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-sensitive resin composition containing a resin (A1) comprising repeating units represented by the general formula (1) described in the specification, a sensitizing or radiation-sensitive resin composition containing a resin (A2) comprising repeating units represented by the general formula (2) described in the specification, a sensitizing or radiation-sensitive film using the sensitizing or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

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. More specifically, 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 that can be suitably utilized in an ultra-microlithography process applicable to manufacturing processes for ultra-Large Scale Integration (LSI) and high-capacity microchips, mold-making processes for nanoimprinting, and manufacturing processes for high-density information recording media, as well as other photofabrication processes. Background Technology

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication by lithography using a resist composition is performed. Recently, with the high integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron or quarter-micron range has become required. Accordingly, there is a trend toward shorter wavelengths in exposure wavelengths, such as from the g-line to the i-line, and further to KrF excimer laser light, and currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source is being developed. In addition, as a technology to further increase resolution, the so-called immersion method, which involves filling the space between the projection lens and the sample with a high refractive index liquid (hereinafter also referred to as "immersion liquid"), has been under development.

[0003] In addition, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) is currently being developed in addition to excimer laser light. Accordingly, resist compositions that are effectively responsive to various active light rays or radiation are being developed.

[0004] Patent Document 1 discloses a resist composition comprising a polymer having a group having a carbonate structure in a side chain.

[0005] Patent document 2 discloses a resist composition comprising a polymer or copolymer containing a specific halogen atom-containing group and a group having a specific carbonate structure. Prior art literature

[0006] Patent Document 1: Japanese Published Patent Application No. Sho 63-139343 Patent Document 2: Japanese Published Patent Application No. Hei 4-104250 The problem to be solved

[0007] However, the resist compositions described in Patent Documents 1 and 2 had room for improvement in terms of exposure latitude (EL) performance.

[0008] The present invention aims to provide a photosensitive or radiation-sensitive resin composition having excellent EL performance. In addition, the present invention aims to provide a photosensitive or radiation-sensitive film using the said photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. means of solving the problem

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

[0010] [1]

[0011] A desensitizing photoreceptor or radiation-reducing resin composition containing a resin (A1) having repeating units represented by the following general formula (1).

[0012] [Chemical Formula 1]

[0013]

[0014] Among general formulas (1),

[0015] Ra, Rb, and Rc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0016] L represents a single bond, -COO-, or a group represented by the general formula (1-1).

[0017] Y represents the group represented by the general formula (1-2).

[0018] Among general formula (1-1),

[0019] L1 represents a single bond or -COO-.

[0020] X1 represents an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group.

[0021] L2 represents -O- or -COO-.

[0022] *1 indicates the bonding site with the carbon atom to which Rb bonds, and *2 indicates the bonding site with Y.

[0023] In the case where L represents a group represented by the general formula (1-1), Rc and X1 may combine to form a ring.

[0024] Among general formulas (1-2),

[0025] Rd, Re, Rf, and Rg each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0026] X2 represents a single bond or an oxygen atom.

[0027] When X2 is a single bond, Rh represents an aryl group, a heteroaryl group, an alkene group, or an alkene group.

[0028] When X2 is an oxygen atom, Rh represents an aryl group, a heteroaryl group, an aromatic acyl group, a heteroaromatic acyl group, an alkyne group, or an alkene group.

[0029] m represents 0 or 1, and n represents an integer from 0 to 2.

[0030] However, either m or n is 0 and the other is an integer.

[0031] In the case of m=1, X2 is a single bond.

[0032] If Rh is an aryl group, n is 0 or 2, or L represents a single bond, -COO-, or a group represented by general formula (1-1), and L1 is -COO-.

[0033] *3 indicates the binding site with L.

[0034] [2]

[0035] A desensitizing light-sensitive or radiation-sensitive resin composition containing a resin (A2) having repeating units represented by the following general formula (2).

[0036] [Chemical Formula 2]

[0037]

[0038] Among general formulas (2),

[0039] Ri, Rj, and Rk each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0040] Rl and Rm each independently represent a hydrogen atom or an aryl group.

[0041] Ar1 represents a heteroarylene group or an arylene group that does not have an iodine atom.

[0042] Ar2 represents an aryl group.

[0043] Rk and Ar1 may combine to form a ring.

[0044] [3]

[0045] A desensitizing or radiation-reducing resin composition described in [2], wherein Rl and Rm in the above general formula (2) both represent hydrogen atoms.

[0046] [4]

[0047] The above resin (A1) has repeating units having aromatic groups that are different from the repeating units represented by the above general formula (1), or,

[0048] A deactivating photoreactive or radiation-reducing resin composition described in any one of [1] to [3], wherein the resin (A2) has repeating units having aromatic groups that are different from the repeating units represented by the general formula (2).

[0049] [5]

[0050] A desensitizing photoreactive or radiation-reducing resin composition described in [4], wherein the repeating unit having the above aromatic group is a repeating unit represented by the following formula (N-1).

[0051] [Chemical Formula 3]

[0052]

[0053] In equation (N-1), R 101 , R 102 and R 103 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. provided that R 102 is Ar A It may combine with to form a ring, and in that case, R 102 represents a single bond or an alkylene group. L A represents a single bond or a divalent linker. Ar A represents an aromatic group. k represents an integer from 0 to 5.

[0054] [6]

[0055] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [5], wherein the resin (A1) or resin (A2) comprises repeating units having groups that decompose by the action of acid.

[0056] [7]

[0057] A desensitizing photoreactive or radiation-reducing resin composition described in [6], comprising less than 30 mol% of repeating units having groups that decompose by the action of the above acid, with respect to the total repeating units of resin (A1) or resin (A2).

[0058] [8]

[0059] A photosensitive or radiation-sensitive resin composition described in [6] or [7], comprising at least one repeating unit having a group that decomposes by the action of the above acid, selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3).

[0060] [Chemical Formula 4]

[0061]

[0062] In equation (M-1), R 11 , R 12 and R 13 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M1 represents a divalent linker containing an aromatic group. R 14 , R 15 and R 16 Each represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group independently. 14 , R 15 and R 16 Two of them may combine to form a ring.

[0063] In equation (M-2), R 21 , R 22 and R23 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M2 represents a divalent linker containing an aromatic group. R 24 , R 25 and R 26 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 25 and R 26 It may combine to form a ring. L M2 The aromatic group included in is R 22 or R 24 It may be combined with to form a ring.

[0064] In Equation (M-3), R 31 , R 32 and R 33 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M3 represents a divalent linker containing an aromatic group. R 34 and R 35 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 36 It represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R 35 and R 36 It may combine to form a ring.

[0065] [9]

[0066] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [8], further containing a compound (B) that generates acid upon irradiation with active light or radiation.

[0067]

[10]

[0068] A photosensitive or radiation-sensitive resin composition described in [9], wherein the above compound (B) has a group that decomposes by the action of acid.

[0069]

[11]

[0070] A photosensitive or radiation-sensitive resin composition described in [9] or

[10] , wherein the above compound (B) is represented by the following formula (U-1).

[0071] [Chemical Formula 5]

[0072]

[0073] In formula (U-1), L U1 represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 may be the same or different. g represents an integer from 1 to 5. X U1 represents the g+1 linker. M U1 + It represents sulfonium ions or iodine ions.

[0074]

[12]

[0075] A photosensitive or radiation-sensitive resin composition described in any one of [9] to

[11] , wherein the above compound (B) is represented by the following formula (U-2).

[0076] [Chemical Formula 6]

[0077]

[0078] In equation (U-2), L U1 represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 It may be the same or different. RU1 represents a substituent. R U1 If this plural exists, the plural R U1 It may be the same or different. R U1 If this plural exists, the plural R U1 They may combine to form a ring. g1 represents an integer from 1 to 5. g2 represents an integer from 0 to 4. M U1 + It represents sulfonium ions or iodine ions.

[0079]

[13]

[0080] A photosensitive or photosensitive film formed using a photosensitive or photosensitive resin composition described in any one of [1] to

[12] .

[0081]

[14]

[0082] A pattern forming method comprising a process of forming a resist film using a photosensitive or radiation-sensitive resin composition described in any one of [1] to

[12] , a process of exposing the resist film to light, and a process of developing the exposed resist film using a developer.

[0083]

[15]

[0084] A method for manufacturing an electronic device comprising the pattern forming method described in

[14] . Effects of the invention

[0085] The present invention provides a chromogenic or radiation-sensitive resin composition having excellent EL performance. Furthermore, the present invention provides a chromogenic or radiation-sensitive film using the chromogenic or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device. Specific details for implementing the invention

[0086] The present invention will be described in detail below.

[0087] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0088] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB).

[0089] In this specification, "light" means active light or radiation.

[0090] In this specification, "exposure" includes, unless specifically explained otherwise, exposure by emission spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, etc., as well as drawing by particle beams such as electron beams and ion beams.

[0091] In this specification, "~" is used to mean including the values ​​listed before and after it as lower and upper limits.

[0092] In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0093] 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 (HLC-8120GPC manufactured by Tosho Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10μL, column: TSK gel Multipore HXL-M manufactured by Tosho Corporation, column temperature: 40℃, flow rate: 1.0mL / min, detector: differential refractive index detector).

[0094] Regarding the notation of a group (atomic group) in this specification, unless contrary to the spirit of the present invention, notations that do not specify substitution or non-substitution include groups that include substituents along with groups that do not have substituents. For example, the term "alkyl group" includes not only alkyl groups that do not have substituents (non-substituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group comprising at least one carbon atom.

[0095] As for the substituents, monovalent substituents are preferred unless otherwise specified. Examples of substituents include monovalent nonmetal groups excluding hydrogen atoms, and, for example, can be selected from the following substituents T.

[0096] (Substituent T)

[0097] As substituent T, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acrylyl, methacryloyl, and methoxalyl groups; sulfaneyl groups; alkylsulfaneyl groups such as methylsulfaneyl and tert-butylsulfaneyl groups; arylsulfaneyl groups such as phenylsulfaneyl and p-tolylsulfaneyl groups; alkyl groups; alkenyl groups; Examples include cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups, etc. In addition, if these substituents may have one or more additional substituents, a group having one or more substituents selected from the above substituents as additional substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) is also included as an example of substituent T.

[0098] In this specification, the bonding direction of the divalent groups indicated is not limited unless specifically explained. For example, in a compound represented by the formula “XYZ”, if Y is -COO-, Y may be -CO-O- or -O-CO-. The compound may be “X-CO-OZ” or “XO-CO-Z”.

[0099] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value obtained by calculation based on the database of Hammett 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.

[0100] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0101] In addition, pKa is also determined by molecular orbital calculations. Specifically, this method involves H in an aqueous solution based on thermodynamic cycles. + One method is to calculate it by calculating the dissociation free energy. 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.

[0102] 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, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on the DFT (density functional method) is adopted.

[0103] In this specification, pKa refers to "pKa in an aqueous solution" as described above; however, if pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0104] In this specification, "solid content" refers to a component that forms a photosensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered a solid content even if its nature is in a liquid state.

[0105] [Resin composition for light-sensitive or radiation-sensitive resins]

[0106] The sensitizing or radiation-sensitive resin composition of the present invention is a sensitizing or radiation-sensitive resin composition containing a resin (A1) having repeating units represented by the following general formula (1).

[0107] [Chemical Formula 7]

[0108]

[0109] Among general formulas (1),

[0110] Ra, Rb, and Rc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0111] L represents a single bond, -COO-, or a group represented by the general formula (1-1).

[0112] Y represents the group represented by the general formula (1-2).

[0113] Among general formula (1-1),

[0114] L1 represents a single bond or -COO-.

[0115] X1 represents an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group.

[0116] L2 represents -O- or -COO-.

[0117] *1 indicates the bonding site with the carbon atom to which Rb bonds, and *2 indicates the bonding site with Y.

[0118] In the case where L represents a group represented by the general formula (1-1), Rc and X1 may combine to form a ring.

[0119] Among general formulas (1-2),

[0120] Rd, Re, Rf, and Rg each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0121] X2 represents a single bond or an oxygen atom.

[0122] When X2 is a single bond, Rh represents an aryl group, a heteroaryl group, an alkene group, or an alkene group.

[0123] When X2 is an oxygen atom, Rh represents an aryl group, a heteroaryl group, an aromatic acyl group, a heteroaromatic acyl group, an alkyne group, or an alkene group.

[0124] m represents 0 or 1, and n represents an integer from 0 to 2.

[0125] However, either m or n is 0 and the other is an integer.

[0126] In the case of m=1, X2 is a single bond.

[0127] If Rh is an aryl group, n is 0 or 2, or L represents a single bond, -COO-, or a group represented by general formula (1-1), and L1 is -COO-.

[0128] *3 indicates the binding site with L.

[0129] In addition, the sensitizing or radiation-sensitive resin composition of the present invention is a sensitizing or radiation-sensitive resin composition containing a resin (A2) having repeating units represented by the following general formula (2).

[0130] [Chemical Formula 8]

[0131]

[0132] Among general formulas (2),

[0133] Ri, Rj, and Rk each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0134] Rl and Rm each independently represent a hydrogen atom or an aryl group.

[0135] Ar1 represents a heteroarylene group or an arylene group that does not have an iodine atom.

[0136] Ar2 represents an aryl group.

[0137] Rk and Ar1 may combine to form a ring.

[0138] Hereinafter, the light-sensitive or radiation-sensitive resin composition of the present invention is also referred to as the "composition of the present invention." Additionally, resin (A1) and resin (A2) are collectively referred to as "resin (A)."

