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

A photosensitive or radiation-sensitive resin composition containing a resin having a specific repeating unit (i), a specific repeating unit (ii), and a specific repeating unit (iii), wherein, when the repeating unit (ii) has a group that is decomposed by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid is not equivalent to the repeating unit (i); a photosensitive or radiation-sensitive film using the photosensitive 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 been required. Accordingly, there is a trend toward shorter 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 or radiation are being developed.

[0004] For example, Patent Document 1 describes a resist composition containing a repeating unit having a group that generates a phenolic hydroxyl group by the action of an acid, and a resin containing a phenolic hydroxyl group or a fluoroalcohol group. Prior art literature

[0005] International Publication No. 2018 / 56369 The problem to be solved

[0006] However, in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less), it has become difficult to establish high-level line width roughness (LWR) performance, pattern shape, and long-term stability.

[0007] LWR performance refers to the ability to reduce the LWR of a pattern.

[0008] The present invention aims to provide a photosensitive or radiation-sensitive resin composition capable of establishing high-level LWR performance, pattern shape, and long-term stability in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less). Furthermore, the present invention aims to provide a photosensitive or radiation-sensitive film using the said photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device. means of solving the problem

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

[0010] [1]

[0011] A desensitizing photo- or radiation-desensitizing resin composition containing a resin having the following repeating unit (i), the following repeating unit (ii), and the following repeating unit (iii). However, if the repeating unit (ii) has a group that decomposes by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid does not correspond to the repeating unit (i).

[0012] (i) a repeating unit having a phenolic hydroxyl group, and a monomer corresponding to said repeating unit, wherein the ClogP value of the anionic state in which the hydrogen atom of said phenolic hydroxyl group is dissociated is -7.50 or greater and less than -1.20.

[0013] (ii) a repeating unit having a phenolic hydroxyl group, and furthermore, in a monomer corresponding to the repeating unit, the repeating unit having a ClogP value of -0.70 or higher and less than 5.00 in the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated.

[0014] (iii) Repeating unit having a group that does not have a phenolic hydroxyl group and decomposes upon the action of an acid to increase polarity

[0015] [2]

[0016] A photosensitive or radiation-sensitive resin composition described in [1], wherein the repeating unit (i) is a repeating unit having two or more phenolic hydroxyl groups.

[0017] [3]

[0018] A photosensitive or radiation-sensitive resin composition described in [1] or [2], wherein the repeating unit (i) above is a repeating unit represented by the following general formula (a-1).

[0019] [Chemical Formula 1]

[0020]

[0021] Among the general formula (a-1),

[0022] R a1It represents a hydrogen atom or an alkyl group.

[0023] L 1 represents a single bond, or -C(=O)O-.

[0024] m represents an integer from 0 to 2.

[0025] n represents an integer between 2 and 3.

[0026] R a2 It represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these.

[0027] l represents an integer from 0 to 4, and if l is 2 or greater, multiple R a2 They may be identical or different from each other, and may combine to form a ring.

[0028] [4]

[0029] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [3], wherein the repeating unit (ii) above is a repeating unit represented by the following general formula (a-2).

[0030] [Chemical Formula 2]

[0031]

[0032] Among general formula (a-2),

[0033] R a2 represents a hydrogen atom or an alkyl group.

[0034] L 2 represents a single bond, or -C(=O)O-.

[0035] o represents an integer from 0 to 2.

[0036] p represents an integer from 1 to 2.

[0037] R a4It represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these.

[0038] q represents an integer from 0 to 4, and if q is 2 or greater, multiple R a4 They may be identical or different from each other, and may combine to form a ring.

[0039] [5]

[0040] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [4], wherein the repeating unit (iii) is at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (a-3) and a repeating unit represented by the following general formula (a-4).

[0041] [Chemical Formula 3]

[0042]

[0043] Among the general formula (a-3),

[0044] R a5 , R a15 Each represents a hydrogen atom or an alkyl group independently.

[0045] L 3 represents a single bond, or -C(=O)O-.

[0046] r represents an integer from 0 to 2.

[0047] s represents an integer from 0 to 4.

[0048] R p1 It represents the energy that is depleted by the action of acid.

[0049] t represents an integer from 0 to 4.

[0050] R p2 represents the energy that is dehydrated by the action of acid.

[0051] At least one of s or t is an integer greater than or equal to 1. u represents an integer from 0 to (5+r×4-st).

[0052] R a6 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these. If u is 2 or more, multiple R a6 They may be identical or different from each other, and may combine to form rings. Also, R a6 and R p1 , R a6 and R p2 , R p1 and R p2 Each may combine with others to form a ring. R a15 and L 3 These combining directional rings may combine with each other to form a ring.

[0053] [Chemical Formula 4]

[0054]

[0055] Among general formula (a-4),

[0056] R a7 It represents a hydrogen atom or an alkyl group.

[0057] R p3 It represents the energy that is depleted by the action of acid.

[0058] [6]

[0059] A desensitizing photoreactive or radiation-reducing resin composition described in any one of [1] to [5], wherein the repeating unit (iii) is a repeating unit represented by the general formula (a-3).

[0060] [7]

[0061] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [6], wherein the repeating unit (i) and the repeating unit (ii) are repeating units that do not have groups decomposed by the action of acid.

[0062] [8]

[0063] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [7], further containing a compound that generates acid upon irradiation with active light or radiation.

[0064] [9]

[0065] A photosensitive or photosensitive film formed by a photosensitive or photosensitive resin composition described in any one of [1] to [8].

[0066]

[10]

[0067] A pattern forming method comprising: a process of forming a photosensitive or photosensitive film on a substrate by means of a composition described in any one of [1] to [8]; a process of exposing the photosensitive or photosensitive film to light; and a process of developing the exposed photosensitive or photosensitive film using a developer.

[0068]

[11]

[0069] A method for manufacturing an electronic device comprising the pattern forming method described in

[10] . Effects of the invention

[0070] According to the present invention, a desensitizing light-sensitive or radiation-sensitive resin composition can be provided that can establish high-level LWR performance, pattern shape, and stability over time in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less).

[0071] In addition, the present invention may provide a photosensitive or radiation-sensitive film using the photosensitive 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

[0072] The present invention will be described in detail below.

[0073] 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.

[0074] 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).

[0075] In this specification, "light" means active light or radiation.

[0076] 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.

[0077] In this specification, "~" is used to mean including the values ​​described before and after it as lower and upper limits.

[0078] 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.

[0079] 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 GPC (Gel Permeation Chromatography) 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).

[0080] 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.

[0081] 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.

[0082] (Substituent T)

[0083] 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.

[0084] 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".

[0085] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, it is a value obtained by calculation based on a 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.

[0086] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0087] 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 thereto. Additionally, while there are multiple software programs capable of performing DFT, Gaussian 16 can be cited as an example.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] <Resin composition that is sensitive to light or radiation>

[0092] The photosensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "composition of the present invention") is,

[0093] A desensitizing photo- or radiation-desensitizing resin composition containing a resin having the following repeating unit (i), the following repeating unit (ii), and the following repeating unit (iii). However, if the repeating unit (ii) has a group that decomposes by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid does not correspond to the repeating unit (i).

[0094] (i) a repeating unit having a phenolic hydroxyl group, and a monomer corresponding to said repeating unit, wherein the ClogP value of the anionic state in which the hydrogen atom of said phenolic hydroxyl group is dissociated is -7.50 or greater and less than -1.20.

[0095] (ii) a repeating unit having a phenolic hydroxyl group, and furthermore, in a monomer corresponding to the repeating unit, the repeating unit having a ClogP value of -0.70 or higher and less than 5.00 in the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated.

[0096] (iii) Repeating unit having a group that does not have a phenolic hydroxyl group and decomposes upon the action of an acid to increase polarity

[0097] According to the composition of the present invention, by adopting the above configuration, it is possible to obtain a light-sensitive or radiation-sensitive resin composition that can establish LWR performance, pattern shape, and stability over time to a high degree in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less).

[0098] The reason is not clear, but it is presumed to be as follows.

[0099] It is known that in a resist composition, a resin having a repeating unit having a hydrophilic acid group, such as a repeating unit derived from dihydroxystyrene (DHS), and a repeating unit having a group that decomposes upon the action of an acid and increases polarity is used. However, as a result of the inventors' investigation, it was found that there are issues regarding LWR performance, pattern shape, and stability over time. The group that decomposes upon the action of an acid and increases polarity is a hydrophobic group, and the inventors estimated that the poor compatibility of the resin is caused by the large difference in hydrophilicity between the hydrophilic acid group and the hydrophobic group.

[0100] In addition to the two repeating units mentioned above, the inventors considered adding various repeating units, but repeating units such as the repeating unit derived from parahydroxystyrene (PHS) still have hydrophilic acid groups and did not lead to improvement.

[0101] The inventors have discovered, through careful examination, that the above performance is improved by using a repeating unit having a hydrophobic acid group more hydrophobic than PHS. It is believed that compatibility is improved by achieving a balance of hydrophilicity differences as a whole resin, with the hydrophilic group of the acid group in the repeating unit derived from the above-described DHS and the hydrophobic group of the repeating unit that is decomposed by the action of the acid and has increased polarity, by having an appropriate hydrophilic group between the hydrophilic group of the acid group in the repeating unit that is decomposed by the action of the acid and has increased polarity.

[0102] Furthermore, the inventors discovered that the ClogP value contributes to the hydrophobicity difference in each repeating unit, and thus completed the present invention.

[0103] The present invention comprises a resin having the repeating unit (i), the repeating unit (ii), and the repeating unit (iii). The repeating unit (i) is thought to be a repeating unit having the most hydrophilic group, and the repeating unit (iii) is thought to be a repeating unit having the most hydrophobic group. The repeating unit (ii) is thought to have a group having properties between the two. By using a resin having these three types of repeating units (i), repeating unit (ii), and repeating unit (iii), aggregation between repeating units (i) or between repeating units (iii) is difficult to occur due to the presence of the repeating unit (ii), which has properties intermediate between repeating unit (i) and repeating unit (iii) in terms of hydrophilicity. Furthermore, it is thought that the compatibility between resins tends to be very high in the present invention. As a result, it is thought that the above composition of the present invention can establish LWR performance, pattern formation, and long-term stability at a high level.

