Photosensitive radioactive or radiosensitive linear resin compositions, photosensitive radioactive or radiosensitive linear films, patterning methods, and manufacturing methods of electronic devices.

Abstract

The present invention provides a photosensitive radioactive or radioactive linear resin composition, a photosensitive radioactive or radioactive linear film using the above-mentioned photosensitive radioactive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing an electronic device. The photosensitive radioactive or radioactive linear resin composition comprises: a resin containing repeating units having acid groups with a pKa of 8.0 or more and 12.0 or less, repeating units having acid groups with a pKa of less than 8.0 (a2), and repeating units containing at least one fluorine atom and not having acid groups with a pKa of 12.0 or less (a3); a resin containing repeating units having phenolic hydroxyl groups (b1) and repeating units having groups that decompose under the action of acid and increase in polarity (b2), and not containing repeating units that generate acid by irradiation with photochemical rays or radiation; and a compound that generates acid by irradiation with photochemical rays or radiation.

Description

Technical Field

[0001] This invention relates to photosensitive radioactive or radioactive linear resin compositions, photosensitive radioactive or radioactive linear films, patterning methods, and manufacturing methods of electronic devices. More specifically, this invention relates to ultra-microlithography processes applicable to manufacturing processes of large-scale integrated circuits (LSI) and high-capacity microchips, nanoimprint dies fabrication processes, and high-density information recording media, as well as photosensitive radioactive or radioactive linear resin compositions, photosensitive radioactive or radioactive linear films, patterning methods, and manufacturing methods of electronic devices suitable for other photosensitive etching processes. Prior Technology

[0002] Previously, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations), microfabrication was achieved using photoresist lithography. In recent years, with the increasing integration of integrated circuits, there is a demand for forming ultra-fine patterns in sub-micron or quarter-micron regions. Accompanying this, the exposure wavelength has shifted from gamma rays to i-rays, and further to KrF excimer lasers, showing a trend towards shorter wavelengths. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as the light source has been developed. Furthermore, as a technique to further improve resolution, a liquid immersion method is being developed, in which a high-refractive-index liquid (hereinafter referred to as "immersion solution") is filled between the projection lens and the sample.

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is also under development. Along with this, photoresist compositions that effectively sense various photochemical rays or radiation have been developed.

[0004] As resins that can be used in photosensitive or radiosensitive linear resin compositions, various resins are known, such as resins containing fluorine atoms described in Patent Documents 1 and 2. In addition, Patent Document 3 describes a pattern forming method, which includes the steps of forming a film from a photosensitive radioactive or radiosensitive linear resin composition, and forming a top coating containing a resin containing fluorine atoms on the film. [Previous Technical Documents] [Patent Literature]

[0005] Patent Document 1: Japanese Patent Application Publication No. 2013-15590 Patent Document 2: Japanese Patent Application Publication No. 2011-33844 Patent Document 3: Japanese Patent Application Publication No. 2014-178542 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] Fluorine-containing resins, typically hydrophobic resins, are added to photosensitive or radiosensitive linear resin compositions and are unevenly distributed on the surface of the photosensitive or radiosensitive linear film, thus hydrophobizing the surface. However, when the inventors of this invention studied photosensitive or radiosensitive linear resin compositions containing conventional hydrophobic resins, they found that there was room for improvement in the line width roughness (LWR) performance during pattern formation. LWR performance refers to the ability to reduce the LWR of a pattern. Furthermore, for photosensitive or radiosensitive linear resin compositions, the manufacturing process should require that the time elapsed from exposure to post-exposure baking (PEB) has little impact on performance; that is, PED (Post Exposure Time Delay) stability is excellent.