[0139] The composition of the present invention is typically a resist composition, and may be a positive-type resist composition or a negative-type resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.

[0140] The composition of the present invention may be a chemically amplified type resist composition or a non-chemically amplified type resist composition.

[0141] A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0142] The reason why the resist composition of the present invention has excellent EL performance is not clearly evident in detail, but the inventors presume as follows. However, the present invention is by no means limited by the following presumed mechanism.

[0143] The resin (A) contained in the composition of the present invention comprises a group having multiple bonds such as an aromatic group, an alkenyl group, an alkyneyl group, and a repeating unit having a polar group such as -C(=O)-, -C(=O)O-, or -OC(=O)O-. Since the resin (A) has high compatibility with other repeating units having multiple bonds such as an aromatic group, and also has high compatibility with the salts of the sulfonium salts when the composition of the present invention contains such salts, a homogeneous resist film can be formed. In addition, these polar groups have appropriate affinity for water-based developers and organic solvent developers. Due to these properties, the resist film using the resin of the present invention is developed faithfully to the exposed pattern during development, and as a result, it is believed that the composition of the present invention containing the resin (A) has improved EL performance.

[0144] First, the various components of the composition of the present invention will be described in detail below.

[0145] [Suzy (A)]

[0146] If the resin (A) included in the composition of the present invention is resin (A1), it includes a repeating unit represented by the general formula (1). If the resin (A) included in the composition of the present invention is resin (A2), it includes a repeating unit represented by the general formula (2).

[0147] A repeating unit included in the group consisting of the repeating unit represented by the above general formula (1) and the repeating unit represented by the above general formula (2) is also called a “repeting unit (T)”. The repeating unit (T) is a repeating unit having a group having multiple bonds such as an aromatic group, an alkene group, an alkyne group, etc., and a polar group such as -C(=O)-, -C(=O)O-, -OC(=O)O-.

[0148] <Repetition unit represented by general formula (1)>

[0149] The resin (A1) includes a repeating unit represented by the following general formula (1).

[0150] [Chemical Formula 9]

[0151]

[0152] Among the above general formula (1),

[0153] Ra, Rb, and Rc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0154] L represents a single bond, -COO-, or a group represented by the general formula (1-1).

[0155] Y represents the group represented by the general formula (1-2).

[0156] Among general formula (1-1),

[0157] L1 represents a single bond or -COO-.

[0158] X1 represents an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group.

[0159] L2 represents -O- or -COO-.

[0160] *1 indicates the bonding site with the carbon atom to which Rb bonds, and *2 indicates the bonding site with Y.

[0161] In the case where L represents a group represented by the general formula (1-1), Rc and X1 may combine to form a ring.

[0162] Among general formulas (1-2),

[0163] Rd, Re, Rf, and Rg each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0164] X2 represents a single bond or an oxygen atom.

[0165] When X2 is a single bond, Rh represents an aryl group, a heteroaryl group, an alkene group, or an alkene group.

[0166] When X2 is an oxygen atom, Rh represents an aryl group, a heteroaryl group, an aromatic acyl group, a heteroaromatic acyl group, an alkyne group, or an alkene group.

[0167] m represents 0 or 1, and n represents an integer from 0 to 2.

[0168] However, either m or n is 0 and the other is an integer.

[0169] In the case of m=1, X2 is a single bond.

[0170] If Rh is an aryl group, n is 0 or 2, or L represents a single bond, -COO-, or a group represented by general formula (1-1), and L1 is -COO-.

[0171] *3 indicates the binding site with L.

[0172] In general formula (1), Ra, Rb and Rc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0173] The alkyl groups represented by Ra, Rb, and Rc may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0174] The cycloalkyl groups represented by Ra, Rb, and Rc may be monocyclic cycloalkyl groups such as cyclopentyl groups or cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, or adamantyl groups. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Additionally, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0175] Examples of halogen atoms represented by Ra, Rb, and Rc include fluorine, chlorine, bromine, and iodine atoms.

[0176] The alkyl group included in the alkoxycarbonyl group represented by Ra, Rb, and Rc may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group included in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0177] It is preferable that Ra and Rc represent hydrogen atoms.

[0178] It is preferable that Rb represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferable that it is a hydrogen atom or a methyl group.

[0179] In general formula (1), L represents a single bond, -COO- or a group represented by general formula (1-1).

[0180] Among general formula (1-1),

[0181] L1 represents a single bond or -COO-.

[0182] X1 represents an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group.

[0183] L2 represents -O- or -COO-.

[0184] *1 indicates the bonding site with the carbon atom to which Rb bonds, and *2 indicates the bonding site with Y.

[0185] As for the alkylene group represented by X1, for example, a straight-chain or branched-chain alkylene group having 1 to 20 carbon atoms may be used. The alkylene group is preferably a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group or an ethylene group.

[0186] The cycloalkylene group represented by X1 may be a contribution obtained by removing any hydrogen atom from a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group, or a contribution obtained by removing any hydrogen atom from a polycyclic cycloalkyl group such as a norvonyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with vinylene groups.

[0187] The cycloalkylene group is preferably a cycloalkylene group having 3 to 12 carbon atoms, preferably a monocyclic cycloalkylene group having 3 to 12 carbon atoms, more preferably a monocyclic cycloalkylene group having 3 to 7 carbon atoms, and even more preferably a cyclopentylene group or a cyclohexylene group.

[0188] As for the arylene group represented by X1, an arylene group having 6 to 20 carbon atoms is preferred, an arylene group having 6 to 15 carbon atoms is more preferred, and a phenylene group or a naphthylene group is more preferred.

[0189] The heteroarylene group represented by X1 is preferably an aromatic group comprising at least one heteroatom selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms in reduction. The number of reducing atoms in the heteroarylene group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroarylene group is preferably 1 to 19, and more preferably 3 to 14.

[0190] The above alkylene group, cycloalkylene group, arylene group, and heteroarylene group may have substituents.

[0191] X1 preferably represents an arylene group, and more preferably represents a phenylene group.

[0192] In general formula (1-2), Rd, Re, Rf and Rg each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.

[0193] The alkyl groups represented by Rd, Re, Rf, and Rg may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0194] The cycloalkyl groups represented by Rd, Re, Rf, and Rg may be monocyclic cycloalkyl groups such as cyclopentyl groups or cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, or adamantyl groups. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Additionally, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0195] As for the aryl groups represented by Rd, Re, Rf, and Rg, an aryl group having 6 to 20 carbon atoms is preferred, an aryl group having 6 to 15 carbon atoms is more preferred, and a phenyl group or a naphthyl group is more preferred.

[0196] The heteroaryl group represented by Rd, Re, Rf, and Rg is preferably an aromatic group comprising at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms in reduction. The number of reducing atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 14.

[0197] The above alkyl group, cycloalkyl group, aryl group, and heteroaryl group may have substituents.

[0198] It is preferable that Rd and Re are each independently a hydrogen atom, a carbon-1 to carbon-3 alkyl group, or a phenyl group, and it is more preferable that both are hydrogen atoms.

[0199] Rf and Rg are each preferably independently a hydrogen atom, a carbon-1 to carbon-3 alkyl group, or a phenyl group, and it is more preferable that at least one of them is a hydrogen atom.

[0200] In general formula (1-2), Rh represents an aryl group, a heteroaryl group, an alkyne group, or an alkene group when X2 is a single bond. When X2 is an oxygen atom, Rh represents an aryl group, a heteroaryl group, an aromatic acyl group, a heteroaromatic acyl group, an alkyne group, or an alkene group.

[0201] The aryl group represented by Rh is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and more preferably a phenyl group or a naphthyl group.

[0202] The heteroaryl group represented by Rh is preferably an aromatic group comprising at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms in reduction. The number of reducing atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 14.

[0203] The alkyne group represented by Rh may be in a straight chain or a branched chain, and an alkyne group having 2 to 20 carbon atoms is preferred, and an alkyne group having 2 to 15 carbon atoms is more preferred. Examples of alkyne groups include an etyne group and a propagyl group.

[0204] The alkeneyl group represented by Rh may be a straight chain or a branched chain, and an alkeneyl group having 2 to 20 carbon atoms is preferred, and an alkeneyl group having 2 to 15 carbon atoms is more preferred. Examples of alkeneyl groups include vinyl groups and allyl groups.

[0205] An aryl carbonyl group can be cited as an aromatic acyl group represented as Rh. As for the aryl group in the aryl carbonyl group, the aryl group as Rh described above can be cited, and the preferred example is the same.

[0206] As a heteroaromatic acyl group represented as Rh, a heteroaryl carbonyl group may be cited. As a heteroaryl group within the heteroaryl carbonyl group, the heteroaryl group as Rh described above may be cited, and the preferred example is the same.

[0207] Rh may have substituents and may form a ring by combining with Rd or Re. Additionally, if Rh has multiple substituents, they may combine to form a ring.

[0208] Rh is preferably an aryl group, and more preferably a phenyl group.

[0209] The repeating unit represented by general formula (1) is preferably not to have an iodine atom, and more preferably not to have a halogen atom.

[0210] Either m or n is 0, and the other is an integer. Here, an integer represents an integer greater than or equal to 0. In a preferred embodiment, either m or n is 0, and the other is an integer greater than or equal to 1.

[0211] Specific examples of repeating units represented by general formula (1) are shown below, but are not limited to these.

[0212] [Chemical Formula 10]

[0213]

[0214] [Chemical Formula 11]

[0215]

[0216] The content of the repeating unit represented by the general formula (1) in the resin (A1) is preferably 1 mol% or more with respect to the total repeating unit in the resin (A1), more preferably 3 mol% or more, and more preferably 5 mol% or more. In addition, the content of the repeating unit represented by the general formula (1) in the resin (A1) is preferably 100 mol% or less with respect to the total repeating unit in the resin (A1), more preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 70 mol% or less.

[0217] The type of repeating unit represented by the general formula (1) included in the resin (A1) may be one type or two or more types. If two or more types are included, it is preferable that the total content of them be within the range of the above suitable content.

[0218] <Repetition unit represented by general formula (2)>

[0219] The resin (A2) includes a repeating unit represented by the following general formula (2).

[0220] [Chemical Formula 12]

[0221]

[0222] Among general formulas (2),

[0223] Ri, Rj, and Rk each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0224] Rl and Rm each independently represent a hydrogen atom or an aryl group.

[0225] Ar1 represents a heteroarylene group or an arylene group that does not have an iodine atom.

[0226] Ar2 represents an aryl group.

[0227] Rk and Ar1 may combine to form a ring.

[0228] In general formula (2), Ri, Rj and Rk each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0229] The alkyl groups represented by Ri, Rj, and Rk may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0230] The cycloalkyl groups represented by Ri, Rj, and Rk may be monocyclic cycloalkyl groups such as cyclopentyl groups or cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, or adamantyl groups. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Additionally, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0231] Examples of halogen atoms represented by Ri, Rj, and Rk include fluorine, chlorine, bromine, and iodine atoms.

[0232] The alkyl group included in the alkoxycarbonyl group represented by Ri, Rj, and Rk may be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group included in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0233] It is desirable that Ri, Rj, and Rk are all hydrogen atoms.

[0234] In general formula (2), Rl and Rm each independently represent a hydrogen atom or an aryl group.

[0235] As for the aryl groups represented by Rl and Rm, an aryl group having 6 to 20 carbon atoms is preferred, an aryl group having 6 to 15 carbon atoms is more preferred, and a phenyl group or a naphthyl group is more preferred. The aryl group may have a substituent.

[0236] It is preferable that at least one of Rl and Rm represents a hydrogen atom, and more preferable that both represent hydrogen atoms.

[0237] In general formula (2), Ar1 represents a heteroarylene group or an arylene group that does not have an iodine atom.

[0238] The heteroarylene group represented by Ar1 is preferably an aromatic group comprising at least one heteroatom selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms in reduction. The number of reducing atoms in the heteroarylene group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroarylene group is preferably 1 to 19, and more preferably 3 to 14.

[0239] In the arylene group that does not have an iodine atom represented by Ar1, the arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and more preferably a phenylene group or a naphthylene group.

[0240] The group represented by Ar1 may have substituents, but it is preferable not to have iodine atoms, and more preferable not to have halogen atoms.

[0241] Ar1 is preferably an arylene group that does not have an iodine atom, and more preferably a phenylene or naphthylene group that does not have a halogen atom.

[0242] In general formula (2), Ar2 represents an aryl group.

[0243] The aryl group represented by Ar2 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and more preferably a phenyl group or a naphthyl group.

[0244] Ar2 may have substituents. If it has multiple substituents, they may combine to form a ring.

[0245] The repeating unit represented by general formula (2) is preferably not to have an iodine atom, and more preferably not to have a halogen atom.

[0246] Specific examples of repeating units represented by general formula (2) are shown below, but are not limited to these.

[0247] [Chemical Formula 13]

[0248]

[0249] The content of the repeating unit represented by the general formula (2) in the resin (A2) is preferably 1 mol% or more with respect to the total repeating unit in the resin (A2), more preferably 3 mol% or more, and more preferably 5 mol% or more. In addition, the content of the repeating unit represented by the general formula (2) in the resin (A2) is preferably 100 mol% or less with respect to the total repeating unit in the resin (A2), more preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 70 mol% or less.

[0250] The type of repeating unit represented by the general formula (2) included in the resin (A2) may be one type or two or more types. If two or more types are included, it is preferable that the total content of them be within the range of the above suitable content.

[0251] <Repeating unit with aromatic groups>

[0252] It is preferable that the resin (A) includes repeating units having aromatic groups (also called "repeating units (Ar)").