[0104] In addition, although the detailed reason is unclear, it was also found that when the repeating unit (ii) contains a group that is decomposed by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid is not equivalent to the repeating unit (i), and thus the above effect of the present invention is clearly manifested.

[0105] 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.

[0106] The composition of the present invention may be a chemically amplified type resist composition or a non-chemically amplified type resist composition. Typically, the composition of the present invention is a chemically amplified type resist composition.

[0107] 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 typically a resist film.

[0108] First, the various components of the composition of the present invention will be described in detail below.

[0109] [Suzy (A)]

[0110] The resin (A) included in the composition of the present invention is a resin having the following repeating unit (i), the following repeating unit (ii), and the following repeating unit (iii). However, if the repeating unit (ii) has a group that is decomposed by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid does not correspond to the repeating unit (i).

[0111] (i) a repeating unit having a phenolic hydroxyl group, and a monomer corresponding to said repeating unit, wherein the ClogP value of the anionic state in which the hydrogen atom of said phenolic hydroxyl group is dissociated is -7.50 or greater and less than -1.20.

[0112] (ii) a repeating unit having a phenolic hydroxyl group, and furthermore, in a monomer corresponding to the repeating unit, the repeating unit having a ClogP value of -0.70 or higher and less than 5.00 in the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated.

[0113] (iii) Repeating unit having a group that does not have a phenolic hydroxyl group and decomposes upon the action of an acid to increase polarity

[0114] Below, each iteration unit is explained.

[0115] In this specification, a phenolic hydroxyl group represents a hydroxyl group bonded to an aromatic hydrocarbon group.

[0116] In addition, the ClopP values ​​for repeating unit (i) and repeating unit (ii) were calculated using ChemDraw 20 by calculating the structure in the anionic state where the proton of the hydroxyl group is dissociated.

[0117] (Repetition unit (i))

[0118] In the monomer corresponding to the repeating unit (i), the ClogP value of the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated is -7.50 or higher and less than -1.20.

[0119] The above ClogP value is -7.50 or higher, preferably -6.00 or higher, and more preferably -4.50 or higher. If the above ClogP value is less than -7.50, the hydrophilicity becomes excessively strong, and there is a possibility that the compatibility of the resulting resin (A) will deteriorate.

[0120] The above ClogP value is less than -1.20, preferably -2.00 or less, and more preferably -3.00 or less. If the above ClogP value is -1.20 or higher, the polarity of the resin decreases, so there is a possibility that the compatibility of the low-molecular-weight material used in combination with the obtained resin (A) will deteriorate.

[0121] The monomer corresponding to the repeating unit (i) represents the monomer before polymerization.

[0122] The above repeating unit (i) is preferably a repeating unit having two or more phenolic hydroxyl groups.

[0123] The upper limit of the number of phenolic hydroxyl groups in the repeating unit (i) is not particularly limited, but is preferably 3.

[0124] "The anionic state in which the hydrogen of the above phenolic hydroxyl group is dissociated" refers to the anionic state in which all hydrogen atoms of the two or more phenolic hydroxyl groups are dissociated when the above repeating unit (i) is a repeating unit having two or more phenolic hydroxyl groups.

[0125] The above-mentioned repeating unit (i) is preferably a repeating unit represented by the following general formula (a-1).

[0126] [Chemical Formula 5]

[0127]

[0128] Among the general formula (a-1),

[0129] R a1 It represents a hydrogen atom or an alkyl group.

[0130] L 1 represents a single bond, or -C(=O)O-.

[0131] m represents an integer from 0 to 2.

[0132] n represents an integer between 2 and 3.

[0133] R a2 It represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these.

[0134] l represents an integer from 0 to 4, and if l is 2 or greater, multiple R a2 They may be identical or different from each other, and may combine to form a ring.

[0135] R a1 As for the alkyl group, it 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.

[0136] m represents an integer from 0 to 2, preferably 0 or 1, and more preferably 0. The aromatic ring in general formula (a-1) becomes benzene when m represents 0, becomes naphthalene when m represents 1, and becomes anthracene when m represents 2.

[0137] n represents an integer between 2 and 3, and it is preferable to represent 2.

[0138] R a2 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0139] R a2 As the alkyl group, it 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 10 is preferred, and 1 to 6 is more preferred. R a2 The methylene group included in the alkyl group may be substituted with at least one of -CO- and -O-.

[0140] R a2 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. R a2 As for the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0141] R a2 The alkyl group included in the alkoxy group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0142] R a2The number of carbon atoms in the aryl group included in the aryloxy group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the aryloxy groups, the phenyl group is most preferable.

[0143] R a2 The alkyl group included in the alkylthio group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkylthio group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0144] R a2 The number of carbon atoms in the aryl group included in the arylthio group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the arylthio groups, the phenyl group is most preferable.

[0145] R a2 The number of carbon atoms in the aryl group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. R a2 As for the aryl group, the phenyl group is the most desirable.

[0146] R a2 The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of sulfur atoms, nitrogen atoms, and oxygen atoms. The number of heteroatoms included in the heteroaryl group is preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 2 to 20, and more preferably 3 to 15. The heteroaryl group may be monocyclic or polycyclic. R a2 Examples of heteroaryl groups include, for instance, cyanyl groups, furanyl groups, benzothienyl groups, dibenzothienyl groups, benzofuranyl groups, pyrrole groups, oxazoleyl groups, thiazoleyl groups, pyridyl groups, isothienyl groups, thiadiazoleyl groups, etc.

[0147] A group formed by combining two or more of these is not particularly limited, but, for example, may be a group formed by combining at least one selected from the group consisting of an ester group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, and a carboxyl group.

[0148] l represents an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0 or 1.

[0149] The above-mentioned alkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, aryl group, arylthio group, heteroaryl group, ester group, carboxyl group, or a combination of two or more of these may further have substituents.

[0150] R a2 It may or may not have energy that is decomposed by the action of acid.

[0151] As for the group that is decomposed by the action of acid (acid-decomposing group), the acid-decomposing group in the repeating unit (iii) described later can be cited.

[0152] In the monomer corresponding to the repeating unit (i), the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated and the ClogP value of the anionic state are shown below, but the present invention is not limited thereto.

[0153] [Chemical Formula 6]

[0154]

[0155] Specific examples of monomers corresponding to repeating unit (i) are shown below, but the present invention is not limited to these.

[0156] [Chemical Formula 7]

[0157]

[0158] The content of repeating unit (i) is preferably 5 mol% or more with respect to the total repeating unit in the resin (A), more preferably 10 mol% or more, and more preferably 15 mol% or more. In addition, the content of repeating unit (i) is preferably 80 mol% or less with respect to the total repeating unit in the resin (A), more preferably 70 mol% or less, and more preferably 60 mol% or less.

[0159] The repeating unit (i) included in the resin (A) may be of one type or two or more types. If two or more types are included, it is preferable that the total content be within the range of the above suitable content.

[0160] (Repetition unit (ii))

[0161] In the monomer corresponding to the repeating unit (ii), the ClogP value of the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated is -0.70 or higher and less than 5.00.

[0162] The above ClogP value is -0.70 or higher, preferably -0.50 or higher, and more preferably 0.00 or higher. If the above ClogP value is less than -0.70, the hydrophilicity increases, and there is a possibility that the compatibility of the resulting resin (A) will deteriorate.

[0163] The above ClogP value is less than 5.00, preferably 4.00 or less, and more preferably 2.50 or less. If the above ClogP value is 5.00 or more, hydrophobicity increases, and there is a possibility that the compatibility of the resulting resin (A) will deteriorate.

[0164] The monomer corresponding to the repeating unit (ii) represents the monomer prior to polymerization.

[0165] The above repeating unit (ii) is a repeating unit having one phenolic hydroxyl group, and may be a repeating unit having one or more phenolic hydroxyl groups.

[0166] The upper limit of the number of phenolic hydroxyl groups in the repeating unit (ii) is not particularly limited, but it is preferably 2.

[0167] "The anionic state in which the hydrogen of the above phenolic hydroxyl group is dissociated" refers to the anionic state in which all hydrogen atoms of the two phenolic hydroxyl groups are dissociated when the above repeating unit (ii) is a repeating unit having two phenolic hydroxyl groups.

[0168] The above-mentioned repeating unit (ii) is preferably a repeating unit represented by the following general formula (a-2).

[0169] [Chemical Formula 8]

[0170]

[0171] Among general formula (a-2),

[0172] R a3 It represents a hydrogen atom or an alkyl group.

[0173] L 2 represents a single bond, or -C(=O)O-.

[0174] o represents an integer from 0 to 2.

[0175] p represents an integer from 1 to 2.

[0176] R a4 It represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these.

[0177] q represents an integer from 0 to 4, and if q is 2 or greater, multiple R a4 They may be identical or different from each other, and may combine to form a ring.

[0178] R a3 As for the alkyl group, it 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.

[0179] o represents an integer from 0 to 2, preferably 0 or 1, and more preferably 0. The aromatic ring in general formula (a-2) becomes benzene when o represents 0, becomes naphthalene when o represents 1, and becomes anthracene when o represents 2.

[0180] p represents an integer from 1 to 2, and it is preferable to represent 1.

[0181] R a4 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0182] R a4 As the alkyl group, it 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 10 is preferred, and 1 to 6 is more preferred. R a4 The methylene group included in the alkyl group may be substituted with at least one of -CO- and -O-.

[0183] R a4 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. R a4 As for the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0184] R a4 The alkyl group included in the alkoxy group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0185] R a4The number of carbon atoms in the aryl group included in the aryloxy group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the aryloxy groups, the phenyl group is most preferable.

[0186] R a4 The alkyl group included in the alkylthio group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkylthio group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0187] R a4 The number of carbon atoms in the aryl group included in the arylthio group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the arylthio groups, the phenyl group is most preferable.

[0188] R a4 The number of carbon atoms in the aryl group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. R a4 As for the aryl group, the phenyl group is the most desirable.