[0008] The present invention was made in view of the above-mentioned problems, and its objective is to provide a photosensitive or radiosensitive linear resin composition with excellent LWR performance and PED stability. Furthermore, the objective of this invention is to provide a photosensitive or radiosensitive linear film using the above-mentioned photosensitive radiosensitive or radiosensitive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices. [Methods for solving problems]

[0009] The inventors have discovered that the above-mentioned problems can be solved by using a resin comprising repeating units having acid groups with a pKa of 8.0 or more and 12.0 or less, repeating units having acid groups with a pKa of less than 8.0, and repeating units containing at least one fluorine atom and not having acid groups with a pKa of 12.0 or less.

[0010] That is, the inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[0011] [1] A photosensitive radioactive or radiosensitive linear resin composition comprising at least the following (A), (B) and (C). (A) A repeating unit (a1) comprising an acid group having a pKa of 8.0 or more and 12.0 or less, represented by the following general formula (a1-1) or (a1-2). Repeating units (a2) with acid groups having a pKa less than 8.0, and A resin containing at least one fluorine atom and without repeating units (a3) ​​of acid groups with a pKa of less than 12.0. (B) Contains repeating units (b1) having phenolic hydroxyl groups, and Repeating unit (b2) with groups that decompose under acidic conditions and have increased polarity. Furthermore, the resin does not contain repeating units that produce acid through exposure to photochemical rays or radiation. (C) Compounds that produce acids through exposure to photochemical rays or radiation.

[0012] [Chemical Formula 1]

[0013] In the above general formula, Ra1 represents a hydrogen atom or an alkyl group. Ra2 represents a halogen atom, alkyl, aryl, heteroaryl, alkoxy, alkylthio, alkoxycarbonyl, or alkylcarbonyloxy. When there are complex numbers of Ra², these complex numbers of Ra² can be the same or different. L1 represents a single bond or -C(=O)O-. L2 represents a linker consisting of at least one of the groups consisting of a single bond, or selected from -C(=O)O-, alkyl, cycloalkyl and aryl groups. m represents an integer from 0 to 2. n1 represents an integer greater than or equal to 1 and less than (5+2m). n2 represents an integer from 1 to 3. k1 represents an integer greater than 0 and less than (5+2m-n1). [2] As described in [1], the photosensitive radioactive or radiosensitive linear resin composition, wherein the repeating unit (a1) is represented by the general formula (a1-1), and m in the general formula (a1-1) represents 0 or 1. [3] The photosensitive radioactive or radiosensitive linear resin composition as described in [1] or [2], wherein the repeating unit (a1) is represented by the general formula (a1-1), and L1 in the general formula (a1-1) represents a single bond. [4] The photosensitive radioactive or radiosensitive linear resin composition as described in any one of [1] to [3], wherein the repeating unit (a3) ​​comprises an alkyl group having three or more fluorine atoms as substituents. [5] The photosensitive radioactive or radiosensitive linear resin composition as described in any one of [1] to [4], wherein the repeating unit (a3) ​​is represented by the following general formula (a3-1).

[0014] [Chemical Formula 2]

[0015] In general formula (a3-1), Ra3 represents a hydrogen atom or an alkyl group. Ra4 represents an alkyl group having three or more fluorine atoms as substituents. [6] The photosensitive radioactive or radiosensitive linear resin composition as described in any one of [1] to [5], wherein the pKa of the acid group of the repeating unit (a2) is 0.0 or more and 6.0 or less. [7] The photosensitive radioactive or radiosensitive linear resin composition as described in any one of [1] to [6], wherein the repeating unit (a2) is represented by the following general formula (a2-1).