[0253] It is preferable that the repeating unit (Ar) be different from either the repeating unit represented by general formula (1) or the repeating unit represented by general formula (2).

[0254] The repeating unit (Ar) may be a repeating unit having an acid-degrading group as described below, or a repeating unit different from a repeating unit having an acid-degrading group.

[0255] The repeating unit (Ar) is preferably a repeating unit represented by the following equation (N-1).

[0256] [Chemical Formula 14]

[0257]

[0258] In equation (N-1), R 101 , R 102 and R 103 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. provided that R 102 is Ar A It may combine with to form a ring, and in that case, R 102 represents a single bond or an alkylene group. L A represents a single bond or a divalent linker. Ar A represents an aromatic group. k represents an integer from 0 to 5.

[0259] R 101 , R 102 and R 103 The alkyl group represented as such may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred.

[0260] R 101 , R 102 and R 103 The cycloalkyl group represented by the above may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0261] R 101 , R 102and R 103 Examples of halogen atoms that appear as such include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0262] R 101 , R 102 and R 103 The alkyl group included in the alkoxycarbonyl group shown as such may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0263] L in Equation (N-1) A represents a single bond or a divalent linker.

[0264] L A The divalent connector represented by is not particularly limited, but for example, -COO-, -CONR 64 Examples include -, alkylene groups, or groups formed by combining two or more of these groups. The above R 64 represents a hydrogen atom or an alkyl group.

[0265] The above alkylene group is not particularly limited, but an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, is preferred.

[0266] R 64 As for the alkyl group in which α represents an alkyl group, examples include alkyl groups having 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or fewer carbon atoms are preferred.

[0267] Ar in Equation (N-1) A represents an aromatic group, and more specifically, an aromatic group of (k+1). The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0268] The description, specific examples, and preferred range of the divalent aromatic group when k is 1 are L in the formula (M-1) described below. M1 It is identical to the aromatic group included in this.

[0269] Ar A The aromatic group represented by may have a substituent. The substituents are not particularly limited, but examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl groups.

[0270] As for the (k+1) valence aromatic group in the case where k is an integer greater than or equal to 2, a group formed by removing (k-1) arbitrary hydrogen atoms from a divalent aromatic group can be cited.

[0271] Ar A It is preferable that it represents an aromatic group having 6 to 18 carbon atoms, and more preferable that it represents a benzene group, a naphthalene group, or a biphenylene group.

[0272] The repeating unit represented by formula (N-1) preferably has a hydroxystyrene structure. That is, Ar A It is desirable to represent a benzene ring.

[0273] k represents an integer from 0 to 5, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0274] Specific examples of repeating units (Ar) are shown below, but are not limited thereto. Among the following structural formulas, G 1 and G 2 Each represents independently a hydrogen atom, a methyl group, a cyano group, a hydroxyl group, or a hydroxymethyl group. f1 represents an integer from 0 to 3.

[0275] [Chemical Formula 15]

[0276]

[0277] When the resin (A) contains repeating units (Ar), the content of the repeating units (Ar) in the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% or more with respect to the total repeating units in the resin (A). In addition, the content of the repeating units (Ar) in the resin (A) is preferably 90 mol% or less with respect to the total repeating units in the resin (A), more preferably 85 mol% or less, and more preferably 80 mol% or less.

[0278] When the resin (A) contains a repeating unit (Ar), the repeating unit (Ar) in the resin (A) may be of one type or two or more types. When two or more types are included, it is preferable that the total content thereof be within the range of the above suitable content.

[0279] <Repeating unit having an acid-degrading group>

[0280] The resin (A) may include repeating units having acid-degradable groups (groups that decompose by the action of acid). If the resin (A) includes repeating units having acid-degradable groups, the resin (A) is an acid-degradable resin. When the resin (A) is an acid-degradable resin, typically, the polarity of the resin (A) increases due to the action of acid, solubility in an alkaline developer increases, and solubility in an organic solvent decreases. Furthermore, when the resin (A) is an acid-degradable resin, in a pattern formation method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic developer is used as the developer, a negative-type pattern is suitably formed.

[0281] A repeating unit having an acid-degrading group may be the same repeating unit as repeating unit (T), or may be a repeating unit different from repeating unit (T), but it is preferable that it be a repeating unit different from repeating unit (T).

[0282] It is desirable that the acid-decomposing group be a group that is decomposed by the action of acid to generate a polar group.

[0283] It is desirable for the acid-degrading group to have a structure in which the polar group is protected by the group that is detached by the action of the acid (detacher).

[0284] As the above polar group, an alkali-soluble group is preferred, and examples include an acidic group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group.

[0285] Examples of groups that are removed by the action of acid include the groups represented by equations (Y1) to (Y4).

[0286] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0287] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0288] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0289] Equation (Y4): -C(Rn)(H)(Ar)

[0290] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (straight or branched), an alkenyl group (straight or branched), or an alkyneyl group (straight or branched). Additionally, when 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.

[0291] 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.

[0292] Two of Rx1 to Rx3 may combine to form a ring (either a monoring or a polyring).

[0293] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred, and alkyl groups having 1 to 5 carbon atoms are more preferred.

[0294] The number of carbon atoms in the cycloalkyl groups of Rx1 to Rx3 is preferably 3 to 20, and more preferably 4 to 15. As for the cycloalkyl group, it may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group. That is, Rx1 to Rx3 may be cycloalkenylene groups.

[0295] As for the aryl groups of Rx1 to Rx3, aryl groups having 6 to 10 carbon atoms are preferred, and examples include phenyl groups, naphthyl groups, and anthryl groups.

[0296] As for the aralkyl groups of Rx1 to Rx3, it is preferable to have a group in which one hydrogen atom of the alkyl groups of Rx1 to Rx3 described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples include a benzyl group.

[0297] As for the alkene groups of Rx1 to Rx3, an alkene group having 2 to 20 carbon atoms may be used, and an alkene group having 2 to 10 carbon atoms is preferred, for example, a vinyl group or an allyl group is preferred.

[0298] As for the alkyne groups of Rx1 to Rx3, alkyne groups having 2 to 20 carbon atoms may be used, alkyne groups having 2 to 10 carbon atoms are preferred, and for example, an etyne group is preferred.

[0299] As for the ring formed by combining two of Rx1 to Rx3, a cycloalkyl group is preferred. As for the cycloalkyl group formed by combining two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0300] 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, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, the cycloalkyl group may have one or more ethylene groups constituting the cycloalkane ring substituted with a vinylene group.

[0301] The group represented by formula (Y1) or formula (Y2) is preferably, for example, in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are combined to form the cycloalkyl group described above.

[0302] 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 each other 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.

[0303] In addition, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with, for example, one or more methylene groups having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group.

[0304] Also, R 38 It may combine with other substituents on the main chain of the repeating unit to form a ring. R 38 The group formed by the bonding of other substituents on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0305] 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.

[0306] Preferably, the resin (A) comprises at least one selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3). The repeating unit represented by the following formula (M-1), the repeating unit represented by the following formula (M-2), and the repeating unit represented by the following formula (M-3) are repeating units having an acid-degradable group. The repeating unit selected from the group consisting of the repeating unit represented by the following formula (M-1), the repeating unit represented by the following formula (M-2), and the repeating unit represented by the following formula (M-3) is also referred to as a "repeating unit (M)".

[0307] The repeating unit (M) is a repeating unit having a group that is decomposed by the action of acid.

[0308] [Chemical Formula 16]

[0309]

[0310] In equation (M-1), R 11 , R 12 and R 13 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M1 represents a divalent linker containing an aromatic group. R 14 , R 15 and R 16 Each represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group independently. 14 , R 15 and R 16 Two of them may combine to form a ring.

[0311] In equation (M-2), R 21 , R 22 and R 23 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M2represents a divalent linker containing an aromatic group. R 24 , R 25 and R 26 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 25 and R 26 It may combine to form a ring. L M2 The aromatic group included in is R 22 or R 24 It may be combined with to form a ring.

[0312] In Equation (M-3), R 31 , R 32 and R 33 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M3 represents a divalent linker containing an aromatic group. R 34 and R 35 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 36 It represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R 35 and R 36 It may combine to form a ring.

[0313] The repetition unit represented by the above equation (M-1) is explained.

[0314] R 11 , R 12 and R 13 The alkyl group represented as such may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred.

[0315] R 11 , R 12 and R 13The cycloalkyl group represented by the above may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0316] R 11 , R 12 and R 13 Examples of halogen atoms that appear as such include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0317] R 11 , R 12 and R 13 The alkyl group included in the alkoxycarbonyl group shown as such may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0318] L M1 It represents a divalent linker containing an aromatic group.

[0319] L M1 The aromatic group included here can be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0320] L M1 It is preferable that the aromatic group included here be a divalent group.

[0321] L M1When the included aromatic group is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but, for example, 6 to 20 is preferred, and 6 to 14 is more preferred. The aromatic hydrocarbon group is preferably a phenylene group or a naphthylene group, and is more preferred to be a phenylene group.

[0322] In addition, the aromatic hydrocarbon group is formed by removing two hydrogen atoms from a condensed ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is condensed with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.).

[0323] L M1 When the included aromatic group is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. It is preferable that the aromatic heterocyclic group includes at least one heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms in the reduction. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but, for example, 2 to 18 is preferred, 3 to 15 is more preferred, and 4 to 12 is more preferred. The number of reducing atoms in the aromatic heterocyclic group is not particularly limited, but, for example, 5 to 20 is preferred, and 6 to 15 is more preferred. Examples of aromatic heterocyclic groups include, for instance, five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isooxazole, thiazole, isothiazole, triazole, thiophene, and furan, or groups formed by removing two hydrogen atoms from six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine.

[0324] In addition, the aromatic heterocyclic group comprises two hydrogen atoms from a condensed cyclic compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the above-mentioned 5-membered aromatic heterocyclic compound or the above-mentioned 6-membered aromatic heterocyclic compound is condensed with at least one selected from the group consisting of the above-mentioned 5-membered aromatic heterocyclic compound, the above-mentioned 6-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., 5-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, etc.), and 6-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.). It also contributes to the effort made by removal.

[0325] L M1 In addition to the aromatic group, it may also contain other divalent groups.

[0326] Other divalent groups include, for example, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, and groups formed by connecting multiple of these.

[0327] L M1 In the case where other divalent groups are included, it is preferable that the other divalent groups be located closer to the main chain of the resin (A) than the aromatic groups.

[0328] R 14 , R 15 and R 16 The alkyl group represented by may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. R 14 , R 15 and R 16 The alkyl group represented by may be substituted with at least one of -CO- and -O- by a methylene group.

[0329] R 14 , R 15 and R 16 The cycloalkyl group represented by such a group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15.

[0330] R 14 , R 15 and R 16 The number of carbon atoms in the aryl group represented by is not particularly limited, but, for example, 6 to 20 is preferred, and 6 to 14 is more preferred. R 14 , R 15 and R 16 As for the aryl group, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0331] R 14 , R 15 and R 16 As for the Aralkillgi appearing as, the aforementioned R 14 , R 15 and R 16 One hydrogen atom among the alkyl groups represented as, the above-described R 14 , R 15 and R 16 A group substituted with an aryl group (preferably a phenyl group) is preferred, and examples include a benzyl group.

[0332] R 14 , R 15 and R 16 The alkenyl group shown may be either a straight chain or a branched chain. The number of carbon atoms in the alkenyl group is not particularly limited, but 2 to 5 is preferred, and 2 to 3 is more preferred. As for the alkenyl group, a vinyl group is preferred.

[0333] R 14 , R 15 and R16 Two of them may combine to form a ring. R 14 , R 15 and R 16 As for the ring formed by the combination of two of them, a cycloalkyl ring is preferred. The cycloalkane ring may be a monocyclic cycloalkane ring or a polycyclic cycloalkane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Additionally, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0334] Each of the above groups in formula (M-1) may have a substituent, and as a substituent, for example, the above substituent T can be used.

[0335] Specific examples of the repeating unit represented by Equation (M-1) are shown below, but are not limited thereto.

[0336] [Chemical Formula 17]

[0337]

[0338] The repetition unit represented by the above equation (M-2) is explained.

[0339] R 21 , R 22 and R 23 The description, specific examples, and preferred ranges for R in the above-described formula (M-1) are as follows. 11 , R 12 and R 13 It is identical to.

[0340] L M2 The description, specific examples, and preferred ranges for are L in the above-described formula (M-1). M1 It is identical to.

[0341] R 24 , R 25 and R 26Description, specific examples, and preferred ranges for the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by, are R in the formula (M-1) described above. 14 , R 15 and R 16 It is identical to.

[0342] R 25 and R 26 They may combine to form a ring. R 25 and R 26 The ring formed by this combination is preferably a non-aromatic ring, and more preferably a non-aromatic ring having 5 to 8 reducing atoms.

[0343] L M2 The aromatic group included in is R 22 or R 24 It may combine with to form a ring. L M2 Aromatic groups included in and R 22 or R 24 The ring formed by the combination is preferably a non-aromatic ring, and more preferably a non-aromatic ring having 5 to 8 reducing atoms.

[0344] Each of the above groups in formula (M-2) may have a substituent, and as a substituent, for example, the above substituent T can be used.

[0345] Specific examples of the repeating unit represented by Equation (M-2) are shown below, but are not limited thereto.

[0346] [Chemical Formula 18]

[0347]

[0348] The repetition unit represented by the above equation (M-3) is explained.

[0349] R 31 , R 32 and R 33 The description, specific examples, and preferred ranges for R in the above-described formula (M-1) are as follows. 11 , R 12 and R 13 It is identical to.