[0189] R a4 The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of sulfur atoms, nitrogen atoms, and oxygen atoms. The number of heteroatoms included in the heteroaryl group is preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 2 to 20, and more preferably 3 to 15. The heteroaryl group may be monocyclic or polycyclic. R a4 Examples of heteroaryl groups include, for instance, cyanyl groups, furanyl groups, benzothienyl groups, dibenzothienyl groups, benzofuranyl groups, pyrrole groups, oxazoleyl groups, thiazoleyl groups, pyridyl groups, isothienyl groups, thiadiazoleyl groups, etc.

[0190] A group formed by combining two or more of these is not particularly limited, but, for example, may be a group formed by combining at least one selected from the group consisting of an ester group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, and a carboxyl group.

[0191] q represents an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0 or 1.

[0192] The above-mentioned alkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, aryl group, heteroaryl group, ester group, carboxyl group, or a combination of two or more of these may further have substituents.

[0193] R a4 It may or may not have energy that is decomposed by the action of acid.

[0194] As for the group that is decomposed by the action of acid (acid-decomposing group), the acid-decomposing group in the repeating unit (iii) described later can be cited.

[0195] If the above repeating unit (ii) has a group that is decomposed by the action of an acid, the repeating unit after the above repeating unit (ii) is decomposed by the action of an acid does not correspond to the above repeating unit (i).

[0196] In the monomer corresponding to the repeating unit (ii), the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated and the ClogP value of the anionic state are shown below, but the present invention is not limited thereto.

[0197] [Chemical Formula 9]

[0198]

[0199] Specific examples of monomers corresponding to repeating units (ii) are shown below, but the present invention is not limited to these.

[0200] [Chemical Formula 10]

[0201]

[0202] In terms of LWR performance, pattern shape, and stability over time, it is preferable that the repeating unit (i) and the repeating unit (ii) are repeating units that do not have groups that decompose by the action of acid.

[0203] The content of repeating unit (ii) is preferably 5 mol% or more with respect to the total repeating unit in resin (A), more preferably 10 mol% or more, and more preferably 15 mol% or more. In addition, the content of repeating unit (ii) is preferably 80 mol% or less with respect to the total repeating unit in resin (A), more preferably 70 mol% or less, and more preferably 60 mol% or less.

[0204] The repeating unit (ii) included in the resin (A) may be of one type or two or more types. If two or more types are included, it is preferable that the total content be within the range of the above suitable content.

[0205] (Repetition unit (iii))

[0206] The repeating unit (iii) has a group that is decomposed by the action of acid and has increased polarity.

[0207] The resin (A) included in the composition of the present invention is a resin that contains a group (also called an "acid-degradable group") that decomposes upon the action of an acid and increases polarity.

[0208] Resin (A) is an acid-degradable resin, and in a pattern forming 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.

[0209] The acid-degradable group is typically a group that decomposes upon the action of an acid to generate a polar group. It is desirable for the acid-degradable group to have a structure in which the polar group is protected by the action of an acid (detachable group). Typically, the polarity of the resin (A) increases upon the action of an acid, thereby increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.

[0210] 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.

[0211] As for the group that is removed by the action of acid (removal group), for example, the group represented by equations (Y1) to (Y4) can be cited.

[0212] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0213] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0214] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0215] Equation (Y4): -C(Rn)(H)(Ar)

[0216] 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), or an alkeneyl 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. Each of the above groups may further have substituents.

[0217] 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.

[0218] Two of Rx1 to Rx3 may combine to form a ring (either a monoring or a polyring).

[0219] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0220] As for the cycloalkyl groups of Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0221] 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.

[0222] As for the aralkyl groups of Rx1 to Rx3, it is preferable to have one hydrogen atom among the alkyl groups of Rx1 to Rx3 described above substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples include a benzyl group.

[0223] As for the alkene groups of Rx1~Rx3, a vinyl group is preferred.

[0224] 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.

[0225] 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, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0226] 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.

[0227] 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 rings. 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] The repeating unit (iii) is preferably at least one repeating unit selected from the group consisting of the repeating unit represented by the following general formula (a-3) and the repeating unit represented by the following general formula (a-4).

[0232] [Chemical Formula 11]

[0233]

[0234] Among the general formula (a-3),

[0235] R a5 , R a15 Each represents a hydrogen atom or an alkyl group independently.

[0236] L 3 represents a single bond, or -C(=O)O-.

[0237] r represents an integer from 0 to 2.

[0238] s represents an integer from 0 to 4.

[0239] R p1 It represents the energy that is depleted by the action of acid.

[0240] t represents an integer from 0 to 4.

[0241] R p2 represents the energy that is dehydrated by the action of acid.

[0242] At least one of s or t is an integer greater than or equal to 1. u represents an integer from 0 to (5+r×4-st).

[0243] R a6 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these. If u is 2 or more, multiple R a6 They may be identical or different from each other, and may combine to form rings. Also, R a6 and R p1 , R a6 and R p2 , R p1 and R p2 Each may combine with others to form a ring. R a15 and L 3 These combining directional rings may combine with each other to form a ring.

[0244] [Chemical Formula 12]

[0245]

[0246] Among general formula (a-4),

[0247] R a7 It represents a hydrogen atom or an alkyl group.

[0248] R p3 It represents the energy that is depleted by the action of acid.

[0249] (Repetition unit represented by the general formula (a-3))

[0250] R a5As for the alkyl group, it 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.

[0251] The alkyl group may have additional substituents.

[0252] r represents an integer from 0 to 2, preferably 0 or 1, and more preferably 0. The aromatic ring in general formula (a-3) becomes benzene when r represents 0, naphthalene when r represents 1, and anthracene when r represents 2.

[0253] s represents an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0 or 1.

[0254] R p1 represents a group that is removed by the action of an acid. Groups removed by the action of an acid are not particularly limited, but can be represented by the above-described equations (Y1) to (Y4).

[0255] -OR in general formula (a-3) p1 Silver, due to the action of acid R p1 This detaches and generates a hydroxyl group.

[0256] t represents an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0 or 1. At least one of s or t is an integer greater than or equal to 1.

[0257] R p2 represents a group that is removed by the action of an acid. The group removed by the action of an acid is not particularly limited, but can be represented by the above-described equations (Y1) to (Y4).

[0258] -COOR in general formula (a-3) p2 is, due to the action of acid R p1 This detaches and generates a carboxyl group.

[0259] R a6 It represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these.

[0260] R a6 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms or iodine atoms are preferred.

[0261] R a6 As the alkyl group, it 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 10 is preferred, and 1 to 6 is more preferred. R a6 The methylene group included in the alkyl group may be substituted with at least one of -CO- and -O-.

[0262] R a6 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. R a4 As for the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0263] R a6 The alkyl group included in the alkoxy group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkoxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0264] R a6 The number of carbon atoms in the aryl group included in the aryloxy group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the aryloxy groups, the phenyl group is most preferable.

[0265] R a6 The alkyl group included in the alkylthio group may be either a straight chain or a branched chain. The number of carbon atoms in the alkyl group included in the alkylthio group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0266] R a6 The number of carbon atoms in the aryl group included in the arylthio group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. R a2 Among the aryl groups included in the arylthio groups, the phenyl group is most preferable.

[0267] R a6 The number of carbon atoms in the aryl group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. R a4 As for the aryl group, the phenyl group is the most desirable.

[0268] R a6 The heteroaryl group preferably comprises at least one heteroatom selected from the group consisting of sulfur atoms, nitrogen atoms, and oxygen atoms. The number of heteroatoms included in the heteroaryl group is preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 2 to 20, and more preferably 3 to 15. The heteroaryl group may be monocyclic or polycyclic. R a4 Examples of heteroaryl groups include, for instance, cyanyl groups, furanyl groups, benzothienyl groups, dibenzothienyl groups, benzofuranyl groups, pyrrole groups, oxazoleyl groups, thiazoleyl groups, pyridyl groups, isothienyl groups, thiadiazoleyl groups, etc.

[0269] A group formed by combining two or more of these is not particularly limited, but, for example, may be a group formed by combining at least one selected from the group consisting of an ester group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, and a carboxyl group.

[0270] The above-mentioned alkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, aryl group, heteroaryl group, ester group, carboxyl group, or a combination of two or more of these may further have substituents.

[0271] If u is 2 or greater, multiple R a6 They may be identical or different from each other, and may combine to form rings. Also, R a6 and R p1 , R a6 and R p2 , R p1 and R p2 Each of them may combine with others to form a ring.

[0272] Multiple R a6 The rings formed by combining these rings are not particularly limited, but may be simple or polycyclic. R a6 and R p1 , R a6 and R p2 , R p1 and R p2 The rings formed by combining with each other are not particularly limited, but may be single rings or multiple rings.

[0273] (Repetition unit represented by general formula (a-4))

[0274] R a7 As for the alkyl group, it 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.

[0275] The alkyl group may have additional substituents.

[0276] R p3 represents a group that is removed by the action of an acid. Groups removed by the action of an acid are not particularly limited, but can be represented by the above-described equations (Y1) to (Y4).

[0277] -COOR in general formula (a-4) p3 Silver, due to the action of acid R p3 This detaches and generates a carboxyl group.

[0278] Specific examples of the repeating unit (iii) are shown below, but the present invention is not limited to these.

[0279] Additionally, in the formula, Rx represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Z represents a substituent, and if multiple substituents are present, they are independent. p represents 0 or a positive integer.

[0280] Also, in the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms.

[0281] [Chemical Formula 13]

[0282]

[0283] [Chemical Formula 14]

[0284]

[0285] [Chemical Formula 15]

[0286]

[0287] [Chemical Formula 16]

[0288]

[0289] [Chemical Formula 17]

[0290]

[0291] [Chemical Formula 18]

[0292]

[0293] [Chemical Formula 19]

[0294]

[0295] [Chemical Formula 20]

[0296]

[0297] [Chemical Formula 21]

[0298]

[0299] [Chemical Formula 22]

[0300]

[0301] [Chemical Formula 23]

[0302]

[0303] [Chemical Formula 24]

[0304]

[0305] [Chemical Formula 25]

[0306]

[0307] [Chemical Formula 26]

[0308]

[0309] Repeating unit (iii) does not have a phenolic hydroxyl group.