[0016] [Chemical Formula 3]

[0017] In general formula (a2-1), Ra5 represents a hydrogen atom or an alkyl group. L3 represents a linker group consisting of a single bond or at least one of the groups selected from alkyl, cycloalkyl, and aryl groups. p represents an integer from 1 to 3. [8] A photosensitive radioactive or radiosensitive linear resin composition comprising at least (AX), (B) and (C) below. (AX) contains repeating units (ax1) with an acid group having a pKa of 8.0 or higher and 12.0 or lower. Repeating units (a2) with acid groups having a pKa less than 8.0, and A repeating unit (a3) ​​containing at least one fluorine atom and no acid group with a pKa below 12.0, wherein the resin film made solely of resin has a dissolution rate of 0.002 nm / s or higher in an alkaline developing solution. (B) Contains repeating units (b1) having phenolic hydroxyl groups, and Repeating unit (b2) with groups that decompose under acidic conditions and have increased polarity. Furthermore, the resin does not contain repeating units that produce acid through exposure to photochemical rays or radiation. (C) Compounds that produce acids through exposure to photochemical rays or radiation. [9] The photosensitive or radiosensitive linear resin composition as described in [8], wherein the film made solely of resin of the above (AX) dissolves at a rate of 0.01 nm / s or more in an alkaline developing solution.

[10] A photosensitive ray or radiosensitive linear membrane formed from a photosensitive ray or radiosensitive linear resin composition described in any one of [1] to [9].

[11] A pattern forming method comprising: a process of forming a photosensitive radioactive or radioactive linear resin composition on a substrate using any one of [1] to [9]; a process of exposing the photosensitive radioactive or radioactive linear film; and a process of developing the exposed photosensitive radioactive or radioactive linear film using a developing solution.

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

[11] . [Invention Effects]

[0018] According to the present invention, a photosensitive or radiosensitive linear resin composition with excellent LWR performance and PED stability can be provided. Furthermore, according to the present invention, it is possible to provide a photosensitive or radiosensitive linear film using the above-described photosensitive radiosensitive or radiosensitive linear resin composition, a pattern forming method, and a manufacturing method for electronic devices. Implementation

[0019] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0020] In this specification, "photochemical rays" or "radiation" refers to, for example, the brightline spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, the term "light" refers to photochemical rays or radiation. In this specification, the term "exposure" unless otherwise specified includes not only exposure using bright-line spectra such as mercury lamps, far-ultraviolet rays such as excimer lasers, extreme ultraviolet rays, X-rays and EUV, but also depiction using particle beams such as electron beams and ion beams. In this specification, the term "~" is used to indicate that the values ​​before and after it are included as lower and upper limits.

[0021] In this specification, (meth)acrylate means at least one of acrylate and methacrylate. Also, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid.

[0022] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (also known as "molecular weight distribution") (Mw / Mn) of the resin are defined as polystyrene conversion values ​​obtained by GPC determination using a GPC (Gel Permeation Chromatography) apparatus (Tosoh HLC-8120GPC, solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector)

[0023] Regarding the use of groups (atomic clusters) in this specification, as long as it does not depart from the spirit of this invention, any expression that does not specify substitution or non-substitution includes both groups without substituents and groups containing substituents. For example, the term "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred.

[0024] Unless otherwise specified, the bonding orientation of the divalent groups described in this specification is not particularly limited. For example, in compounds represented by the formula "XYZ", when Y is -COO-, Y can be either -CO-O- or -O-CO-. The above compounds can be either "X-CO-OZ" or "XO-CO-Z".

[0025] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution. Specifically, it is a value calculated using software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0026] Furthermore, pKa can also be obtained using molecular orbital calculations. One specific method is to calculate it using the H+ dissociation free energy in aqueous solution based on thermodynamic cycles. Regarding methods for calculating the H+ dissociation free energy, for example, it can be calculated using DFT (Density Functional Theory), but it is not limited to this; various other methods have been reported in the literature. In addition, there are several software programs that can perform DFT, such as Gaussian16.

[0027] In this specification, pKa, as mentioned above, refers to the value obtained by using software package 1 to calculate the value based on a database of Hammett substituent constants and known literature values. However, when pKa cannot be calculated using this method, the value obtained by using Gaussian 16 based on DFT (density functional theory) is adopted. In this specification, pKa, as shown above, refers to "pKa in aqueous solution". However, if the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0028] In this specification, "solid component" refers to a component that forms a photosensitive or radiosensitive linear film and does not contain solvents. Furthermore, any component that forms a photosensitive or radiosensitive linear film is considered a solid component even if it is in liquid form.