[0350] L M3 The description, specific examples, and preferred ranges for are L in the above-described formula (M-1). M1 It is identical to.

[0351] R 34 , R 35 and R 36 Description, specific examples, and preferred ranges for the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by, are R in the formula (M-1) described above. 14 , R 15 and R 16 It is identical to.

[0352] R 35 and R 36 They may combine to form a ring. R 35 and R 36 The ring formed by this combination is preferably a non-aromatic ring, and more preferably a non-aromatic ring having 5 to 8 reducing atoms.

[0353] Each of the above groups in formula (M-3) may have a substituent, and as a substituent, for example, the above substituent T can be used.

[0354] Specific examples of the repeating unit represented by Equation (M-3) are shown below, but are not limited thereto.

[0355] [Chemical Formula 19]

[0356]

[0357] Specific examples of repeating units including acid-degradable groups other than repeating units (M) are shown below, but are not limited thereto.

[0358] [Chemical Formula 20]

[0359]

[0360] [Chemical Formula 21]

[0361]

[0362] When the resin (A) comprises repeating units having acid-degradable groups, the content of repeating units having acid-degradable groups in the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more with respect to the total repeating units in the resin (A). In addition, the content of repeating units having acid-degradable groups in the resin (A) is preferably 60 mol% or less with respect to the total repeating units in the resin (A), more preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably less than 30 mol%.

[0363] When the resin (A) includes repeating units having acid-degradable groups, the repeating units having acid-degradable groups in the resin (A) may be of one type or two or more types. When two or more types are included, it is preferable that their total content be within the range of the above suitable content.

[0364] <Repeating unit having a fluorine atom, a bromine atom, or an iodine atom, without an acid-degrading group>

[0365] The resin (A) may have a repeating unit having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as "unit X") that does not have an acid-degradable group, separate from the above-described repeating unit having an acid-degradable group. It is preferable that the repeating unit having a fluorine atom, a bromine atom, or an iodine atom that does not have an acid-degradable group be different from other types of repeating units, such as the above-described repeating unit (Ar), the below-described repeating unit having a lactone group, a sulfonate group, or a carbonate group, and the repeating unit having a photo-generating group.

[0366] As unit X, the repeating unit represented by equation (C) is preferred.

[0367] [Chemical Formula 22]

[0368]

[0369] L5 represents a single bond or an ester group. R9 represents an alkyl group that may have a hydrogen atom, or a fluorine atom, or an iodine atom. R 10 It represents an alkyl group that may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a combination thereof.

[0370] Specific examples of repeating units having a fluorine atom or an iodine atom include, for instance, the repeating units described in

[0116] –

[0117] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0371] When the resin (A) contains unit X, the content of unit X may be 5 mol% or more and 10 mol% or more with respect to the total repeating unit in the resin (A). In addition, the content of unit X may be 50 mol% or less and 40 mol% or less with respect to the total repeating unit in the resin (A).

[0372] It is also desirable that resin (A) does not contain unit X.

[0373] <Repeating unit having a lactone, sulfonate, or carbonate group>

[0374] The resin (A) may have repeating units having a lactone group, a sulfonate group or a carbonate group (hereinafter also referred to as "unit Y").

[0375] It is also desirable that the unit Y does not have acid groups such as hydroxyl groups and hexafluoropropanol groups.

[0376] As for the lactone group or sulfon group, it is sufficient to have a lactone structure or a sulfon structure. The lactone structure or sulfon structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sulfon structure. Among these, it is more preferable that another ring structure is condensed to the 5- to 7-membered ring lactone structure in a manner forming a bicyclo structure or a spyro structure, or that another ring structure is condensed to the 5- to 7-membered ring sulfon structure in a manner forming a bicyclo structure or a spyro structure.

[0377] As for the carbonate group, a cyclic carbonate ester group is preferred.

[0378] For repeating units having cyclic carbonate ester groups, for example, reference may be made to

[0127] –

[0133] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0379] The resin (A) preferably has repeating units having a lactone group, a sulfon group, or a carbonate group formed by removing one or more hydrogen atoms from a reducing atom of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-22), a sulfon structure represented by any one of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any one of the following formulas (CC1-1) to (CC1-2), and the lactone group, sulfon group, or carbonate group may be directly bonded to the main chain. For example, the reducing atom of the lactone group, sulfon group, or carbonate group may constitute the main chain of the resin (A). The lactone group, sulfon group, and carbonate group may have substituents.

[0380] R in the following structural formula L represents a substituent. R L If this plural exists, the plural R L It may be the same or different. R LExamples include C1-C8 alkyl groups, C4-C10 cycloalkyl groups, C1-C8 alkoxy groups, C2-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. If multiple e1s exist, the multiple e1s may be identical or different. If e1 is 2 or more, multiple Rs exist. L may be identical or different, and multiple Rs exist. L They may combine to form a ring.

[0381] [Chemical Formula 23]

[0382]

[0383] As repeating units having a lactone group, a sulfonate group or a carbonate group, for example, a repeating unit represented by the following formula (AI-2) can be cited.

[0384] [Chemical Formula 24]

[0385]

[0386] In formula (AI-2), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Substituents that may be present in the alkyl group of Rb0 include hydroxyl groups and halogen atoms.

[0387] Examples of halogen atoms of Rb0 include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. It is preferable that Rb0 be a hydrogen atom or a methyl group.

[0388] Ab represents a single bond, an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a combination thereof. Among these, as Ab, a single bond or a linker represented as -Ab1-CO2- is preferred. Ab1 is a straight-chain or branched-chain alkylene group or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0389] V represents a group formed by removing one hydrogen atom from a reducing atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22), a group formed by removing one hydrogen atom from a reducing atom of a sulfone structure represented by any one of formulas (SL1-1) to (SL1-3), or a group formed by removing one hydrogen atom from a reducing atom of a cyclic carbonate ester structure represented by any one of formulas (CC1-1) to (CC1-2).

[0390] When the resin (A) contains unit Y, the content of unit Y may be 1 mol% or more and 10 mol% or more with respect to the total repeating unit in the resin (A). In addition, the content of unit Y may be 80 mol% or less and 70 mol% or less with respect to the total repeating unit in the resin (A).

[0391] It is also desirable that the resin (A) does not contain the unit Y.

[0392] <Repeating unit with a mine generator>

[0393] Resin (A) may have repeating units having a group that generates acid upon irradiation with active light or radiation (also called a "photo-generator").

[0394] As a repeating unit having a mine generator, the repeating unit represented by Equation (4) can be cited.

[0395] [Chemical Formula 25]

[0396]

[0397] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linker. L 42 represents a divalent connector. R 40 It represents a structural region that decomposes upon irradiation with active light or radiation, generating acid in the side chain.

[0398] L 41 It is preferable that it represents a single bond or a divalent linker, and represents a single bond or an ester bond (-COO-).

[0399] L 42 It is preferable that the linker is composed of at least one selected from the group consisting of alkylene groups, cycloalkylene groups, arylene groups, -O-, -CO-, -S-, -SO-, -SO2-, and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, e.g., alkyl groups, cycloalkyl groups, aryl groups, etc.).

[0400] The alkylene group may be either a straight chain or a branched chain. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred.

[0401] The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.

[0402] The number of carbon atoms in the arylene group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred.

[0403] The alkylene group, cycloalkylene group, and arylene group may have a substituent, and the above substituent T may be used as a substituent.

[0404] R 40It is desirable that the cause be represented by the following formula (S4-1).

[0405] [Chemical Formula 26]

[0406]

[0407] In Equation (S4-1), Q - represents the acid residue, and M + Silver represents a cation. * indicates L 41 Indicates the connection location with.

[0408] Acid residue is a substance formed by the dissociation of protons from acid.

[0409] Q - is a carboxylate anion group (COO - ), sulfonate anion group (SO3 - ), or sulfonamide group (N - -SO2R N1 It appears as. R N1 The organic group represents an organic group, and examples include organic groups having 1 to 10 carbon atoms, and alkyl groups, fluoroalkyl groups, or aryl groups are preferred, and sulfonate anionic groups are more preferred.

[0410] M + The description, specific examples, and preferred ranges regarding M in the description of compound (B) described below. + It is identical to.

[0411] Specific examples of repeating units having a light generator include, for instance, the repeating units described in

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327, the repeating units described in

[0094] of International Patent Publication No. 2018 / 193954, and the repeating units described in

[0138] of International Patent Publication No. 2022 / 024928. The above descriptions are incorporated herein by reference.

[0412] Examples of the repeating units represented by Equation (4) include the repeating units described in paragraphs

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327 and the repeating units described in paragraph

[0094] of International Patent Publication No. 2018 / 193954.

[0413] When the resin (A) comprises repeating units having a photon generator, the content of the repeating units having a photon generator is preferably 1 mol% or more with respect to the total repeating units in the resin (A), more preferably 3 mol% or more, and particularly preferably 5 mol% or more. In addition, the content of the repeating units having a photon generator is preferably 40 mol% or less with respect to the total repeating units in the resin (A), more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

[0414] It is also desirable that the resin (A) does not include repeating units having a photogenerative unit.

[0415] <Repetition unit represented by Equation (V-1) or Equation (V-2)>

[0416] The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).

[0417] It is also desirable that the repetition unit represented by the following equation (V-1) and the repetition unit represented by the following equation (V-2) are different from each of the repetition units described above.

[0418] [Chemical Formula 27]

[0419]

[0420] In formulas (V-1) and (V-2), R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. As for the alkyl group, a straight-chain, branched-chain, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. n3 represents an integer from 0 to 6. n4 represents an integer from 0 to 4. X4 is a methylene group, an oxygen atom, or a sulfur atom.

[0421] As for the repeating unit represented by formula (V-1) or formula (V-2), for example, the repeating unit described in paragraph

[0100] of International Publication No. 2018 / 193954 can be cited.

[0422] <Repetitive unit to reduce main chain motility>

[0423] The resin (A) may have a high glass transition temperature (Tg) in that it can suppress excessive diffusion of generated acid or pattern collapse during development. Tg may be greater than 90°C, greater than 100°C, greater than 110°C, or greater than 125°C. In terms of excellent dissolution rate in the developer, Tg may be 400°C or lower, or 350°C or lower.

[0424] In the present specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit included in the polymer is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to the total repeating unit in the polymer is calculated. Next, the Tg for each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152 et al.), and the values ​​are summed to obtain the Tg (°C) of the polymer.

[0425] The bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). The calculation of Tg by the bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0426] Regarding repeating units for reducing the motility of the main chain, the contents of

[0144] –

[0160] of International Publication No. 2022 / 024928 are adopted.

[0427] <Repeating unit having at least one group selected from lactone groups, sulfonate groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups>

[0428] The resin (A) may have repeating units having at least one group selected from lactone groups, sulfonate groups, carbonate groups, hydroxyl groups, cyano groups and alkali-soluble groups.

[0429] As repeating units having a lactone group, a sulfonate group, or a carbonate group in the resin (A), the repeating units described in <Repeating units having a lactone group, a sulfonate group, or a carbonate group> above may be used. The preferred content is also as described in <Repeating units having a lactone group, a sulfonate group, or a carbonate group> above.

[0430] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity.

[0431] The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having a dicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.

[0432] It is preferable that the repeating unit having a hydroxyl group or a cyano group does not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of Japanese Patent Publication No. 2014-098921.

[0433] The resin (A) may have repeating units having alkali-soluble groups.

[0434] Examples of alkali-soluble groups include, for instance, carboxyl groups, sulfonamide groups, sulfonilimide groups, bissulfonilimide groups, and aliphatic alcohol groups in which the α-position is substituted with an electron-reducing group (e.g., hexafluoroisopropanol groups), and carboxyl groups are preferred. By including repeating units having alkali-soluble groups in the resin (A), the resolution is improved, particularly for contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

[0086] of Japanese Patent Publication No. 2014-098921.

[0435] <Repeating unit having a hydrocarbon structure and not exhibiting acid decomposition>

[0436] The resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposition. This can reduce the leaching of low molecular weight components from the resist film into the immersion solution during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecaneyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0437] <Repeating unit represented by Equation (III) that has neither a hydroxyl group nor a cyano group>

[0438] Resin (A) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0439] [Chemical Formula 28]

[0440]

[0441] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl group or a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0442] Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of Japanese Patent Publication No. 2014-098921.

[0443] <Other repeating units>

[0444] Additionally, Suji (A) may have other repeating units other than the repeating unit described above.

[0445] Resin (A) may have repeating units selected from the group consisting of, for example, repeating units having oxathiane groups, repeating units having oxazolone groups, repeating units having dioxane groups, and repeating units having hydantoin groups. Examples of such repeating units include those described in

[0170] of International Publication No. 2022 / 024928.

[0446] Regarding Suji (A), additionally, the contents of

[0171] –

[0172] of International Publication No. 2022 / 024928 may be referenced.

[0447] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization).

[0448] There are no particular restrictions on the method of introducing repeating units (T) into the resin, and they may be introduced by polymerizing a monomer having an ammonium salt structure, or by acting an alkylating agent, etc. on a resin having repeating units having an amine structure. In addition, they may be introduced by a nucleus substitution reaction of a low molecular weight amine with respect to repeating units having a separating group introduced into the resin.

[0449] As a polystyrene equivalent value by the GPC method, the weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, more preferably 3,000 to 20,000, and particularly preferably 5,000 to 15,000.

[0450] The degree of dispersion of the resin (A) (also referred to as "molecular weight distribution," "Pd," or "Mw / Mn") is preferably 1 to 5, more preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, and the sidewalls of the resist pattern are smoother and the roughness is also excellent.