[0310] The repeating unit (iii) is preferably a repeating unit represented by the above general formula (a-3).

[0311] The content of the repeating unit (iii) is preferably 5 mol% or more with respect to the total repeating unit in the resin (A), more preferably 10 mol% or more, and more preferably 15 mol% or more. In addition, the content of the repeating unit (iii) is preferably 70 mol% or less with respect to the total repeating unit in the resin (A), more preferably 60 mol% or less, and more preferably 50 mol% or less.

[0312] The repeating unit (iii) included in the resin (A) may be of one type or two or more types. If two or more types are included, it is preferable that the total content be within the range of the above suitable content.

[0313] Resin (A) is a resin having repeating unit (i), repeating unit (ii), and repeating unit (iii).

[0314] In a preferred embodiment, the sum of the content of repeating unit (i), the content of repeating unit (ii), and the content of repeating unit (iii) is preferably 70 mol% or more with respect to the total repeating unit in resin (A), more preferably 80 mol% or more, and more preferably 90 mol% or more.

[0315] In addition, as a preferred embodiment, resin (A) may have only repeating unit (i), repeating unit (ii), and repeating unit (iii).

[0316] (Other repeating units)

[0317] A number (A) may have other repeating units in addition to repeating units (i), repeating unit (ii), and repeating unit (iii).

[0318] Other repeating units are explained below.

[0319] (Repeating unit with polarity)

[0320] A repeating unit having a polarity is a repeating unit different from repeating unit (i), repeating unit (ii), and repeating unit (iii).

[0321] Examples of polar groups of repeating units having polar groups include hydroxyl groups, lactone groups, sulfonate groups, lactam groups, imide groups, amide groups, sulfonamide groups, carbonate groups, uretain groups, urea groups, nitrile groups, sulfoxide groups, sulfonyl groups, etc. The polar group may be an acid group. As for the polar group, a hydroxyl group or a lactone group is preferred, an aromatic hydroxyl group is more preferred, and a phenolic hydroxyl group is even more preferred.

[0322] As a repeating unit including a polarity, it is preferable to be a repeating unit represented by the following general formula (S3).

[0323] The repeating unit having a polarity is preferably a repeating unit represented by the following general formula (S3).

[0324] [Chemical Formula 27]

[0325]

[0326] Among the general formula (S3), R 101 , R 102 and R 103 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 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.

[0327] L A represents a single link or a divalent link.

[0328] Ar A represents directional ventilation.

[0329] k represents an integer from 1 to 5.

[0330] R in general formula (S3) 101 , R102 and R 103 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 101 , R 102 and R 103 The description, specific examples, and preferred ranges for Ra1 to Ra3 in the general formula (S1) described above are the same as the description, specific examples, and preferred ranges for Ra1 to Ra3.

[0331] Ar in general formula (S3) A represents an aromatization, and more specifically, represents an aromatization of (k+1). In the case where k is 1, the divalent aromatization is preferably a divalent aromatization comprising, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, tolylene group, naphthylene group, or anthraceneylene group, or a heterocyclic ring such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, or thiazole ring. The above aromatization may have a substituent.

[0332] As a specific example of a (k+1)-valent directional ventilation 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 the above-described specific example of a divalent directional ventilation can be cited.

[0333] The (k+1) directional ventilation may have additional substituents.

[0334] The substituents that may have a (k+1) valence aromatic group 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; aryl groups such as phenyl groups; and hydroxyl groups.

[0335] Multiple substituents may combine to form a ring.

[0336] 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.

[0337] L in general formula (S3) A represents a single bond or a divalent linker.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] The repeating unit represented by general formula (S3) preferably has a hydroxystyrene structure. That is, Ar A It is desirable to represent a benzene ring.

[0342] It is preferable that k represents an integer from 1 to 3, and more preferable that it represents 1 or 2.

[0343] Specific examples of repeating units having polarity are shown below, but are not limited thereto.

[0344] In the case where a repeating unit having a polar group has a phenolic hydroxyl group, the ClogP value of the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated in the monomer corresponding to said repeating unit is also shown. The ClogP value is measured by the method described above.

[0345] [Chemical Formula 28]

[0346]

[0347] The content of repeating units having polar groups in the resin (A) is not particularly limited, but is preferably 5 mol% or more with respect to the total repeating units in the resin (A), more preferably 10 mol% or more, and even more preferably 15 mol% or more. In addition, the content of repeating units having polar groups is preferably 30 mol% or less with respect to the total repeating units in the resin (A), more preferably 25 mol% or less, and even more preferably 20 mol% or less.

[0348] The repeating unit having a polar group included in the resin (A) may be of one type or two or more types. If two or more types are included, it is preferable that the total content be within the range of the above suitable content.

[0349] (Repeating unit having an acid-degrading group)

[0350] Resin (A) may include, as other repeating units, repeating units having acid-degradable groups.

[0351] A repeating unit having an acid-degrading group is a repeating unit different from repeating unit (i), repeating unit (ii), and repeating unit (iii).

[0352] (Repeating unit having a lactone, sulfonate, or carbonate group)

[0353] The resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of a lactone group, a sulfonate group, and a carbonate group.

[0354] It is also desirable that the unit Y does not have acid groups such as hydroxyl groups and hexafluoropropanol groups.

[0355] 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.

[0356] For Suji (A), reference may be made to

[0120] –

[0134] of International Publication No. 2022 / 024928.

[0357] (A repeating unit having neither an acid-degrading group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom)

[0358] The resin (A) may have a repeating unit (hereinafter also referred to as unit X) that has neither an acid-degradable group nor an acid group, and has a fluorine atom, a bromine atom, or an iodine atom, separately from the repeating unit described above.

[0359] It is preferable that the <repeating unit having neither an acid-degrading group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom> referred to herein is different from the <repeating unit having a lactone group, a sulfonate group, or a carbonate group> and the <repeating unit having a photo-generating group> described later.

[0360] As unit X, the repeating unit represented by Equation (C) is preferred.

[0361] [Chemical Formula 29]

[0362]

[0363] 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.

[0364] Repeating units having fluorine atoms or iodine atoms are exemplified below.

[0365] [Chemical Formula 30]

[0366]

[0367] The content of unit X is preferably 0 mol% or more with respect to the total repeating unit in resin (A), more preferably 5 mol% or more, and more preferably 10 mol% or more. In addition, as an upper limit value, it is preferably 50 mol% or less with respect to the total repeating unit in resin (A), more preferably 45 mol% or less, and more preferably 40 mol% or less.

[0368] The total content of repeating units comprising at least one of a fluorine atom, a bromine atom, and an iodine atom among the repeating units of resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, and particularly preferably 40 mol% or more with respect to the total repeating units of resin (A). The upper limit is not particularly limited, but, for example, is 100 mol% or less with respect to the total repeating units of resin (A).

[0369] Additionally, as repeating units comprising at least one of a fluorine atom, a bromine atom, and an iodine atom, examples include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and also having an acid-degrading group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and also having an acid group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0370] (Repeating unit having a mine generator)

[0371] The resin (A) may have a repeating unit other than the above that has a repeating unit having a group (hereinafter also referred to as a "photo-generating group") that generates acid upon irradiation with active light or radiation (preferably electron beam or extreme ultraviolet light).

[0372] As a repeating unit having a mine generator, the repeating unit represented by Equation (4) can be cited.

[0373] [Chemical Formula 31]

[0374]

[0375] R 41 It represents silver, a hydrogen atom, or a methyl group. L 41 It 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.

[0376] Repeating units having a mine generator are exemplified below, but are not limited to these.

[0377] [Chemical Formula 32]

[0378]

[0379] [Chemical Formula 33]

[0380]

[0381] In addition, the repeating unit represented by Equation (4) can be, for example, the repeating unit described in paragraphs

[0094] to

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

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

[0382] When the resin (A) includes 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), and more preferably 5 mol% or more. In addition, as an upper limit, it is preferably 40 mol% or less with respect to the total repeating units in the resin (A), more preferably 35 mol% or less, and more preferably 30 mol% or less.

[0383] (The repeating unit represented by Equation (V-1) or Equation (V-2))

[0384] The number (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).

[0385] It is preferable that the iteration unit represented by the following equations (V-1) and (V-2) be a different iteration unit from the above-described iteration unit.

[0386] [Chemical Formula 34]

[0387]

[0388] During the meal,

[0389] 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 or a fluorinated alkyl group having 1 to 6 carbon atoms), 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.

[0390] n3 represents an integer from 0 to 6.

[0391] n4 represents an integer from 0 to 4.

[0392] X4 is a methylene group, an oxygen atom, or a sulfur atom.

[0393] The repeating unit represented by equation (V-1) or (V-2) is exemplified below.

[0394] As for the repeating unit represented by formula (V-1) or (V-2), for example, the repeating unit described in paragraph

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

[0395] (Repetitive unit to reduce the motility of the main chain)

[0396] In order to suppress excessive diffusion of generated acid or pattern collapse during development, it is preferable for the resin (A) to have a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, more preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, in terms of excellent dissolution rate in the developer, Tg is preferably 400°C or lower, and more preferably 350°C or lower.

[0397] In addition, in this 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 sum is given as the Tg of the polymer (°C).

[0398] 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 calculation software MDL Polymer (MDL Information Systems, Inc.).

[0399] In order to increase the Tg of resin (A) (preferably, to make the Tg greater than 90°C), it is desirable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e).

[0400] (a) Introduction of bulky substituents into the main chain

[0401] (b) Introduction of multiple substituents into the main chain

[0402] (c) Introduction of substituents that induce interactions between the resins (A) near the main chain

[0403] (d) Main chain formation in cyclic structures

[0404] (e) Connection of the annular structure to the main chain

[0405] In addition, it is preferable that the resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher.

