak R08 (Manufactured by DIC Co., Ltd., fluorine and silicone-based surfactant)

[1101] H-3: PF656 (Manufactured by OMNOVA, fluorinated surfactant)

[1102] 〔solvent〕

[1103] The solvents shown in Table 3 are listed below.

[1104] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1105] F-2: Propylene glycol monomethyl ether (PGME)

[1106] F-3: Propylene Glycol Monoethyl Ether (PGEE)

[1107] F-4: Cyclohexanone

[1108] F-5: Cyclopentanone

[1109] F-6: 2-heptanone

[1110] F-7: Ethyl lactate

[1111] F-8: γ-beautyllactone

[1112] F-9: Propylene carbonate

[1113] [Preparation of Resist Composition]

[1114] Each component shown in Table 3 was mixed to achieve a solid content concentration of 2.0 mass%. Subsequently, the obtained mixture was filtered by passing it through a polyethylene filter with a pore diameter of 50 nm first, a nylon filter with a pore diameter of 10 nm, and finally a polyethylene filter with a pore diameter of 5 nm in sequence to prepare a resist composition (Re-1 to Re-70, Re'-1 to Re'-5).

[1115] In addition, solid content refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples.

[1116] Also, in the table, the "Amount" column indicates the content (mass%) of each component relative to the total solid content in the resist composition.

[1117] [Table 3-1]

[1118]

[1119] [Table 3-2]

[1120]

[1121] [Table 3-3]

[1122]

[1123] [Pattern Formation]

[1124] [EUV Exposure, Organic Solvent Development]

[1125] A composition AL412 (manufactured by Brewer Science) for forming a sublayer was applied to a silicon wafer with a diameter of 12 inches and baked at 205°C for 60 seconds to form a sublayer with a thickness of 20 nm. On top of this, a resist composition shown in Table 3 was applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1126] Pattern irradiation was performed on a silicon wafer having a resist film obtained using an EUV lithography device (Exitech Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) so that the average line width of the obtained pattern was 20 nm. In addition, as a reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 was used.

[1127] After exposure, the resist film was baked at 90°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

[1128] 〔evaluation〕

[1129] <Defect Evaluation (Defect Inhibition)>

[1130] The pattern obtained by the above method was evaluated by counting the number of defects per silicon wafer using UVision5 (AMAT) and SEMVisionG4 (AMAT) according to the following evaluation criteria. The lower the number of defects, the better the defect suppression performance.

[1131] "A": Number of defects 50 or less

[1132] "B": Number of defects greater than 50 and less than or equal to 100

[1133] "C": Number of defects greater than 100 and less than or equal to 200

[1134] "D": Number of defects exceeds 200 and is 300 or less

[1135] "E": Number of defects exceeds 300 and is 400 or less

[1136] "F": Number of defects greater than 400 and less than or equal to 500

[1137] "G": Number of defects greater than 500 and less than or equal to 600

[1138] "H": Number of defects exceeds 600 and is 700 or less

[1139] "I": Number of defects exceeds 700 and is 800 or less

[1140] Roughness Performance (LWR Performance, nm)

[1141] The pattern obtained by the method described above was observed from the top of the pattern using a scanning electron microscope (SEM (Hitachi Seisakusho S-9380II)). The line width of the pattern was observed at 250 locations, and the measurement deviation was evaluated using 3σ to obtain LWR (line width roughness) (nm). The smaller the LWR value, the better the roughness performance.

[1142] Also, LWR performance (nm) is preferred in the order of 5.0 nm or less, 4.7 nm or less, 4.4 nm or less, 4.1 nm or less, 3.8 nm or less, 3.5 nm or less, and 3.2 nm or less.

[1143] The results of the evaluation are shown in Table 4 below.

[1144] [Table 4-1]

[1145]

[1146] [Table 4-2]

[1147]

[1148] As shown in Table 4 above, it was confirmed that the resist composition of the present invention has excellent roughness performance when an ultrafine pattern is formed by organic solvent development, and can also suppress the occurrence of defects in the pattern. On the other hand, these performances were insufficient in the resist composition of the comparative example.

[1149] [EUV Exposure, Alkaline Solution Development]

[1150] A composition AL412 (manufactured by Brewer Science) for forming a sublayer was applied to a silicon wafer with a diameter of 12 inches and baked at 205°C for 60 seconds to form a sublayer with a thickness of 20 nm. On top of this, a resist composition shown in Table 4 was applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1151] Pattern irradiation was performed on a silicon wafer having a resist film obtained using an EUV lithography device (Exitech Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) so that the average line width of the obtained pattern was 20 nm. In addition, as a reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 was used.

[1152] After exposure, the resist film was baked at 90°C for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. Afterward, the film was spin-dried to obtain a positive pattern.

[1153] Using the obtained positive type pattern, the pattern defect occurrence and roughness performance were evaluated in the same manner as described above.

[1154] The evaluation results are shown in Table 5 below.

[1155] [Table 5-1]

[1156]

[1157] [Table 5-2]

[1158]

[1159] As shown in Table 5 above, it was confirmed that the resist composition of the present invention has excellent roughness performance even when a pattern is formed by an alkaline phenomenon, and can also suppress the occurrence of defects in the pattern. On the other hand, these performances were insufficient in the resist composition of the comparative example.

Claims

Claim 1 (A) A resin having a repeating unit having an aromatic ring having an organic group having a halogen atom and a halogen-free substituent, and (Y) an ionic compound having a halogen atom in a cation portion, wherein the content of the ionic compound (Y) is 5.0 mass% or more with respect to the total solid content of the composition, the ionic compound having a halogen atom. Claim 2 (A) a resin having a repeating unit having an organic group having a halogen atom or a halogen atom and an aromatic ring having a halogen-free substituent, (Y) an ionic compound having a halogen atom in a cation portion, and (Z) an ionic compound having an acid-degradable group of any one of the following formulas (Y1), (Y2), and (Y4) in a cation portion; wherein the content of the ionic compound (Y) is 5.0 mass% or more with respect to the total solid content of the composition, the toxic photocatalytic or radiation-degradable resin composition. Formula (Y1): -C(Rx1)(Rx2)(Rx3) Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y4): -C(Rn)(H)(Ar) Among Formulas (Y1) and (Y2), Rx1 to Rx3 are each independently an alkyl group, It represents an alkeneyl group, a cycloalkyl group, or an aryl group. Two of Rx1 to Rx3 may be combined to form a monocyclic or polycyclic group. In formula (Y4), Ar represents an aromatic group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be combined with each other to form a non-aromatic ring. Claim 3 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the resin (A) has repeating units having a lactone structure. Claim 4 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the resin (A) has repeating units having a polycyclic lactone structure. Claim 5 A desensitizing photoreceptive or radiation-reducing resin composition according to claim 1 or claim 2, wherein the resin (A) has repeating units represented by the following formula (4). [Chemical Formula 1] In equation (4), X 11 R represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group. 11 Each represents an alkyl group independently. Two Rs 11 It may combine to form a ring. Claim 6 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the content of the ionic compound (Y) is 10.0 mass% or more with respect to the total solid content of the composition. Claim 7 A photosensitive or radiation-sensitive film formed by the photosensitive or radiation-sensitive resin composition described in claim 1 or claim 2. Claim 8 A pattern forming method comprising: a process of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition described in claim 1 or claim 2; a process of exposing the photosensitive or radiation-sensitive film to light; and a process of developing the exposed photosensitive or radiation-sensitive film using a developer and forming a pattern. Claim 9 A method for manufacturing an electronic device comprising the pattern forming method described in claim 8.

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