[0451] The content of resin (A) in the composition of the present invention is preferably 40.0 to 99.9 mass% with respect to the total solid content of the composition of the present invention, and more preferably 60.0 to 95.0 mass%.

[0452] Resin (A) may be used as a single type or as two or more types. In addition, resin (A1) and resin (A2) may be used in combination. When two or more types are used, it is preferable that their total content be within the range of the above suitable content.

[0453] [Suzy (F)]

[0454] The composition of the present invention may contain, in addition to resin (A), a resin other than resin (A).

[0455] Examples of resins other than resin (A) include a resin that does not contain repeating units (T) and also contains repeating units having acid-degradable groups (also called “resin (F”)).

[0456] The description, specific examples, and preferred range of repeating units that may be included in the resin (F) are the same as those in the resin (A) described above (except for the repeating unit (T)).

[0457] When the composition of the present invention comprises a resin (F), it is preferable that the content of the resin (F) is 1 to 90 mass% with respect to the total resin in the composition of the present invention, more preferable that it is 1 to 75 mass%, and particularly preferable that it is 1 to 50 mass%.

[0458] When the composition of the present invention includes a resin (F), it is preferable that the content of the resin (A) is 10 to 99 mass% with respect to the total resin in the composition of the present invention, more preferable that it is 25 to 99 mass%, and particularly preferable that it is 50 to 99 mass%.

[0459] [Compounds that generate acid upon irradiation with active light or radiation (B)]

[0460] The composition of the present invention may contain a compound (B) (also simply referred to as "compound (B)") that generates acid upon irradiation with active light or radiation.

[0461] Compound (B) is a compound (photo-generating agent) that generates acid upon irradiation with active light or radiation. Compound (B) is also referred to as a "photo-generating agent."

[0462] 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.

[0463] When the photogenerator is in the form of a low molecular weight compound, the molecular weight of the photogenerator is preferably 3,000 or less, more preferably 2,000 or less, and more preferably 1,000 or less. The lower limit is not particularly restricted, but 100 or more is preferred.

[0464] When the photogenerator is in a form introduced into a part of the polymer, it may be introduced into a part of at least one of resin (A) and resin (F), or it may be introduced into a resin different from resin (A) and resin (F). When resin (A) and resin (F) do not have repeating units having the photogenerator described above, the composition of the present invention preferably contains compound (B), which is a compound different from resin (A) and resin (F). When at least one of resin (A) and resin (F) has repeating units having a photogenerator, the composition of the present invention may include a separate compound (B), or it may not include it.

[0465] It is also desirable for the photogenerator to be in the form of a low-molecular-weight compound.

[0466] The photogenerative agent is preferably a compound that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation, and more preferably a compound that generates an acid with a pKa of -15 or more and less than -1.

[0467] As for photocatalytic agents, for example, "M + X - Examples include compounds (onium salts) that appear as such, and it is preferable that the compound be one that generates an organic acid upon exposure to light.

[0468] Examples of the above organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0469] "M + X- In compounds represented as ", M + It is desirable to represent a cation and an organic cation.

[0470] There are no particular restrictions on the organic cation. The valence of the organic cation may be 1 or 2 or higher.

[0471] Among these, as the above organic cation, a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0472] [Chemical Formula 29]

[0473]

[0474] In the above formula (ZaI), R 201 , R 202 , and R 203 Each represents an organic group independently.

[0475] R 201 , R 202 , and R 203 The number of carbon atoms in the organic group as is preferably 1 to 30, and more preferably 1 to 20. 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 and pentylene groups), and -CH2-CH2-O-CH2-CH2-.

[0476] Suitable embodiments of the organic cation in formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0477] First, we will explain the cation (ZaI-1).

[0478] The cation (ZaI-1) is R of the above formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group.

[0479] 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.

[0480] 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, and -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group.

[0481] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0482] As for the aryl group included in the arylsulfonium cation, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. 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.

[0483] The alkyl group or cycloalkyl group having the arylsulfonium cation 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 more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0484] R 201 ~R 203 As substituents that may be present in the aryl group, alkyl group, and cycloalkyl group, alkyl group (e.g., 1 to 15 carbon atoms), cycloalkyl group (e.g., 3 to 15 carbon atoms), aryl group (e.g., 6 to 14 carbon atoms), alkoxy group (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy group (e.g., 1 to 15 carbon atoms), halogen atom (e.g., fluorine and iodine), hydroxyl group, carboxyl group, ester group, sulfinyl group, sulfonyl group, alkylthio group, or phenylthio group is preferred.

[0485] The above substituent may have additional substituents if possible, and it is also preferable that the above alkyl group has a halogen atom as a substituent and becomes an alkyl halide group such as a trifluoromethyl group.

[0486] It is also desirable for the above substituents to form acid-degradable groups by any combination.

[0487] In addition, the acid-degradable group is intended to be a group that decomposes by the action of acid to generate a polar group, and it is desirable that the polar group is protected by a structure in which it is detached by the action of acid. The above-mentioned polar group and detacher are as described above.

[0488] Next, the cation (ZaI-2) will be explained.

[0489] The cation (ZaI-2) is R in the formula (ZaI). 201 ~R 203 These are cations that, independently, represent organic groups that do not possess an aromatic ring. An aromatic ring also includes aromatic rings containing heteroatoms.

[0490] R 201 ~R 203 The number of carbon atoms in an organic group that does not have an aromatic ring as such is preferably 1 to 30, and more preferably 1 to 20.

[0491] R 201 ~R 203 As for, 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.

[0492] R 201 ~R 203 Examples of the alkyl 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, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).

[0493] R 201 ~R 203 It may be further substituted by silver, halogen atoms, alkoxy groups (e.g., carbon 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0494] R 201 ~R 203 It is also desirable for the substituents to independently form acid-degradable groups by any combination of substituents.

[0495] Next, the cation (ZaI-3b) is described.

[0496] The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0497] [Chemical Formula 30]

[0498]

[0499] Among the formula (ZaI-3b), 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.

[0500] R 6c and R 7c Each represents, independently, a hydrogen atom, an alkyl group (e.g., a t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0501] R x and R y Each represents, independently, an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0502] R 1c ~R 7c , and, R x and R y It is also desirable for the substituents to independently form acid-degradable groups by any combination of substituents.

[0503] R 1c ~R 5c Any 2 or more of, R 5c and R 6c , R6c and R 7c , R 5c and R x , and R x and R y Each of these may combine with one another to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

[0504] 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. Examples of rings include 3 to 10-membered rings, 4 to 8-membered rings are preferred, and 5 or 6-membered rings are more preferred.

[0505] 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 heteroatoms such as oxygen atoms.

[0506] R 5c and R 6c , and R 5c and R x As for the group formed by bonding, a single bond or an alkylene group is preferred. Examples of alkylene groups include methylene groups and ethylene groups.

[0507] R 1c ~R 5c , R 6c , R 7c , R x , R y , and, 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 The rings formed by each of them combining with one another may have substituents.

[0508] Next, the cation (ZaI-4b) is described.

[0509] The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0510] [Chemical Formula 31]

[0511]

[0512] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8.

[0513] R 13 It represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (it may be the cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents.

[0514] R 14 R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), an alkyl group, an alkyl halide group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (it may be the cycloalkyl group itself or a group containing 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.

[0515] R 15 Each represents, independently, an alkyl group, a cycloalkyl group, or a naphthyl group. Two Rs 15 They may combine to form a ring. Two R 15When atoms combine to form a ring, heteroatoms such as oxygen atoms or nitrogen atoms may be included within the ring framework.

[0516] In one embodiment, two R 15 It is preferable that the groups are alkylene groups and bond with each other to form a ring structure. In addition, the alkyl group, the cycloalkyl group, and the naphthyl group, and two R groups 15 Rings formed by combining with each other may have substituents.

[0517] In formula (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

[0518] R 13 ~R 15 , and, R x and R y It is also desirable for each substituent to independently form an acid-degradable group by any combination of substituents.

[0519] Next, we will explain Equation (ZaII).

[0520] In formula (ZaII), R 204 and R 205 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0521] R 204 and R 205 As the aryl group, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. 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, etc. Examples of the backbone of an aryl group having a heterocyclic group include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0522] R 204 and R 205 As for the alkyl group and cycloalkyl group, 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) is preferred.

[0523] 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 the aryl group, alkyl group, and cycloalkyl group may have include, for example, an alkyl group (e.g., C1 to C15), a cycloalkyl group (e.g., C3 to C15), an aryl group (e.g., C6 to C15), an alkoxy group (e.g., C1 to C15), a halogen atom, a hydroxyl group, and a phenylthione group. Also, R 204 and R 205 It is also desirable for the substituents to independently form acid-degradable groups by any combination of substituents.

[0524] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0525] [Chemical Formula 32]

[0526]

[0527] [Chemical Formula 33]

[0528]

[0529] "M + X - In compounds represented as ", X - represents an organic anion.

[0530] Organic anions are not particularly limited and may include organic anions of 1 or 2 or higher valence.

[0531] As for the organic anion, an anion with a significantly low ability to cause a nucleation reaction is preferred, and a non-nucleational anion is more preferred.

[0532] Examples of non-nucleated anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0533] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a straight-chain or branched-chain alkyl group or a cycloalkyl group, and a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms is preferred.

[0534] The above alkyl group may be, for example, a fluoroalkyl group (it may have a substituent other than a fluorine atom. It may also be a perfluoroalkyl group).

[0535] As for the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a tolyl group, and a naphthyl group.

[0536] The alkyl groups, cycloalkyl groups, and aryl groups mentioned above may have substituents. Substituents are not particularly limited, but examples include halogen atoms such as nitro groups, fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably 1 to 15 carbon atoms), alkyl groups (preferably 1 to 10 carbon atoms), cycloalkyl groups (preferably 3 to 15 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably 2 to 7 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably 2 to 7 carbon atoms), alkylthio groups (preferably 1 to 15 carbon atoms), alkylsulfonyl groups (preferably 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably 6 to 20 carbon atoms).

[0537] As for the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferred.

[0538] Examples of aryl-kil groups having 7 to 14 carbon atoms include benzyl groups, phenethyl groups, naphthylmethyl groups, naphthylethyl groups, and naphthylbutyl groups.

[0539] Examples of sulfonylimide anions include saccharin anions.

[0540] As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferred. As substituents of these alkyl groups, examples 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.

[0541] In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond with each other to form a ring structure. This increases the acid strength.

[0542] 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.

[0543] As non-nucleated anions, 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, a bis(alkylsulfonyl)imide anion in which an alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferred. 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.

[0544] As a non-nucleated anion, an anion represented by the following formula (AN1) is also preferred.

[0545] [Chemical Formula 34]

[0546]

[0547] In equation (AN1), R 1 and R 2 Each represents, independently, a hydrogen atom or a substituent.

[0548] Substituents are not particularly limited, but non-electron-reducing groups are preferred. Examples of non-electron-reducing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.

[0549] As for groups that are not electron-producing groups, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR' are preferred independently. R' is a monovalent hydrocarbon group.

[0550] As the monovalent hydrocarbon group represented by the above R', for example, alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propeneyl, and buteneyl groups; monovalent straight-chain or branched-chain hydrocarbon groups such as alkyneyl groups such as ethyneyl, propaneyl, and butyneyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norborneyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropeneyl, cyclobuteneyl, cyclopenteneyl, and norbornenyyl groups; aryl groups such as phenyl, tolyl, xylyl, mesethyl, naphthyl, methylnaphthyl, anthryl, and methylanthyl groups; Examples of monovalent aromatic hydrocarbon groups include benzyl groups, phenethyl groups, phenylpropyl groups, naphthylmethyl groups, and anthrylmethyl groups, as well as aralkyl groups.

[0551] Among them, R 1 and R 2 Each of the following is independently preferred: a hydrocarbon group (a cycloalkyl group is preferred) or a hydrogen atom.

[0552] L represents a divalent connector.

[0553] If there are multiple Ls, each L may be identical or different.

[0554] Examples of divalent linkers include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. Among these, as divalent linkers, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene groups, -COO-alkylene groups, or -CONH-alkylene groups are preferred, and -O-CO-O-, -O-CO-O-alkylene groups, -COO-, -CONH-, -SO2-, or -COO-alkylene groups are more preferred.

[0555] As for L, for example, a group represented by the following formula (AN1-1) is preferred.

[0556] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0557] Among the formulas (AN1-1), * a is R in equation (AN1) 3 Indicates the connection location with.

[0558] * b is -C(R in Equation (AN1) 1 )(R 2 Indicates the connection position with )-.

[0559] X and Y each independently represent integers from 0 to 10, and integers from 0 to 3 are preferred.

[0560] R 2a and R 2b Each represents, independently, a hydrogen atom or a substituent.

[0561] R 2a and R 2bIn cases where each exists in multiple instances, R exists in multiple instances 2a and R 2b Each can be the same or different.

[0562] However, if Y is 1 or greater, -C(R in Equation (AN1) 1 )(R 2 CR that directly combines with )- 2b R in 2 2b is, other than a fluorine atom.

[0563] Q is, * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents.

[0564] Provided that X+Y in Equation (AN1-1) is 1 or greater, and also, R in Equation (AN1-1) 2a and R 2b If everyone is entirely hydrogen atoms, Q is, * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents.

[0565] * A is R in equation (AN1) 3 Indicates the joint position on the side, and * B is -SO3 in formula (AN1). -Indicates the joint position on the side.

[0566] In equation (AN1), R 3 Silver represents an organic group.