[0029] <Photosensitive or radiosensitive linear resin composition> The photosensitive radioactive or radioactive linear resin composition of the present invention (also referred to as "the composition of the present invention") contains at least the following (A), (B) and (C) photosensitive or radioactive linear resin compositions. (A) A repeating unit (a1) comprising an acid group having a pKa of 8.0 or more and 12.0 or less, represented by the following general formula (a1-1) or (a1-2). Repeating units (a2) with acid groups having a pKa less than 8.0, and A resin containing at least one fluorine atom and without repeating units (a3) ​​of acid groups with a pKa of less than 12.0. (B) Contains repeating units (b1) having phenolic hydroxyl groups, and Repeating unit (b2) with groups that decompose under acidic conditions and have increased polarity. Furthermore, the resin does not contain repeating units that produce acid through exposure to photochemical rays or radiation. (C) Compounds that produce acids through exposure to photochemical rays or radiation.

[0030] [Chemical Formula 4]

[0031] In the above general formula, Ra1 represents a hydrogen atom or an alkyl group. Ra2 represents a halogen atom, alkyl, aryl, heteroaryl, alkoxy, alkylthio, alkoxycarbonyl, or alkylcarbonyloxy. When there are complex numbers of Ra², these complex numbers of Ra² can be the same or different. L1 represents a single bond or -C(=O)O-. L2 represents a linker consisting of at least one of the groups consisting of a single bond, or selected from -C(=O)O-, alkyl, cycloalkyl and aryl groups. m represents an integer from 0 to 2. n1 represents an integer greater than or equal to 1 and less than (5+2m). n2 represents an integer from 1 to 3. k1 represents an integer greater than 0 and less than (5+2m-n1).

[0032] The reasons why the present invention can provide a photosensitive radioactive or radioactive linear resin composition with excellent LWR performance and PED stability have not been explained in detail, but the inventors presume the following: Component (A) of the present invention comprises repeating units having acid groups with a pKa of 8.0 or higher and 12.0 or lower, repeating units having acid groups with a pKa of less than 8.0, and repeating units containing at least one fluorine atom and not having acid groups with a pKa of 12.0 or lower. The interaction between this resin and the acid-degradable resin of component (B) is within an appropriate range, therefore, it is considered to have excellent LWR performance and PED stability. Furthermore, for the same reason, it is considered to have excellent resolution, and excellent LWR performance can be maintained even after a certain period of time since the preparation of the photosensitive radioactive or radioactive linear resin composition.

[0033] In the composition of the present invention, (A), (B) and (C) are preferably separate components.

[0034] The composition of this invention is typically a photoresist composition, which can be a positive photoresist composition or a negative photoresist composition. The composition of this invention can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development. The photoresist composition of this invention can be a chemically amplified photoresist composition or a non-chemically amplified photoresist composition. Typically, the composition of this invention is a chemically amplified photoresist composition. The photosensitive radioactive or radiosensitive linear film formed from the components of the present invention is typically a photoresist film. Hereinafter, the various components of the composition of the present invention will be described in detail.

[0035] [(A) ingredient] The (A) component contained in the composition of the present invention is a resin represented by the above general formula (a1-1) or (a1-2), comprising a repeating unit (a1) having an acid group having a pKa of 8.0 or more and 12.0 or less, a repeating unit (a2) having an acid group having a pKa of less than 8.0, and a repeating unit (a3) ​​containing at least one fluorine atom and not having an acid group having a pKa of 12.0 or less. Component (A) is also known as "resin (A)".