[0406] In addition, the type of repeating unit having a Tg of 130°C or higher in the homopolymer is not particularly limited, and it is sufficient if it is a repeating unit having a Tg of 130°C or higher in the homopolymer calculated by the Bicerano method. In addition, depending on the type of functional group among the repeating units represented by Equations (A) to (E) described below, it corresponds to a repeating unit having a Tg of 130°C or higher in the homopolymer.

[0407] As an example of a specific means of achieving (a) above, a method of introducing a repeating unit represented by formula (A) into resin (A) can be cited.

[0408] [Chemical Formula 35]

[0409]

[0410] In Equation (A), R A represents a group containing a polycyclic structure. R x represents a hydrogen atom, a methyl group, or an ethyl group. A group comprising a polycyclic structure is a group comprising multiple ring structures, and the multiple ring structures may or may not be condensed.

[0411] Specific examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] –

[0119] of International Publication No. 2018 / 193954.

[0412] As an example of a specific means of achieving (b) above, a method of introducing a repeating unit represented by Equation (B) into resin (A) can be cited.

[0413] [Chemical Formula 36]

[0414]

[0415] In Equation (B), R b1 ~R b4 Each independently represents a hydrogen atom or an organic group, and R b1 ~R b4 At least two of them represent organic groups.

[0416] If at least one of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, the types of other organic groups are not particularly limited.

[0417] Also, in cases where none of the organic groups are groups in which a ring structure is directly connected to the main chain of the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.

[0418] Specific examples of the repeating unit represented by formula (B) include those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0419] As an example of a specific means of achieving (c) above, a method of introducing a repeating unit represented by formula (C) into resin (A) can be cited.

[0420] [Chemical Formula 37]

[0421]

[0422] In Equation (C), R c1 ~R c4 Each independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of them is a group containing hydrogen atoms that are hydrogen bondable within 3 atoms from the main chain carbon. Among these, in order to induce interactions between the main chains of the resin (A), it is preferable to have hydrogen atoms that are hydrogen bondable within 2 atoms (more near the main chain).

[0423] Specific examples of the repeating unit represented by formula (C) include those described in paragraphs

[0119] –

[0121] of International Publication No. 2018 / 193954.

[0424] As an example of a specific means of achieving (d) above, a method of introducing a repeating unit represented by Equation (D) into resin (A) can be cited.

[0425] [Chemical Formula 38]

[0426]

[0427] In formula (D), "Cyclic" represents a group forming a main chain in a cyclic structure. The number of constituent atoms of the ring is not particularly limited.

[0428] Specific examples of the repeating unit represented by formula (D) include those described in paragraphs

[0126] –

[0127] of International Publication No. 2018 / 193954.

[0429] As an example of a specific means of achieving (e) above, a method of introducing a repeating unit represented by E into resin (A) can be cited.

[0430] [Chemical Formula 39]

[0431]

[0432] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of organic groups may include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups that may have substituents.

[0433] "Cyclic" is a cyclic group containing carbon atoms of the main chain. The number of atoms included in the cyclic group is not particularly limited.

[0434] Specific examples of the repeating unit represented by formula (E) include those described in paragraphs

[0131] –

[0133] of International Publication No. 2018 / 193954.

[0435] (Repeating unit having at least one group selected from lactone groups, sulfonate groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups)

[0436] 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.

[0437] As repeating units having a lactone group, a sulfon group, or a carbonate group in the resin (A), the repeating units described in <Repeating units having a lactone group, a sulfon group, or a carbonate group> above may be cited. The preferred content is also as described in <Repeating units having a lactone group, a sulfon group, or a carbonate group> above.

[0438] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity.

[0439] 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.

[0440] 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.

[0441] The resin (A) may have repeating units having alkali-soluble groups.

[0442] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonilimide groups, bissulfonilimide groups, and aliphatic alcohol groups in which the α-position is substituted with an electron-receptive group (e.g., hexafluoroisopropanol groups), and carboxyl groups are preferred. By including repeating units having alkali-soluble groups in the resin (A), the resolution for contact hole applications is increased. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

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

[0443] (Repeating unit having a hydrocarbon structure and not exhibiting acid decomposition)

[0444] The resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do 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, diadamantyl (meth)acrylate, tricyclodecaneyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0445] (A repeating unit represented by Equation (III) that has neither a hydroxyl group nor a cyano group)

[0446] Resin (A) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0447] [Chemical Formula 40]

[0448]

[0449] 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.

[0450] 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.

[0451] 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.

[0452] In addition to the repeating unit above, the resin (A) may have various repeating units for the purpose of controlling dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0453] As for the resin (A), particularly when the composition of the present invention is used as a desensitizing photo- or radiation-desensitizing resin composition for ArF, it is preferable that all repeating units consist of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all repeating units consist of (meth)acrylate-based repeating units. When all repeating units consist of (meth)acrylate-based repeating units, any of the following may be used: all repeating units are methacrylate-based repeating units, all repeating units are acrylate-based repeating units, or all repeating units are composed of methacrylate-based repeating units and acrylate-based repeating units, and it is preferable that the acrylate-based repeating units are 50 mol% or less of the total repeating units.

[0454] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization).

[0455] 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 30,000, and particularly preferably 5,000 to 15,000.

[0456] The dispersion (molecular weight distribution, Pd, Mw / Mn) of the resin (A) 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 dispersion, the better the resolution and resist shape, and the sidewalls of the resist pattern are smoother, and the roughness is also better.

[0457] In the composition of the present invention, the content of resin (A) 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 90.0 mass%.

[0458] The resin (A) may be used as one 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.

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

[0460] The composition of the present invention preferably includes a compound (photoacid generator) that generates acid upon irradiation with active light or radiation.

[0461] 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.

[0462] 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.

[0463] In the case where the photogenerator is introduced into a part of the polymer, it may be introduced into a part of the resin (A) or into a resin different from the resin (A).

[0464] It is preferable that the photogenerator be in the form of a low-molecular-weight compound.

[0465] The photogenerator is preferably a compound that generates an acid with a pKa of -2.0 or higher upon irradiation with active light or radiation, and more preferably a compound that generates an acid with a pKa of -2.0 or higher and 1.0 or lower.

[0466] As for photocatalytic agents, for example, "M + X - Examples include compounds (onium salts) that appear as such, and it is preferable that they be compounds that generate organic acids upon exposure to light.

[0467] 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.

[0468] "M + X - In compounds represented as ", M + Silver represents an organic cation.

[0469] There are no particular restrictions on the organic cation. The valence of the organic cation may be 1 or 2 or higher.

[0470] 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.

[0471] [Chemical Formula 41]

[0472]

[0473] In the above formula (ZaI), R 201 , R 202 , and R 203 Each independently represents an organic group.

[0474] 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-.

[0475] 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.

[0476] First, we will explain the cation (ZaI-1).

[0477] 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.

[0478] The arylsulfonium cation is, R 201 ~R 203 It is okay if everything is Arilgi, R 201 ~R 203 Some of it may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

[0479] 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.

[0480] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0481] 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.

[0482] 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.

[0483] 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.

[0484] 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.

[0485] It is also desirable for the above substituents to form acid-degradable groups by any combination.

[0486] 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.

[0487] Next, the cation (ZaI-2) will be explained.

[0488] 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.

[0489] 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.

[0490] 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.

[0491] 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).

[0492] 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.

[0493] R 201 ~R 203 It is also desirable for the substituents to independently form acid-degradable groups by any combination of substituents.

[0494] Next, the cation (ZaI-3b) is described.

[0495] The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0496] [Chemical Formula 42]

[0497]

[0498] 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.

[0499] 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.

[0500] 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.

[0501] 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.

[0502] 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.

[0503] 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.

[0504] 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.

[0505] 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.

[0506] 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.

[0507] Next, the cation (ZaI-4b) is described.

[0508] The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0509] [Chemical Formula 43]

[0510]

[0511] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8.

[0512] 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.

[0513] 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.

[0514] 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.

[0515] 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.

[0516] 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.

[0517] 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.

[0518] Next, we will explain Equation (ZaII).

[0519] In formula (ZaII), R 204 and R 205 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0520] 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.

[0521] 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.

[0522] 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.

[0523] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0524] [Chemical Formula 44]

[0525]

[0526] [Chemical Formula 45]

[0527]

[0528] [Chemical Formula 46]

[0529]

[0530] "M + X - In compounds represented as ", X -represents an organic anion.

[0531] Organic anions are not particularly limited and may include organic anions of 1 or 2 or higher valence.

[0532] 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.

[0533] 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.

[0534] 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.

[0535] 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).

[0536] 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.

[0537] 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).

[0538] As for the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferred.

[0539] Examples of aryl-kil groups having 7 to 14 carbon atoms include benzyl groups, phenethyl groups, naphthylmethyl groups, naphthylethyl groups, and naphthylbutyl groups.

[0540] Examples of sulfonylimide anions include saccharin anions.

[0541] 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.

[0542] 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.

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

[0544] 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.

[0545] As a non-nucleated anion, an anion represented by the following formula (AN1) is also preferred.

[0546] [Chemical Formula 47]

[0547]

[0548] In equation (AN1), R 1 and R 2 Each represents, independently, a hydrogen atom or a substituent.

[0549] 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.

[0550] 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.

[0551] 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.

[0552] 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.

[0553] L represents a divalent connector.

[0554] If there are multiple Ls, each L may be identical or different.

[0555] 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.

[0556] As for L, for example, a group represented by the following formula (AN1-1) is preferred.

[0557] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0558] Among the formulas (AN1-1), * a is R in equation (AN1) 3 Indicates the connection location with.

[0559] * b -C(R in Equation (AN1) 1 )(R 2 Indicates the connection position with )-.

[0560] X and Y each independently represent integers from 0 to 10, and integers from 0 to 3 are preferred.

[0561] R 2a and R 2b Each represents, independently, a hydrogen atom or a substituent.

[0562] 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.

[0563] 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.

[0564] 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.

[0565] Provided that X+Y in Equation (AN1-1) is 1 or greater, and also, R in Equation (AN1-1) 2a and R 2b If all of them are 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.

[0566] * 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.

[0567] In equation (AN1), R 3 Silver represents an organic group.

[0568] 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.).

[0569] 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).