[0567] The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a straight-chain group (e.g., a straight-chain alkyl group), a branched-chain group (e.g., a branched-chain alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have a substituent. The above organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0568] Among them, R 3 It is preferable that the ring be an organic group having a cyclic structure. The cyclic structure may be a single ring or a polycyclic ring, and may have substituents. In the organic group containing the cyclic structure, it is preferable that the ring be directly bonded to L in formula (AN1).

[0569] The organic group having the above-mentioned cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). The heteroatoms may substitute for one or more carbon atoms forming the cyclic structure.

[0570] The organic group having the above-mentioned cyclic structure is preferably, for example, a hydrocarbon group with a cyclic structure, a lactone group, and a sulfone group. Among these, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group with a cyclic structure.

[0571] The hydrocarbon group of the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents.

[0572] The above cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.), and the number of carbon atoms is preferably 5 to 12.

[0573] As for the above-mentioned lactone group and sulfon group, for example, in any one of the structures represented by the above-described formulas (LC1-1) to (LC1-21) and the structures represented by formulas (SL1-1) to (SL1-3), it is preferable to have a group formed by removing one hydrogen atom from the reducing atom constituting the lactone structure or the sulfon structure.

[0574] As for the non-nucleated anion, it may be a benzenesulfonate anion, and it is preferable to be a benzenesulfonate anion substituted by a branched chain alkyl group or a cycloalkyl group.

[0575] As a non-nucleated anion, an anion represented by the following formula (AN2) is also preferred.

[0576] [Chemical Formula 35]

[0577]

[0578] In equation (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0579] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group not having a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.

[0580] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and more preferably both Xf are fluorine atoms.

[0581] R 4 and R 5represents, respectively, a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. R 4 and R 5 If there are multiple instances of , R 4 and R 5 Each can be the same or different.

[0582] R 4 and R 5 The alkyl group represented by is preferably 1 to 4 carbon atoms. The alkyl group may have a substituent. R 4 and R 5 As for that, a hydrogen atom is preferred.

[0583] L represents a 2-valent linker. The definition of L is the same as L in Equation (AN1).

[0584] W represents an organic group containing a cyclic structure. Among these, it is preferable that it be a cyclic organic group.

[0585] Examples of phantom organic groups include pyrocyclic groups, aryl groups, and complex pyrocyclic groups.

[0586] The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl groups, tricyclodecaneyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups. 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.

[0587] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and anthryl group.

[0588] The complex group may be monocyclic or polycyclic. Among these, if the complex group is polycyclic, it can suppress acid diffusion more effectively. The complex group may or may not be aromatic. Examples of complex groups that are aromatic include the furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of complex groups that are not aromatic include the tetrahydropyran ring, lactone ring, sulfone ring, and decahydroisoquinoline ring. As for the complex group, the furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring is preferred.

[0589] The above-mentioned cyclic organic group may have a substituent. Examples of the substituents include an alkyl group (which may be either straight-chain or branched-chain, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 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.

[0590] As for the anion represented by equation (AN2), SO3 - -CF2-CH2-OCO-(L) q' -W, SO3 - -CF2-CHF-CH2-OCO-(L) q' -W, SO3 - -CF2-COO-(L) q' -W, SO3 - -CF2-CF2-CH2-CH2-(L) q' -W, or, SO3 - -CF2-CH(CF3)-OCO-(L) q'-W is preferred. Here, L, q, and W are the same as in Equation (AN2). q' represents an integer from 0 to 10.

[0591] As a non-nucleated anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0592] [Chemical Formula 36]

[0593]

[0594] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may have additional substituents other than a sulfonate anion and a -(DB) group. Examples of additional substituents that may be included are a fluorine atom and a hydroxyl group.

[0595] n represents an integer greater than or equal to 0. As for n, 1 to 4 is preferred, 2 to 3 is more preferred, and 3 is more preferred.

[0596] D represents a single bond or a divalent linker. Examples of divalent linkers include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfonate group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these.

[0597] B represents a hydrocarbon group.

[0598] As for B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group that may have additional substituents (such as a tricyclohexylphenyl group) is more preferred.

[0599] As a non-nucleated anion, a disulfonamide anion is also desirable.

[0600] The disulfonamide anion is, for example, N - (SO2-R q It is an anion that appears as )2.

[0601] Here, R qrepresents an alkyl group that may have substituents, a fluoroalkyl group is preferred, and a perfluoroalkyl group is more preferred. Two Rs q They may combine to form a ring. Two R q The group formed by mutual bonding is preferably an alkylene group that may have substituents, more preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The number of carbon atoms in the alkylene group is preferably 2 to 4.

[0602] Organic anions may be used as a single type or as two or more types. Specific examples of organic anions are shown below, but are not limited to these.

[0603] [Chemical Formula 37]

[0604]

[0605] It is preferable that the compound (B) has a group that decomposes by the action of an acid, and it is more preferable that it be represented by the following formula (U-1).

[0606] [Chemical Formula 38]

[0607]

[0608] In formula (U-1), L U1 represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 may be the same or different. g represents an integer from 1 to 5. X U1 represents the g+1 linker. M U1 + It represents sulfonium ions or iodine ions.

[0609] In formula (U-1), L U1It represents a single bond or a divalent linker.

[0610] L U1 Examples of the divalent linkers represented by this include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linkers formed by the connection of multiple such groups. U1 As such, an alkylene group, an arylene group, an alkylene group having a fluorine or iodine atom, a -COO-Rt- group, or an -O-Rt- group is preferred. Rt represents an alkylene group or a cycloalkylene group.

[0611] As for the arylene group, a phenylene group is preferred.

[0612] 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 1 to 10 is preferred, and 1 to 3 is more preferred.

[0613] The total number of fluorine atoms and iodine atoms included in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but 2 or more is preferred, 2 to 10 is more preferred, and 3 to 6 is more preferred.

[0614] As for Rt, an alkylene group having 1 to 5 carbon atoms is preferred, and a -CH2- group, -(CH2)2- group, or -(CH2)3- group is more preferred.

[0615] L U1 It is particularly preferable that the group be an arylene group, an alkylene group, or a single bond, and most preferable that the group be a phenylene group or a single bond.

[0616] Among equation (U-1), A U1 It represents the energy that is decomposed by the action of acid.

[0617] It is desirable that the group decomposed by the action of acid has a structure in which the polar group is protected by the group detached by the action of acid (detacher).

[0618] As for the polar group, the polar group described in the repeating unit having the acid-degradable group of the resin (A) described above may be used, among which a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group is preferred, and a carboxyl group or a phenolic hydroxyl group is more preferred.

[0619] As for groups that are removed by the action of acid, for example, groups represented by formulas (Y1) to (Y4) described in the explanation of resin (A) above can be cited.

[0620] In Equation (U-1), g represents an integer from 1 to 5, and it is preferable to represent an integer from 1 to 3.

[0621] In equation (U-1), X U1 represents the g+1 linker.

[0622] X U1 It is preferable that the group be an aromatic group, more preferable that it be an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferable that it be a benzene ring group.

[0623] X U1 It may have substituents.

[0624] In equation (U-1), M U1 + represents a sulfonium ion or an iodine ion. Examples of sulfonium ions and iodine ions include the cation represented by the formula (ZaI) and the cation represented by the formula (ZaII) described above, and the cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), or cation (ZaI-4b) described above are preferred.

[0625] It is more preferable that compound (B) be a compound represented by the following formula (U-2).

[0626] [Chemical Formula 39]

[0627]

[0628] In equation (U-2), L U1represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 It may be the same or different. R U1 represents a substituent. R U1 If this plural exists, the plural R U1 It may be the same or different. R U1 If this plural exists, the plural R U1 They may combine to form a ring. g1 represents an integer from 1 to 5. g2 represents an integer from 0 to 4. M U1 + It represents sulfonium ions or iodine ions.

[0629] L in equation (U-2) U1 , A U1 and M U1 + The description, specific examples, and preferred ranges are each L in the formula (U-1) described above. U1 , A U1 and M U1 + It is the same as that in.

[0630] In equation (U-2), g1 represents an integer from 1 to 5, and it is preferable to represent an integer from 1 to 3.

[0631] g2 in equation (U-2) represents an integer from 0 to 4, preferably an integer from 0 to 2, and particularly preferably 0.

[0632] R in equation (U-2) U1 It is preferable to represent a substituent other than a group that decomposes by the action of acid, and it is more preferable to represent an alkyl group, a cycloalkyl group, or an aryl group.

[0633] The above alkyl group may be in a straight chain or a branched chain, and an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 15 carbon atoms is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. The alkyl group may have a substituent.

[0634] The number of carbon atoms in the above cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. As for the cycloalkyl group, it may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group. For example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0635] The above aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group may have a substituent.

[0636] Below, the anion part (M) in formula (U-1) U1 + Specific examples of other parts are shown, but are not limited to these.

[0637] [Chemical Formula 40]

[0638]

[0639] It is also preferable that the photogenerator be at least one selected from the group consisting of compounds (I) to (II).

[0640] (Compound (I))

[0641] Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, and is a compound that generates an acid including a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation.

[0642] Structural site X: Anion site A1 - and cation site M1 + A structural region composed of, and also forming a first acidic region appearing as HA1 upon irradiation with active light or radiation.

[0643] Structural site Y: Anion site A2 - and cation site M2 + A structural region composed of, and also forming a second acidic region appearing as HA2 upon irradiation with active light or radiation.

[0644] The above compound (I) satisfies the following condition I.

[0645] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation site M2 in the above structural site Y + ul H + A compound PI formed by substitution, wherein the cation site M1 in the structural site X + ul H + The acid dissociation constant a1 derived from the acidic region represented by HA1 formed by substitution, and the cation region M2 in the structural region Y. + ul H +It has an acid dissociation constant a2 derived from the acidic region represented by HA2 formed by substitution, and also, the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0646] Condition I is explained in more detail below.

[0647] If compound (I) is an acid-generating compound having, for example, one first acidic site derived from the structural site X and one second acidic site derived from the structural site Y, then compound PI corresponds to a “compound having HA1 and HA2”.

[0648] To explain more specifically, the acid dissociation constants a1 and a2 of compound PI refer to, in the case where the acid dissociation constants of compound PI are calculated, that compound PI is "A1 - The pKa when it becomes a "compound having HA2" is the acid dissociation constant a1, and the above "A1 - "Compound having HA2" is "A1 - Department A2 - The pKa when it becomes a compound having “ is the acid dissociation constant a2.

[0649] If compound (I) is an acid-generating compound having, for example, two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y, then compound PI corresponds to "a compound having two HA1 and one HA2".

[0650] When the acid dissociation constant of compound PI is calculated, compound PI is "1 A1 - and the acid dissociation constant when it becomes a compound having 1 HA1 and 1 HA2, and "1 A1 - and a compound having one HA1 and one HA2 is "2 A1 - The acid dissociation constant when it becomes a "compound having 1 HA2" corresponds to the aforementioned acid dissociation constant a1. "2 A1- and a compound having 1 HA2 is "2 A1 - Department A2 - The acid dissociation constant when it becomes a "compound having" corresponds to the acid dissociation constant a2. That is, in the case of compound PI, the cation site M1 in the structural site X + ul H + In the case where there are multiple acid dissociation constants derived from the acidic site represented by HA1 formed by substitution, the value of the acid dissociation constant a2 is greater than the largest value among the multiple acid dissociation constants a1. In addition, compound PI is "1 A1 - Let aa be the acid dissociation constant when it becomes a compound having 1 HA1 and 1 HA2, and "1 A1 - and a compound having one HA1 and one HA2 is "2 A1 - When the acid dissociation constant is denoted as ab when it becomes a "compound having one HA2 group," the relationship between aa and ab is aa <ab를 충족시킨다.

[0651] The acid dissociation constants a1 and a2 are obtained by the acid dissociation constant measurement method described above.

[0652] The above compound PI corresponds to an acid that is generated when compound (I) is irradiated with active light or radiation.

[0653] If compound (I) has two or more structural sites X, the structural sites X may each be the same or different. Also, two or more of the above A1 - , and two or more of the above M1 + Each may be the same or different.

[0654] Among compound (I), the above A1 - and the above A2 - , and, the above M1 + and the above M2 + They may be the same or different, respectively, but the above A1 - and the above A2- It is desirable that each be different.

[0655] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if multiple acid dissociation constants a1 exist) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and more preferably 1.0 or more. In addition, the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value if multiple acid dissociation constants a1 exist) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0656] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. In addition, as a lower limit value of the acid dissociation constant a2, -4.0 or more is preferred.

[0657] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. In addition, as a lower limit value of the acid dissociation constant a1, -20.0 or more is preferred.

[0658] Negative ion area A1 - and anion site A2 - The structure is a structural region containing a negatively charged atom or group of atoms, and for example, a structural region selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below.

[0659] Negative ion area A1 - As such, it is desirable to be able to form an acidic region with a small acid dissociation constant, and among them, any one of formulas (AA-1) to (AA-3) is more desirable, and any one of formulas (AA-1) and (AA-3) is more desirable.

[0660] Also, negative ion site A2 - As for, anion site A1 -It is desirable to be able to form an acidic region with a larger acid dissociation constant, and it is more desirable to be any one of formulas (BB-1) to (BB-6), and it is more desirable to be any one of formulas (BB-1) and (BB-4).

[0661] In addition, among the following equations (AA-1) to (AA-3) and equations (BB-1) to (BB-6), * indicates a bonding position.

[0662] In formula (AA-2), R A represents a monovalent organic group. R A The monovalent organic groups that appear are not particularly limited, but examples include cyano groups, trifluoromethyl groups, and methanesulfonyl groups.

[0663] [Chemical Formula 41]

[0664]

[0665] [Chemical Formula 42]

[0666]

[0667] Cation site M1 + and cation site M2 + is a structural region containing a positively charged atom or atomic group, and, for example, can be an organic cation with a charge of 1. In addition, as an organic cation, for example, the M described above + Examples of organic cations that appear as such include.

[0668] (Compound (II))

[0669] Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, and is a compound that generates an acid comprising two or more of the above-mentioned first acidic sites originating from the above-mentioned structural site X and the above-mentioned structural site Z upon irradiation with active light or radiation.

[0670] Structural region Z: Non-ionic region capable of neutralizing acid

[0671] Definition of structural site X among compound (II), and, A1 - and M1 + The definition of is the definition of structural site X in the compound (I) described above, and, A1 - and M1 + It has the same meaning as the definition of, and the mode of suitability is also the same.

[0672] In the above compound (II), the cation site M1 in the structural site X + ul H + In compound PII formed by substitution, the cation site M1 in the structural site X + ul H + The suitable range of the acid dissociation constant a1 derived from the acidic portion represented by HA1 formed by substitution is the same as the acid dissociation constant a1 in the compound PI.

[0673] In addition, if compound (II) is, for example, an acid-generating compound having two first acidic sites originating from the structural site X and the structural site Z, then compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, compound PII is "one A1 - and the acid dissociation constant when it becomes a compound having 1 HA1, and "1 A1 - and a compound having 1 HA1 is "2 A1 - The acid dissociation constant when it becomes a compound having “ is the acid dissociation constant a1.

[0674] The acid dissociation constant a1 is obtained by the above-described method for measuring acid dissociation constants.

[0675] The above compound PII corresponds to the acid that is generated when compound (II) is irradiated with active light or radiation.

[0676] In addition, the two or more structural parts X mentioned above may each be identical or different. Two or more of the above A1 - , and two or more of the above M1 + Each may be the same or different.

[0677] The nonionic site capable of neutralizing acid in structural site Z is not particularly limited, and, for example, it is preferable to be a site containing a group capable of electrostatically interacting with a proton, or a functional group having an electron.

[0678] As functional groups capable of electrostatically interacting with protons, or having electrons, examples include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having nitrogen atoms having non-covalent electron pairs that do not contribute to π-conjugation. A nitrogen atom having non-covalent electron pairs that do not contribute to π-conjugation is, for example, a nitrogen atom having a substructure shown in the following formula.

[0679] [Chemical Formula 43]

[0680] non-shared electron pairs

[0681] Examples of partial structures of functional groups having a group or electron capable of electrostatically interacting with protons include crown ether structures, aza crown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0682] Examples of non-cation sites that compounds (I) and (II) may have are provided.

[0683] [Chemical Formula 44]

[0684]

[0685] [Chemical Formula 45]

[0686]

[0687] ​The content of the photocatalytic agent is not particularly limited, but with respect to the total solid content of the composition of the present invention, it is preferably 0.5 mass% or more, and more preferably 1.0 mass% or more. The content of the photocatalytic agent is preferably 70.0 mass% or less with respect to the total solid content of the composition of the present invention, more preferably 50.0 mass% or less, and more preferably 40.0 mass% or less.

[0688] The photocatalytic agent may be used as a single type or as two or more types. If two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0689] [Acid Diffusion Control Agent]

[0690] The composition of the present invention may further include an acid diffusion control agent.

[0691] The acid diffusion control agent acts as a quencher that traps acid generated from photogenerative agents, etc., during exposure, thereby suppressing the reaction of acid-degradable resins in unexposed areas caused by excess generated acid.

[0692] The types of acid diffusion control agents are not particularly limited, and examples include basic compounds (DA), low-molecular-weight compounds having a nitrogen atom and a group that is detached by the action of acid (DB), and compounds whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation (DC).

[0693] Examples of compounds (DC) include onium salt compounds of acids that are relatively weak acids with respect to acids generated from photogenerative agents (DD), and basic compounds (DE) whose basicity is reduced or lost upon irradiation with active light or radiation.

[0694] Specific examples of basic compounds (DA) include, for instance, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824 and those described in paragraph

[0164] of International Publication No. 2020 / 066824; and specific examples of low molecular weight compounds (DB) having a nitrogen atom and a group that is removed by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824.

[0695] Specific examples of onium salt compounds (DD) that are relatively weak acids with respect to photogenerative agents include, for instance, those described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337.

[0696] In addition to the above, known compounds disclosed in, for example, paragraphs

[0627] –

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

[0095] –

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

[0403] –

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

[0259] –

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 may be suitably used as acid diffusion control agents.

[0697] When an acid diffusion control agent is included in the composition of the present invention, the content of the acid diffusion control agent is preferably 0.1 to 15.0 mass% with respect to the total solid content of the composition of the present invention, and more preferably 0.5 to 15.0 mass%.

[0698] Acid diffusion control agents may be used as a single type or as two or more types. When two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0699] [Hydrophobic Resin]

[0700] The composition of the present invention may further include a hydrophobic resin different from resin (A) and resin (F).

[0701] 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.

[0702] 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.

[0703] In terms of localization to the film surface layer, it is preferable for the hydrophobic resin to have one or more of the following: 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. It is preferable for the hydrophobic resin to have hydrocarbon groups with five or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain.

[0704] Examples of hydrophobic resins include compounds described in paragraphs

[0275] to

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

[0705] When the composition of the present invention includes a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% with respect to the total solid content of the composition of the present invention, and more preferably 0.1 to 15.0 mass%.

[0706] The hydrophobic resin may be used as a single type or as two or more types. When two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0707] [Surfactant]

[0708] 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.

[0709] Fluorine-based and / or silicone-based surfactants are preferred.

[0710] Examples of fluorine-based and / or silicone-based surfactants include the surfactants disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0711] When the composition of the present invention includes a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass% with respect to the total solid content of the composition of the present invention, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%.

[0712] One type of surfactant may be used, or two or more types may be used. If two or more types are used, it is preferable that the total content be within the range of the above suitable content.

[0713] 〔solvent〕

[0714] The composition of the present invention preferably includes a solvent.

[0715] Preferably, the solvent 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).

[0716] Combining the aforementioned solvent with the aforementioned resin is desirable from the perspective of improving the coating properties of the composition of the present invention and reducing the number of defects in the pattern development. Since the aforementioned solvent provides a good balance of the solubility, boiling point, and viscosity of the aforementioned resin, it can suppress non-uniformity in the film thickness of the resist film and the occurrence of precipitates during spin coating.

[0717] Details of component (M1) and component (M2) are described in paragraphs

[0218] –

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein by reference.

[0718] If the solvent further contains components other than components (M1) and (M2), 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.

[0719] 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.

[0720] [Other additives]

[0721] 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 carboxyl group).

[0722] The above "dissolution-inhibiting compound" is a compound with a molecular weight of 3,000 or less that decomposes due to the action of acid and its solubility in an organic developer decreases.

[0723] [Desensitizing photoreactive or radiation-sensitive film, pattern formation method]

[0724] The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive or radiation-sensitive film of the present invention is preferably a resist film.

[0725] The steps of the pattern formation method using the composition of the present invention are not particularly limited, but it is preferable to have the following process.

[0726] Process 1: A process of forming a resist film on a substrate using the composition of the present invention.

[0727] Process 2: Process of exposing the resist film

[0728] Process 3: Process of developing the exposed resist film using a developer solution

[0729] Below, the sequence of each of the above processes will be explained in detail.

[0730] (Process 1: Resist film formation process)

[0731] Process 1 is a process of forming a resist film on a substrate using the composition of the present invention.

[0732] As a method for forming a resist film on a substrate using the composition of the present invention, for example, a method of applying the composition of the present invention onto a substrate may be used.

[0733] In addition, it is preferable to filter the composition of the present invention 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 more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0734] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide) used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or a coater. Spin application using a spinner is preferred as the application method. When performing spin application using a spinner, the rotation speed is preferably 1,000 to 3,000 rpm (rotations per minute).

[0735] After applying the composition of the present invention, the substrate may be dried to form a resist film. Additionally, if necessary, various underlayers (inorganic film, organic film, anti-reflective film) may be formed on the lower layer of the resist film.

[0736] 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.

[0737] The film thickness of the resist film is not particularly limited, but 10 to 120 nm is preferred in that it allows for the formation of fine patterns with higher precision. Among these, when using EUV exposure, the film thickness of the resist film is more preferably 10 to 65 nm, and 15 to 50 nm is more preferred. When using ArF immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, and 15 to 90 nm is more preferred.

[0738] In addition, a top coat may be formed on the upper layer of the resist film using a top coat composition.

[0739] It is preferable that the top coat composition be applied uniformly to the upper layer of the resist film without mixing with the resist film. The top coat is not particularly limited and can be formed by conventionally known top coats by 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.

[0740] For example, it is preferable to form a top coat containing a basic compound as described in Japanese Patent Publication No. 2013-61648 on the resist film. Specific examples of basic compounds that the top coat may contain include basic compounds that may be included in the composition of the present invention.

[0741] It is also preferable that the top coat 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.

[0742] (Process 2: Photolithography Process)

[0743] Process 2 is a process of exposing the resist film.

[0744] As a method of exposure, an active light or radiation can be irradiated onto the formed resist film through a predetermined mask.

[0745] Examples of active light or radiation include infrared rays, visible light, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams, and a wavelength of 250 nm or less is preferred, more preferably 220 nm or less, and far ultraviolet rays with a wavelength of 1 to 200 nm are particularly preferred, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0746] 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.

[0747] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0748] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0749] Heating can be performed using means provided in a conventional exposure machine and / or developer, or by using a hot plate, etc.

[0750] This process is also called post-exposure baking.

[0751] (Process 3: Development Process)

[0752] Process 3 is a process of developing the exposed resist film using a developer and forming a pattern.

[0753] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0754] 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).

[0755] 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.

[0756] 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.

[0757] The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0758] 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 preferably 0.1 to 20 mass%. The pH of the alkaline developer is typically preferably 10.0 to 15.0.

[0759] 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.

[0760] 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.

[0761] 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.

[0762] (Other processes)

[0763] The above pattern forming method preferably includes a process of cleaning using a rinse solution after process 3.

[0764] As a rinsing solution used in the rinsing process after the development process using an alkaline developer, pure water can be used, for example. In addition, an appropriate amount of surfactant may be added to the pure water.

[0765] An appropriate amount of surfactant may be added to the rinse solution.

[0766] The rinsing solution used in the rinsing process after the development process using an organic developer is not particularly limited as long as the pattern is not dissolved, 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.

[0767] 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).

[0768] In addition, the pattern forming method 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).

[0769] 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.

[0770] 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. Oxygen plasma etching is preferred for the dry etching.

[0771] Various materials used in the composition and pattern forming method of the present invention (e.g., solvent, developer, rinsing solution, composition for forming an anti-reflective film, composition for forming a top coat, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit is not specifically restricted, but 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0772] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited, for example. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0773] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials constituting various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible by lining the inside of the device with Teflon (registered trademark).

[0774] 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 or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. There is no particular lower limit, but 0 mass ppt or more is preferred.

[0775] 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 accumulation 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 to maintain desirable developing or rinsing characteristics, it is preferable to have 10 mass% or less, and more preferable to have 5 mass% or less. The lower limit is not particularly limited, but 0.01 mass% or more is preferred.

[0776] 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.

[0777] [Method for manufacturing an electronic device]

[0778] The present specification 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.

[0779] Suitable embodiments of the electronic device of this specification include embodiments mounted in electrical and electronic devices (home appliances, OA (Office Automation), media-related devices, optical devices and communication devices, etc.).

[0780] Examples

[0781] 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.

[0782] The various components used in the resist compositions of the examples and comparative examples are described below.

[0783] Suzy

[0784] As resin (A), A-1 to A-17 were used. Also, as resins other than resin (A), AX-1 to AX-6 were used.

[0785] The structures of A-1 to A-17 and AX-1 to AX-6 are shown below. The content ratio of the following repeating units (content relative to the total repeating units in the resin) is a molar ratio.

[0786] The weight-average molecular weight (Mw) and degree of dispersion (Pd=Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). In addition, the content of repeating units is, 13 It was measured by C-NMR (nuclear magnetic resonance).

[0787] [Chemical Formula 46]

[0788]

[0789] [Chemical Formula 47]

[0790]

[0791] [Chemical Formula 48]

[0792]

[0793] [Chemical Formula 49]

[0794]

[0795] [Chemical Formula 50]

[0796]

[0797] [Chemical Formula 51]

[0798]

[0799] (Synthesis of A-1)

[0800] An example of the synthesis of A-1 is shown below. Other resins (A) were also synthesized in the same way.

[0801] [Chemical Formula 52]

[0802]

[0803] Cyclohexanone (43.1 g) was heated to 85°C under a nitrogen stream. While stirring, a mixed solution of M-1 (18.0 g), M-2 (29.8 g), cyclohexanone (100.5 g), and 2,2'-azobisisobutyrate dimethyl [V-601, manufactured by Fujifilm Wako Junyaku Co., Ltd.] (2.9 g) was added dropwise to the liquid for 3 hours to obtain a reaction solution. After the dropwise addition was finished, the reaction solution was stirred at 85°C for an additional 3 hours. After cooling the obtained reaction solution, it was reprecipitated with 3600 g of ethyl acetate / heptane (mass ratio 1:9), filtered, and the obtained solid was vacuum dried to obtain resin A-1a (40.2 g).