[0570] 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.

[0571] 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.

[0572] The hydrocarbon group of the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents.

[0573] 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.

[0574] 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.

[0575] 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.

[0576] As a non-nucleated anion, an anion represented by the following formula (AN2) is also preferred.

[0577] [Chemical Formula 48]

[0578]

[0579] 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.

[0580] 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.

[0581] 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.

[0582] R 4 and R 5Each represents, independently, 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.

[0583] 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.

[0584] L represents a 2-valent linker. The definition of L is the same as L in Equation (AN1).

[0585] W represents an organic group containing a cyclic structure. Among these, it is preferable that it be a cyclic organic group.

[0586] Examples of phantom organic groups include pyrocyclic groups, aryl groups, and complex pyrocyclic groups.

[0587] 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.

[0588] 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.

[0589] 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.

[0590] 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.

[0591] As an 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.

[0592] As a non-nucleated anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0593] [Chemical Formula 49]

[0594]

[0595] 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.

[0596] 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.

[0597] 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.

[0598] B represents a hydrocarbon group.

[0599] 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.

[0600] As a non-nucleated anion, a disulfonamide anion is also desirable.

[0601] The disulfonamide anion is, for example, N - (SO2-R q It is an anion that appears as )2.

[0602] 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 groups formed by mutual bonding are preferably alkylene groups that may have substituents, more preferably fluoroalkylene groups, and even more preferably perfluoroalkylene groups. The number of carbon atoms in the alkylene groups is preferably 2 to 4.

[0603] In addition, as non-nucleated anions, anions represented by the following formulas (d1-1) to (d1-4) can also be cited.

[0604] [Chemical Formula 50]

[0605]

[0606] [Chemical Formula 51]

[0607]

[0608] In equation (d1-1), R 51 It represents a hydrocarbon group (e.g., an aryl group such as a phenyl group) that may have a substituent (e.g., a hydroxyl group).

[0609] In equation (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).

[0610] Z 2c The hydrocarbon group in the above may be in a straight chain or a branched chain, and may have a cyclic structure. In addition, the carbon atom in the hydrocarbon group (preferably, the carbon atom that is the reducing atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). As for the hydrocarbon group, for example, a group having a norbornyl group that may have a substituent can be provided. The carbon atom forming the norbornyl group may be a carbonyl carbon.

[0611] "Z" in equation (d1-2) 2c -SO3 - It is preferable that the anion be different from the anions represented by the formulas (AN1) to (AN3) described above. For example, Z 2c It is preferable that it be something other than an aryl group. For example, Z 2c -SO3 in - Regarding , the atoms at the α and β positions are preferably atoms other than carbon atoms having a fluorine atom as a substituent. For example, Z 2c is, -SO3 - Regarding this, it is preferable that the atom on the α position and / or the atom on the β position be a reducing atom in the cyclic group.

[0612] In equation (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), and Y 3 represents a straight, branched, or cyclic alkylene, arylene, or carbonyl group, and Rf represents a hydrocarbon group.

[0613] In equation (d1-4), R 53 and R 54 Each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 They may combine with each other to form a ring.

[0614] Organic anions may be used as a single type or as two or more types. Preferred examples are shown below.

[0615] [Chemical Formula 52]

[0616]

[0617] The composition of the present invention is preferably composed of a salt (C) having a group that decomposes by the action of an acid, in order to suppress developmental defects, and more preferably a compound represented by the following general formula (c1) as a photogenerator.

[0618] [Chemical Formula 53]

[0619]

[0620] Among the general formula (c1),

[0621] L represents a single bond or a divalent linker. When there are multiple Ls, the multiple Ls may be identical or different.

[0622] A represents a substance that is decomposed by the action of an acid. When there are multiple As, the multiple As may be identical or different.

[0623] nc represents an integer from 1 to 5.

[0624] Xc represents the n+1 linker.

[0625] Mc + represents a sulfonium ion or an iodine ion.

[0626] In general formula (c1), L represents a single bond or a divalent linker.

[0627] Examples of the divalent linker represented by L include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linkers formed by connecting multiple such groups. Among these, as L, an alkylene group, an arylene group, -arylene group-alkylene group having a fluorine atom or an iodine atom-, a -COO-Rt- group, or an -O-Rt- group is preferred. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0628] As for the arylene group, a phenylene group is preferred.

[0629] 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.

[0630] 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.

[0631] As for Rt, an alkylene group having 1 to 5 carbon atoms is preferred, and a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group is more preferred.

[0632] L is particularly preferably an arylene group, an alkylene group, or a single bond, and most preferably a phenylene group or a single bond.

[0633] In general formula (c1), A represents a group that is decomposed by the action of an acid.

[0634] 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).

[0635] 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.

[0636] As for groups that are removed by the action of acid, for example, groups represented by formulas (Y1) to (Y4) described in the resin (A) above can be cited.

[0637] In general formula (c1), nc represents an integer from 1 to 5. Preferably, nc is an integer from 1 to 3.

[0638] In the general formula (c1), Xc represents an n+1 linker.

[0639] Xc is preferably a directional vent, more preferably a directional vent with 6 to 20 carbon atoms, and more preferably a benzene vent.

[0640] Among the general formula (c1), Mc+ 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, among which the cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) described above are preferably examples.

[0641] The compound represented by the above general formula (c1) is more preferably a compound represented by the following general formula (c2).

[0642] [Chemical Formula 54]

[0643]

[0644] Among the general formula (c2), L, A, nc, and Mc + is L, A, nc, and Mc in the general formula (c1) described above. + It has the same meaning as, and the desirable example is also the same.

[0645] Specific examples of compounds represented by the general formula (c1) are shown below, but are not limited thereto.

[0646] [Chemical Formula 55]

[0647]

[0648] [Chemical Formula 56]

[0649]

[0650] [Chemical Formula 57]

[0651]

[0652] It is also preferable that the photogenerator be at least one selected from the group consisting of compounds (I) to (II).

[0653] (Compound (I))

[0654] 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 comprising 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.

[0655] 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.

[0656] Structural region Y: Anion region 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.

[0657] The above compound (I) satisfies the following condition I.

[0658] 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.

[0659] Condition I is explained in more detail below.

[0660] 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”.

[0661] The acid dissociation constants a1 and a2 of compound PI, to explain more specifically, in the case where the acid dissociation constants of compound PI are calculated, 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.

[0662] 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".

[0663] 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 region 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.

[0664] The acid dissociation constants a1 and a2 are obtained by the acid dissociation constant measurement method described above.

[0665] The above compound PI corresponds to the acid that is generated when compound (I) is irradiated with active light or radiation.

[0666] 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.

[0667] 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.

[0668] 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.

[0669] 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.

[0670] 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.

[0671] 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.

[0672] 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.

[0673] 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).

[0674] In addition, among the following equations (AA-1) to (AA-3) and equations (BB-1) to (BB-6), * indicates a bonding position.

[0675] In formula (AA-2), R A represents a monovalent organic group. R A The monovalent organic group that appears is not particularly limited, but examples include cyano groups, trifluoromethyl groups, and methanesulfonyl groups.

[0676] [Chemical Formula 58]

[0677]

[0678] [Chemical Formula 59]

[0679]

[0680] 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.

[0681] (Compound (II))

[0682] 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.

[0683] Structural region Z: Non-ionic region capable of neutralizing acid

[0684] 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.

[0685] 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.

[0686] 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.

[0687] The acid dissociation constant a1 is obtained by the above-described method for measuring acid dissociation constants.

[0688] The above compound PII corresponds to the acid that is generated when compound (II) is irradiated with active light or radiation.

[0689] 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.

[0690] 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.

[0691] 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.

[0692] [Chemical Formula 60]

[0693] non-shared electron pairs

[0694] 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.

[0695] Examples of non-cation sites that compounds (I) and (II) may have are provided.

[0696] [Chemical Formula 61]

[0697]

[0698] [Chemical Formula 62]

[0699]

[0700] As a photogenerator, compounds B-1 to B-3 used in the examples may be used, for example.

[0701] The content of the photogenerative 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, in order to make the cross-sectional shape of the formed pattern more rectangular. The above content is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, and more preferably 25.0 mass% or less, with respect to the total solid content of the composition of the present invention.

[0702] The photocatalytic agent may be used as a single type or as two or more types.

[0703] [Acid Diffusion Control Agent]

[0704] The composition of the present invention may further include an acid diffusion control agent.

[0705] 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.

[0706] 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).

[0707] Examples of compounds (DC) include onium salt compounds (DD) of acids that are relatively weak acids with respect to acids generated from photogenerative agents (e.g., salts (C), etc.), and basic compounds (DE) whose basicity is reduced or lost upon irradiation with active light or radiation.

[0708] 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.

[0709] 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.

[0710] 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.

[0711] 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%.

[0712] 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.

[0713] [Hypohydrophobic resin]

[0714] The composition of the present invention may further include a hydrophobic resin different from resin (A).

[0715] 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.

[0716] 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.

[0717] 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 may be substituted in the side chain.

[0718] Examples of hydrophobic resins include compounds described in paragraphs

[0275] to

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

[0719] 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%.

[0720] 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.

[0721] [Surfactant]

[0722] 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.

[0723] Fluorine-based and / or silicone-based surfactants are preferred.

[0724] Examples of fluorine-based and / or silicone-based surfactants include the surfactants disclosed in paragraphs

[0218] and

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

[0725] 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%.

[0726] 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.

[0727] [solvent]

[0728] The composition of the present invention preferably includes a solvent.

[0729] 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).

[0730] 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.

[0731] 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.

[0732] 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.

[0733] 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.

[0734] [Other additives]

[0735] 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).

[0736] 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 reduces its solubility in an organic developer.

[0737] The composition of the present invention is suitably used as a photosensitive composition for EUV exposure.

[0738] EUV light has a wavelength of 13.5 nm, which is shorter than that of ArF light (wavelength 193 nm), so the number of incident photons is lower when exposed with the same sensitivity. Consequently, the influence of "photon shot noise," where the number of photons becomes non-uniform probabilistically, is significant, leading to deterioration of line edge roughness (LER) and bridge defects. To reduce photon shot noise, one method is to increase the number of incident photons by increasing the exposure amount, but this is a trade-off with the requirement for high sensitivity.