[0804] After dissolving the above A-1a (40.2g) in ethyl acetate (200g), triethylamine (4.8g) was added and cooled to 0°C, and benzyl chloroformate (5.37g) was added dropwise over 15 minutes. Then, the temperature was raised and heated at 40°C for 6 hours. After cooling the resulting reaction solution, it was washed with water (200g), and the organic layer was reprecipitated with 3000g of ethyl acetate / heptane (mass ratio 1:9). By vacuum drying the obtained solid, resin A-1 (36.6g) was obtained.

[0805] <Compound (B)>

[0806] B-1 to B-6 were used as compounds (B) (photogeneratives). The structures of B-1 to B-6 are shown below.

[0807] [Chemical Formula 53]

[0808]

[0809] Acid Diffusion Control Agent

[0810] D-1 to D-4 were used as acid diffusion control agents. The structures of D-1 to D-4 are shown below.

[0811] [Chemical Formula 54]

[0812]

[0813] Hydrophobic resin

[0814] P-1 was used as the hydrophobic resin. The structure of P-1 is shown below. The content ratio of the repeating units (content relative to the total repeating units in the resin) is a molar ratio. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). Furthermore, the content of the repeating units is, 13 It was measured by C-NMR.

[0815] [Chemical Formula 55]

[0816]

[0817] Surfactants

[0818] The surfactants used are shown below.

[0819] W-1: Megapak F176 (DIC Co., Ltd. Manufactured; Fluorine-based)

[0820] W-2: MegaPac R08 (Manufactured by DIC Co., Ltd.; Fluorine and Silicon-based)

[0821] W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Kagaku High School Co., Ltd.; silicone-based)

[0822] W-4: Troizol S-366 (Manufactured by Troy Chemical Co., Ltd.)

[0823] W-5: KH-20 (Manufactured by AGC Co., Ltd.)

[0824] W-6: PolyFox PF-6320 (Manufactured by OMNOVA Solutions Inc.; Fluorine-based)

[0825] Solvent

[0826] The solvents used are shown below.

[0827] SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0828] SL-2: Propylene glycol monomethyl etherpropionate

[0829] SL-3: 2-heptanone

[0830] SL-4: Ethyl lactate

[0831] SL-5: Propylene glycol monomethyl ether (PGME)

[0832] SL-6: Cyclohexanone

[0833] SL-7: γ-beautyllactone

[0834] SL-8: Propylene carbonate

[0835] <Preparation of Resist Composition>

[0836] The components shown in Table 1 were used in the mass (g) shown in Table 1 and dissolved in the solvent shown in Table 1 to prepare a solution with a solid content concentration of 2.5 mass%, and this was filtered through a polyethylene filter having a pore size of 0.02 μm to obtain resist compositions Re-1 to Re-20 and Re-x1 to Re-x5. Regarding the solvent, the types of compounds used and their mass ratios are listed in Table 1.

[0837] In Table 1, when two or more types of each component were used, the type and amount of each were separated by " / ".

[0838] [Table 1]

[0839]

[0840] [Examples 1-1 to 1-20, and Comparative Examples 1-1 to 1-5]

[0841] <Diagram of the Resist Composition>

[0842] The prepared resist composition was applied using a Tokyo Electron spin coater Mark 8 on a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilasein (HMDS), and dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm.

[0843] Furthermore, the same result is obtained even if the above Si wafer is changed to a chromium substrate.

[0844] <Pattern Formation Method (1): EB Exposure, Alkaline Development (Positive)>

[0845] The wafer coated with the resist film obtained above was patterned using an electron beam lithography device (Advantest Inc.; F7000S, acceleration voltage 50 keV). At this time, lithography was performed to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then dried by rinsing with water for 30 seconds. After that, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds, and then dried by baking at 95°C for 60 seconds.

[0846] <Evaluation Latitude (EL)>

[0847] The optimal exposure amount when resolving a line-and-space pattern with a line width of 50 nm (1:1) using a side-field scanning electron microscope (Hitachi Seisakusho S-9380II) is the sensitivity (Eopt) (μC / cm² 2 I did it as ).

[0848] Based on the obtained sensitivity (Eopt), the exposure amount was calculated when the target value of 50 nm was ±10% (i.e., 55 nm and 45 nm). Then, the exposure latitude (EL, unit: %) defined by the following equation was calculated. The larger the value of EL, the smaller the change in performance due to changes in exposure amount, and the better the result.

[0849] EL(%)=[〔(Exposure amount at which the line width becomes 55nm)-(Exposure amount at which the line width becomes 45nm)〕 / Eopt]×100

[0850] The results are shown in Table 2.

[0851] The result of forming a pattern using the pattern formation method (1) is listed in the “EB exposure” column.

[0852] <Pattern Formation Method (2): EUV Exposure, Alkaline Development (Positive)>

[0853] The wafer coated with the resist film obtained above was pattern-exposed using an EUV exposure device (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, then immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. After that, the wafer was rotated at a speed of 4000 rpm for 30 seconds, then dried by baking at 95°C for 60 seconds.

[0854] <Evaluation Latitude (EL)>

[0855] The optimal exposure amount for resolving line-and-space patterns with a line width of 50 nm (1:1) using a side-field scanning electron microscope (Hitachi Seisakusho S-9380II) is the sensitivity (Eopt) (mJ / cm²). 2 I did it as ).

[0856] Based on the obtained sensitivity (Eopt), the exposure amount was calculated when the target value of 50 nm was ±10% (i.e., 55 nm and 45 nm). Then, the exposure latitude (EL, unit: %) defined by the following equation was calculated. The larger the value of EL, the smaller the change in performance due to changes in exposure amount, and the better the result.

[0857] EL(%)=[〔(Exposure amount at which the line width becomes 55nm)-(Exposure amount at which the line width becomes 45nm)〕 / Eopt]×100

[0858] The results are shown in Table 2.

[0859] The result of forming a pattern using the pattern formation method (2) is listed in the “EUV exposure” column.

[0860] [Table 2]

[0861]

[0862] [Examples 2-3, 2-5–2-10, 2-12, 2-17, and Comparative Example 2-3]

[0863] Among the resist compositions prepared by the above method, the one listed in Table 3 below was used.

[0864] A resist composition was prepared in the same manner as described in the <Description of a Resist Composition> above, and a wafer coated with a resist film was obtained.

[0865] <Pattern formation method (3): EB exposure, organic solvent development (negative)>

[0866] The wafer coated with the resist film obtained above was patterned using an electron beam lithography device (Advantest Inc.; F7000S, acceleration voltage 50 keV). At this time, lithography was performed to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative-type pattern.

[0867] The evaluation was performed using the same method as the aforementioned <evaluation exposure latitude (EL)> in the aforementioned <pattern formation method (1): EB exposure, alkali development (positive)>.

[0868] The results are shown in Table 3.

[0869] The result of forming a pattern using the pattern formation method (3) is listed in the “EB exposure” column.

[0870] <Pattern formation method (4): EUV exposure, organic solvent development (negative)>

[0871] The wafer coated with the resist film obtained above was pattern-exposed using an EUV exposure device (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, then developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative-type pattern.

[0872] The above-described <pattern formation method (2): EUV exposure, alkali development (positive)> was evaluated using the same method as the above-described <evaluation exposure latitude (EL)>.

[0873] The results are shown in Table 3.

[0874] The result of forming a pattern using the pattern formation method (4) is listed in the “EUV exposure” column.

[0875] [Table 3]

[0876]

[0877] From the results of Tables 2 and 3, it was found that the resist composition used in the examples had excellent EL performance.

[0878] Industrial applicability

[0879] The present invention provides a chromogenic or radiation-sensitive resin composition having excellent EL performance. Furthermore, the present invention provides a chromogenic or radiation-sensitive film using the chromogenic or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

[0880] Although the present invention has been described in detail with reference to specific embodiments, it is clear to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0881] In addition, this application is based on Japanese patent application filed on February 22, 2024 (JP 2024-025985), the contents of which are incorporated by reference during this application.

Claims

Claim 1 A desensitizing photoreactive or radiation-reducing resin composition containing a resin (A1) having repeating units represented by the following general formula (1). [Chemical Formula 1] In general formula (1), Ra, Rb, and Rc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L represents a single bond, -COO-, or a group represented by general formula (1-1). Y represents a group represented by general formula (1-2). In general formula (1-1), L1 represents a single bond or -COO-. X1 represents an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group. L2 represents -O- or -COO-. *1 represents the bonding site with the carbon atom to which Rb is bonded, and *2 represents the bonding site with Y. If L represents a group represented by general formula (1-1), Rc and X1 may be bonded to form a ring. In general formula (1-2), Rd, Re, Rf, and Rg each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, Represents an aryl group or a heteroaryl group. X2 represents a single bond or an oxygen atom. If X2 is a single bond, Rh represents an aryl group, a heteroaryl group, an alkyne group, or an alkene group. If X2 is an oxygen atom, Rh represents an aryl group, a heteroaryl group, an aromatic acyl group, a heteroaromatic acyl group, an alkyne group, or an alkene group. m represents 0 or 1, and n represents an integer from 0 to 2. However, either m or n is 0 and the other is an integer. If m=1, X2 is a single bond. If Rh is an aryl group, n is 0 or 2, or L represents a single bond, -COO-, or a group represented by general formula (1-1), and L1 is -COO-. *3 represents the bonding site with L. Claim 2 A desensitizing photoreactive or radiation-reducing resin composition containing a resin (A2) having repeating units represented by the following general formula (2). [Chemical Formula 2] In general formula (2), Ri, Rj, and Rk each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Rl and Rm each independently represent a hydrogen atom or an aryl group. Ar1 represents a heteroarylene group or an arylene group that does not have an iodine atom. Ar2 represents an aryl group. Rk and Ar1 may be combined to form a ring. Claim 3 A desensitizing photoreactive or radiation-reducing resin composition according to claim 2, wherein Rl and Rm in the general formula (2) both represent hydrogen atoms. Claim 4 A desensitizing photoreactive or radiation-reducing resin composition according to claim 1 or claim 2, wherein the resin (A1) has repeating units having aromatic groups that are different from repeating units represented by the general formula (1), or wherein the resin (A2) has repeating units having aromatic groups that are different from repeating units represented by the general formula (2). Claim 5 A photosensitive or radiation-sensitive resin composition according to claim 4, wherein the repeating unit having the aromatic group is a repeating unit represented by the following formula (N-1). [Chemical Formula 3] In equation (N-1), R 101 , R 102 and R 103 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. provided that R 102 is Ar A It may combine with to form a ring, and in that case, R 102 represents a single bond or an alkylene group. L A represents a single bond or a divalent linker. Ar A represents an aromatic group. k represents an integer from 0 to 5. Claim 6 A desensitizing photoreactive or radiation-reducing resin composition according to claim 1 or claim 2, wherein the resin (A1) or resin (A2) comprises repeating units having groups that decompose by the action of an acid. Claim 7 A desensitizing photoreactive or radiation-reducing resin composition according to claim 6, comprising less than 30 mol% of a repeating unit having a group that decomposes by the action of the acid with respect to the total repeating unit of the resin (A1) or resin (A2). Claim 8 A photosensitive or radiation-sensitive resin composition according to claim 6, wherein the repeating unit having a group that decomposes by the action of the acid comprises at least one selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3). [Chemical Formula 4] In equation (M-1), R 11 , R 12 and R 13 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M1 represents a divalent linker containing an aromatic group. R 14 , R 15 and R 16 Each represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group independently. 14 , R 15 and R 16 Two of them may combine to form a ring. In Equation (M-2), R 21 , R 22 and R 23 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M2 represents a divalent linker containing an aromatic group. R 24 , R 25 and R 26 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 25 and R 26 It may combine to form a ring. L M2 The aromatic group included in is R 22 or R 24 It may combine with to form a ring. In formula (M-3), R 31 , R 32 and R 33 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. M3 represents a divalent linker containing an aromatic group. R 34 and R 35 Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkeneyl group independently. 36 It represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R 35 and R 36 It may combine to form a ring. Claim 9 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, further comprising a compound (B) that generates acid upon irradiation with active light or radiation. Claim 10 A photosensitive or radiation-sensitive resin composition according to claim 9, wherein the compound (B) has a group that decomposes by the action of an acid. Claim 11 The photosensitive or radiation-sensitive resin composition of claim 9, wherein the compound (B) is represented by the following formula (U-1). [Chemical Formula 5] In formula (U-1), L U1 represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 may be the same or different. g represents an integer from 1 to 5. X U1 represents the g+1 linker. M U1 + It represents sulfonium ions or iodine ions. Claim 12 The photosensitive or radiation-sensitive resin composition of claim 9, wherein the compound (B) is represented by the following formula (U-2). [Chemical Formula 6] In equation (U-2), L U1 represents a single bond or a divalent linker. L U1 If this plural exists, the plural L U1 It may be the same or different. A U1 It represents the energy that is decomposed by the action of acid. A U1 In cases where this plural exists, the plural A U1 It may be the same or different. R U1 represents a substituent. R U1 If this plural exists, the plural R U1 It may be the same or different. R U1 If this plural exists, the plural R U1 They may combine to form a ring. g1 represents an integer from 1 to 5. g2 represents an integer from 0 to 4. M U1 + It represents sulfonium ions or iodine ions. Claim 13 A photosensitive or radiation-sensitive film formed using the photosensitive or radiation-sensitive resin composition described in claim 1 or claim 2. Claim 14 A pattern forming method comprising: a process of forming a resist film using a photosensitive or radiation-sensitive resin composition described in claim 1 or claim 2; a process of exposing the resist film to light; and a process of developing the exposed resist film using a developer. Claim 15 A method for manufacturing an electronic device comprising the pattern forming method described in claim 14.

Images