[0739] When the value of A obtained by the following equation (1) is high, the absorption efficiency of EUV light and electron beams of the resist film formed from the resist composition is increased, which is effective in reducing photon shot noise. The value of A represents the absorption efficiency of EUV light and electron beams of the mass ratio of the resist film.

[0740] Equation (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)

[0741] The A value is preferably 0.120 or higher. Although there is no specific upper limit, if the A value is too large, the EUV light and electron beam transmittance of the resist film decreases and the optical profile within the resist film deteriorates, making it difficult to obtain a good pattern shape; therefore, 0.240 or lower is preferable, and 0.220 or lower is more preferable.

[0742] In addition, in Equation (1), [H] represents the molar ratio of hydrogen atoms derived from the solid content to the total atoms of the solid content in the sensitizing or radiation-reducing resin composition, [C] represents the molar ratio of carbon atoms derived from the solid content to the total atoms of the solid content in the sensitizing or radiation-reducing resin composition, [N] represents the molar ratio of nitrogen atoms derived from the solid content to the total atoms of the solid content in the sensitizing or radiation-reducing resin composition, [O] represents the molar ratio of oxygen atoms derived from the solid content to the total atoms of the solid content in the sensitizing or radiation-reducing resin composition, [F] represents the molar ratio of fluorine atoms derived from the solid content to the total atoms of the solid content in the sensitizing or radiation-reducing resin composition, and [S] represents the [I] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition.

[0743] For example, when a resist composition comprises an acid-degradable resin, a photogenerative agent, an acid diffusion control agent, and a solvent, the acid-degradable resin, the photogenerative agent, and the acid diffusion control agent correspond to the solid content. That is, the total atoms of the total solid content correspond to the sum of the total atoms derived from the resin, the total atoms derived from the photogenerative agent, and the total atoms derived from the acid diffusion control agent.

[0744] For example, [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids, and, as explained based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the acid-degradable resin, hydrogen atoms derived from the photogenerative agent, and hydrogen atoms derived from the acid diffusion control agent to the sum of the total atoms derived from the acid-degradable resin, the total atoms derived from the photogenerative agent, and the total atoms derived from the acid diffusion control agent.

[0745] If the structure and content of the constituent components of the total solid content in the resist composition are already known, the value of A can be calculated by determining the ratio of the contained atoms. Furthermore, even if the constituent components are unknown, the ratio of the constituent atoms can be calculated for the resist film obtained by evaporating the solvent components of the resist composition using analytical methods such as elemental analysis.

[0746] <Desensitizing photoreactive or radiation-sensitive film, pattern formation method>

[0747] 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.

[0748] 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.

[0749] Process 1: A process of forming a photosensitive or radiation-sensitive film on a substrate using a composition of the present invention.

[0750] Process 2: Process of exposing a photosensitive or photosensitive film

[0751] Process 3: A process of developing the exposed photosensitive or photosensitive film using a developer.

[0752] Below, the sequence of each of the above processes will be explained in detail.

[0753] (Process 1: Process for forming a photosensitive or radioactive film)

[0754] Process 1 is a process of forming a photosensitive or photosensitive film on a substrate by means of the composition of the present invention.

[0755] As a method for forming a photosensitive or photosensitive film on a substrate by means of the composition of the present invention, for example, a method of applying the composition of the present invention onto a substrate may be used.

[0756] 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.

[0757] The composition of the present invention can be applied by a suitable application method, such as a spinner or a coater, onto a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit devices. Spin coating using a spinner is preferred as the application method. When performing spin coating using a spinner, the rotation speed is preferably 1,000 to 3,000 rpm (rotations per minute).

[0758] After applying the composition of the present invention, the substrate may be dried and a photosensitive or radiation-sensitive film may be formed. Additionally, if necessary, various underlay films (inorganic films, organic films, anti-reflective films) may be formed on the underside of the photosensitive or radiation-sensitive film.

[0759] 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.

[0760] The film thickness of the desensitizing or radiation-sensitive 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, 10 to 65 nm is more preferred as the film thickness of the desensitizing or radiation-sensitive film, and 15 to 50 nm is more preferred. When using ArF immersion exposure, 10 to 120 nm is more preferred as the film thickness of the desensitizing or radiation-sensitive film, and 15 to 90 nm is more preferred.

[0761] In addition, a top coat may be formed on the upper layer of a photosensitive or radiation-sensitive film using a top coat composition.

[0762] It is preferable that the top coat composition be uniformly applied to the upper layer of the resist film without mixing with the light-sensitive or radiation-sensitive 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.

[0763] For example, it is preferable to form a top coat containing a basic compound as described in Japanese Patent Publication No. 2013-61648 on a light-sensitive or radiation-sensitive 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.

[0764] 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.

[0765] (Process 2: Photolithography Process)

[0766] Process 2 is a process of exposing a photosensitive or radiation-sensitive film.

[0767] As a method of exposure, an active light or radiation may be irradiated onto a formed desensitizing or radiation-sensitive film through a predetermined mask.

[0768] Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and far ultraviolet light with a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams are particularly preferred.

[0769] 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.

[0770] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0771] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0772] Heating can be performed using means provided in a conventional exposure machine and / or developer, or by using a hot plate, etc.

[0773] This process is also called post-exposure baking.

[0774] (Process 3: Development Process)

[0775] Process 3 is a process of forming a pattern by developing an exposed photosensitive or photosensitive film using a developer.

[0776] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0777] 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).

[0778] 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.

[0779] 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.

[0780] The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0781] 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.

[0782] 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.

[0783] 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.

[0784] 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.

[0785] (Other processes)

[0786] The above pattern forming method preferably includes a process of cleaning using a rinse solution after process 3.

[0787] 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.

[0788] An appropriate amount of surfactant may be added to the rinse solution.

[0789] The rinsing solution used in the rinsing process after the development process using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent may be used. It is preferable to use a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0790] 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).

[0791] In addition, the pattern forming method may include a heating process (Post Bake) after the rinsing process. Through this process, the developer and rinsing solution 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).

[0792] 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.

[0793] 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.

[0794] 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 particularly 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.

[0795] 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.

[0796] 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).

[0797] 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. The lower limit is not particularly restricted, but 0 mass ppt or more is preferred.

[0798] In organic treatment solutions such as rinse solutions, a conductive compound may be added to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and continuous electrostatic discharge. The conductive compound is not particularly limited, but methanol may be cited as an example. The amount added is not particularly limited, but in order to maintain desirable developing or rinsing characteristics, it is preferable to be 10 mass% or less, and more preferable to be 5 mass% or less. The lower limit is not particularly limited, but it is preferable to be 0.01 mass% or more.

[0799] 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.

[0800] Method for manufacturing an electronic device

[0801] The present specification relates to a method for manufacturing an electronic device comprising the pattern forming method described above, and to an electronic device manufactured by the method.

[0802] 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.).

[0803] Examples

[0804] 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.

[0805] The various components used in the resist compositions of the examples and comparative examples are described below.

[0806] Suzy (A)

[0807] As resin (A), P-1 to P-10 were used.

[0808] In addition, RP-1 to RP-4 were used as resins other than resin (A). For convenience, RP-1 to RP-4 are also listed in the column for resin (A) in Table 1 below.

[0809] Resin (A) was used by synthesizing it in accordance with the synthesis method of resin P-1 (Synthesization Example 3) described below.

[0810] Table 1 shows the composition ratio (mol% ratio; corresponding in order from left), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit as described below.

[0811] In addition, the weight-average molecular weight (Mw) and dispersion (Pd=Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). Also, the content of repeating units is, 13 It was measured by C-NMR (nuclear magnetic resonance).

[0812] [Table 1]

[0813]

[0814] The structures of each repeating unit a-1 to a-6, b-1 to b-4, c-1 to c-7, and d-1 shown in Table 1 are shown below.

[0815] In addition, if the following repeating unit is a repeating unit having a phenolic hydroxyl group, the ClogP value of the anionic state in which the hydrogen atom of the phenolic hydroxyl group is dissociated is also shown for the monomer corresponding to said repeating unit. The measurement method is as described above.

[0816] [Chemical Formula 63]

[0817]

[0818] [Chemical Formula 64]

[0819]

[0820] [Chemical Formula 65]

[0821]

[0822] [Chemical Formula 66]

[0823]

[0824] Examples of P-3 synthesis are shown below. Other resins (A) were synthesized in the same way.

[0825] (Synthesis of P-3)

[0826] [Chemical Formula 67]

[0827]

[0828] First, 15.42 g of compound (a-1m-Ac), 11.92 g of compound (b-1m), 17.91 g of compound (c-1m), and 4.61 g of polymerization initiator V-601 (manufactured by Wako Junyaku Kogyo Co., Ltd.) were dissolved in 81.42 g of cyclohexanone. 54.28 g of cyclohexanone was placed in a reaction vessel and dropped into a system at 85°C under a nitrogen gas atmosphere for 4 hours. After heating and stirring the reaction solution for 2 hours, it was cooled to room temperature.

[0829] 111.33 g of methanol and 27.83 g of triethylamine were added to the above reaction solution, heated and stirred at 70°C for 6 hours, and then cooled to room temperature.

[0830] The above reaction solution was diluted by adding 90.47 g of ethyl acetate. The diluted solution was added dropwise to 2714 g of hexane / ethyl acetate = 9 / 1 (mass ratio), the polymer was precipitated, and the solution was filtered. The filtered solid was washed using 300 g of hexane / ethyl acetate = 9 / 1 (mass ratio). Afterward, the solid after washing was subjected to vacuum drying to obtain 27.5 g of resin (P-3).

[0831] The compositional ratio (molar percentage ratio; corresponding in order from left) of each repeating unit in resin (P-3) was 40 / 25 / 35. As described above, the compositional ratio is, 13It was measured by C-NMR. The weight-average molecular weight (Mw) of the resin (P-3) was 6000, and the degree of dispersion (Mw / Mn) was 1.60.

[0832] In addition, the weight-average molecular weight and dispersion of the resin were measured by GPC (carrier: THF) as described above.

[0833] <Mining Agent (B)>

[0834] The structure of the photocatalytic agent (B) used is shown below.

[0835] [Chemical Formula 68]

[0836]

[0837] Acid Diffusion Control Agent

[0838] The structure of the acid diffusion control agent used is shown below.

[0839] [Chemical Formula 69]

[0840]

[0841] Hydrophobic resin

[0842] The structure of the hydrophobic resin used is shown below.

[0843] [Chemical Formula 70]

[0844]

[0845] Surfactants

[0846] The surfactants used are shown below.

[0847] W-1: Megapark R08 (Dai Nippon Ink Kagaku High School Co., Ltd.)

[0848] Solvent

[0849] The solvents used are shown below.

[0850] S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane)

[0851] S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol)

[0852] S-3: Ethyl lactate

[0853] S-4: γ-beautyllactone

[0854] <Preparation of Resist Composition>

[0855] The components shown in Table 2 were dissolved in the solvent shown in Table 2 to prepare a solution with the solid content concentration shown in Table 2, and this was filtered through a polyethylene filter having a pore size of 0.02 μm to prepare a resist composition.

[0856] In addition, solid content refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples.

[0857] In addition, the "Mass %" column in the table indicates the content (mass%) of each component relative to the total solid content in the resist composition. Furthermore, the table lists the types of solvents used and their mass ratios.

[0858] [Table 2]

[0859]

[0860] <Pattern Formation Method (1): EB Exposure, Alkaline Development (Positive)>

[0861] The above resist composition was applied using a Tokyo Electron spin coater Mark 8 onto a 6-inch Si wafer that had been previously treated with hexamethyldisilasein (HMDS), and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Here, 1 inch is 0.0254 m.

[0862] In addition, the same result is obtained even if the above Si wafer is changed to a chromium substrate.

[0863] The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography device (HL750 manufactured by Hitachi Seisakusho Inc., acceleration voltage 50 KeV). At this time, lithography was performed to form a 1:1 line and space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, then developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water, rotated at a rotational speed of 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds, thereby obtaining a resist pattern with a line width of 50 nm and a 1:1 line and space pattern.

[0864] <Performance Evaluation>

[0865] [LWR Performance]

[0866] A line and space pattern (line / space = 1 / 1) with a line width of 50 nm, resolved by the method described above, was observed from the top of the pattern using a scanning electron microscope (SEM (Hitachi Seisakusho S-9380II)). The line width of the pattern was observed at random points (160 points), and the standard deviation (σ) was calculated. The measurement deviation of the line width was evaluated as 3σ (nm), and the value of 3σ was defined as LWR (nm). The smaller the value of LWR, the better the LWR performance.

[0867] [Pattern shape]

[0868] A line and space pattern (line / space = 1 / 1) with a line width of 50 nm, resolved by the method described above, was observed in cross-section using a scanning electron microscope (SEM (Hitachi Seisakusho S-9380II)). The pattern cross-section was evaluated as rectangular if it was vertical, T-top if the bottom of the pattern was thinner than the top, and round top if the top of the pattern was thinner than the bottom. For practical purposes, a rectangular shape is preferred.

[0869] [Long-term stability]

[0870] The amount of exposure when forming a 50nm line and space pattern (line / space = 1 / 1) obtained by the above method was measured and set as the "amount of exposure before time."

[0871] In addition, the above-described resist composition was stored at 40°C for 3 months, and a 50 nm line and space pattern (line / space = 1 / 1) was formed using the same pattern formation method as described above. The amount of exposure when the pattern was formed was measured and referred to as the "amount of exposure after time."

[0872] The rate of change in sensitivity was calculated and evaluated according to the following formula. In addition, B or higher is desirable for practical purposes, and A is more desirable.

[0873] Change in sensitivity rate (%) = Exposure amount after time / Exposure amount before time × 100

[0874] A: Sensitivity change rate less than 1%

[0875] B: Rate of change in sensitivity is 1% or more and less than 2%

[0876] C: Sensitivity change rate is 2% or more and less than 5%

[0877] D: Sensitivity change rate of 5% or more

[0878] Table 3 below shows the resist composition used in each example and comparative example, and the results of each example and comparative example.

[0879] [Table 3]

[0880]

[0881] (EUV lithography)

[0882] (Examples 2-1 to 2-20, Comparative Examples 2-1 to 2-4)

[0883] <Pattern formation method (3): EUV exposure, alkaline development (positive)>

[0884] A composition AL412 (manufactured by Brewer Science) for forming a sublayer was applied onto a silicon wafer and baked at 205°C for 60 seconds to form a sublayer with a thickness of 20 nm. On top of this, a resist composition shown in Table 2 was applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 50 nm.

[0885] Pattern irradiation was performed on a silicon wafer having a resist film obtained using an EUV lithography device (Exitech Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle, a mask with a line size of 50 nm and a line:space ratio of 1:1 was used.

[0886] After exposure, the resist film was baked at 100°C for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. Afterward, the film was spin-dried to obtain a positive pattern.

[0887] <Performance Evaluation>

[0888] Each of the obtained resists was evaluated using the same method as above. The evaluation results are listed in Table 4.

[0889] [Table 4]

[0890]

[0891] From the results of Tables 3 and 4, it was found that the resist composition used in the examples can establish high-level LWR performance, pattern shape, and long-term stability in the formation of ultrafine patterns.

[0892] The resist composition used in Comparative Examples 1-4 includes a resin having repeating unit (i), repeating unit (ii), and repeating unit (iii), but the repeating unit after repeating unit (ii) (specifically, repeating unit b-3, etc.) is decomposed by the action of acid is equivalent to (identical to) repeating unit (i) (specifically, repeating unit a-1), so the effect of the present invention is not obtained.

[0893] Industrial applicability

[0894] According to the present invention, a desensitizing light-sensitive or radiation-sensitive resin composition can be provided that can establish high-level LWR performance, pattern shape, and stability over time in the formation of ultrafine patterns (e.g., line width or space width of 50 nm or less).

[0895] In addition, the present invention may provide a photosensitive or radiation-sensitive film using the photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

[0896] 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.

[0897] This application is based on Japanese patent application filed on August 31, 2022 (JP 2022-138717), the contents of which are incorporated herein by reference.

Claims

Claim 1 A photosensitive or radiation-sensitive resin composition containing a resin having a repeating unit (i) represented by the following general formula (a-1), a repeating unit (ii) represented by the following general formula (a-2), and a repeating unit (iii). provided, provided that if the repeating unit (ii) has a group that decomposes by the action of an acid, the repeating unit after the repeating unit (ii) is decomposed by the action of an acid does not correspond to the repeating unit (i). (i) A repeating unit having a phenolic hydroxyl group, and in a monomer corresponding to the repeating unit, a repeating unit having a ClogP value in an anionic state where the hydrogen atom of the phenolic hydroxyl group is dissociated is -7.50 or higher and less than -1.

20. (ii) A repeating unit having a phenolic hydroxyl group, and in a monomer corresponding to the repeating unit, a repeating unit having a ClogP value in an anionic state where the hydrogen atom of the phenolic hydroxyl group is dissociated is -0.70 or higher and less than 5.

00. (iii) Phenolic A repeating unit that does not have a hydroxyl group and has a group that decomposes upon the action of an acid to increase polarity [Chemical Formula 1] In the general formula (a-1), R a1 represents a hydrogen atom or an alkyl group. 1 represents a single bond, or -C(=O)O-. m represents an integer from 0 to 2. n represents an integer from 2 to 3. R a2 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these. l represents an integer from 0 to 4, and if l is 2 or more, multiple R a2 They may be identical or different, and may combine to form rings.[Chemical Formula 2] In general formula (a-2), R a3 represents a hydrogen atom or an alkyl group. 2 represents a single bond, or -C(=O)O-. o represents an integer from 0 to 2. p represents an integer from 1 to 2. R a4 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these. q represents an integer from 0 to 4, and if q is 2 or more, multiple R a4 They may be identical or different from each other, and may combine to form a ring. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 A photosensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (iii) is at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (a-3) and a repeating unit represented by the following general formula (a-4). [Chemical Formula 3] In general formula (a-3), R a5 , R a15 Each represents a hydrogen atom or an alkyl group independently. 3 represents a single bond, or -C(=O)O-. r represents an integer from 0 to 2. s represents an integer from 0 to 4. R p1 represents the group that is defused by the action of acid. t represents an integer from 0 to 4. R p2 represents the group that is defused by the action of the acid. At least one of s or t is an integer greater than or equal to 1. u represents an integer from 0 to (5+r×4-st). R a6 represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by a combination of two or more of these. If u is 2 or more, multiple R a6 They may be identical or different from each other, and may combine to form rings. Also, R a6 and R p1 , R a6 and R p2 , R p1 and R p2 Each may combine with others to form a ring. R a15 and L 3 These bonding aromatic rings may bond with each other to form a ring.[Chemical Formula 4] In general formula (a-4), R a7 R represents a hydrogen atom or an alkyl group. p3 It represents the energy that is depleted by the action of acid. Claim 6 A desensitizing photoreactive or radiation-reducing resin composition according to claim 5, wherein the repeating unit (iii) is a repeating unit represented by the general formula (a-3). Claim 7 A desensitizing photoreactive or radiation-reducing resin composition according to claim 1, wherein the repeating unit (i) and the repeating unit (ii) are repeating units that do not have groups decomposed by the action of acid. Claim 8 A photosensitive or radiation-sensitive resin composition according to claim 1, further comprising a compound that generates acid upon irradiation with active light or radiation. Claim 9 A photosensitive or radiation-sensitive film formed by the photosensitive or radiation-sensitive resin composition described in claim 1. Claim 10 A pattern forming method comprising: a process of forming a photosensitive or photosensitive film on a substrate according to the composition described in claim 1; a process of exposing the photosensitive or photosensitive film to light; and a process of developing the exposed photosensitive or photosensitive film using a developer. Claim 11 A method for manufacturing an electronic device comprising the pattern forming method described in claim 10.

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