[0036] In this invention, for the monomer (M) corresponding to each repeating unit, the value obtained by calculation using the aforementioned software package 1 (or, if the pKa cannot be calculated by this method, the value obtained using Gaussian 16 based on DFT) is used as the pKa of the acid group possessed by each repeating unit. When the monomer (M) has two or more acid groups, two or more pKa values ​​are also calculated, but in this case, the smallest pKa is used as the pKa of the acid group possessed by its repeating unit.

[0037] (Repeating unit (a1)) The repeating unit (a1) is the repeating unit represented by the above general formula (a1-1) or (a1-2) that has an acid group with a pKa of 8.0 or more and 12.0 or less.

[0038] In the general formula (a1-1), Ra a1 represents a hydrogen atom or an alkyl group. The alkyl group of Ra1 is preferably an alkyl group having 1 to 5 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tributyl, more preferably an alkyl group having 1 to 3 carbons, and even more preferably methyl.

[0039] In general formula (a1-1), Ra2 represents a halogen atom, alkyl, aryl, heteroaryl, alkoxy, alkylthio, alkoxycarbonyl, or alkylcarbonyloxy. Halogen atoms that can be used as Ra2 include fluorine, chlorine, bromine and iodine atoms, with fluorine being the preferred one. The alkyl group of Ra2 is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tributyl, and more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group of Ra2 is preferably phenyl, naphthyl, phenanthryl, anthracene, etc., and more preferably phenyl or naphthyl. The heteroaryl group of Ra2 is preferably a heteroaryl group containing at least one heteroatom selected from the group consisting of sulfur, nitrogen and oxygen atoms. Specifically, it is preferably thienyl, furanyl, benzothienyl, benzofuranyl, pyrroleyl, oxazolyl, thiazolyl, pyridyl, etc., and more preferably thienyl, furanyl, benzothienyl, benzofuranyl. The alkoxy group of Ra2 is preferably an alkoxy group with 1 to 10 carbon atoms, such as methoxy or ethoxy, and more preferably an alkoxy group with 1 to 6 carbon atoms. The alkylthio group of Ra2 is preferably an alkylthio group with 1 to 10 carbon atoms, and more preferably an alkylthio group with 1 to 6 carbon atoms. The alkoxycarbonyl group of Ra2 is preferably an alkoxycarbonyl group with 2 to 10 carbon atoms, and more preferably an alkoxycarbonyl group with 2 to 6 carbon atoms. The alkyl carbonyl group of Ra2 is preferably an alkyl carbonyl group with 2 to 10 carbon atoms, and more preferably an alkyl carbonyl group with 2 to 6 carbon atoms. When there are complex numbers of Ra², these complex numbers of Ra² can be the same or different.

[0040] In the general formula (a1-1), m represents an integer from 0 to 2, preferably 0 or 1, and even more preferably 0. When m represents 0, the aromatic ring in the general formula (a1-1) represents benzene. When m represents 1, the aromatic ring in the general formula (a1-1) represents naphthalene. When m represents 2, the aromatic ring in the general formula (a1-1) represents anthracene.

[0041] In the general formula (a1-1), n1 represents an integer greater than or equal to 1 and less than (5+2m), preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0042] In the general formula (a1-1), k1 represents an integer greater than 0 and less than (5+2m-n1), preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0.

[0043] In the general formula (a1-1), L1 represents a single bond or -C(=O)O-, preferably a single bond.

[0044] In general formula (a1-2), Ra1 represents the same Ra1 as in the aforementioned general formula (a1-1), and the specific examples and preferred ranges are also the same.

[0045] In general formula (a1-2), L2 represents a linker consisting of a single bond or at least one of the group consisting of -C(=O)O-, alkyl, cycloalkyl and aryl groups. As L2, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. As L2, the cycloalkyl group is preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 5 to 15 carbon atoms, and even more preferably a cycloalkyl group with 6 to 10 carbon atoms. The aryl group of L2 is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 10 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. L2 is preferably a linker group composed of -C(=O)O- and an alkyl group, or an aryl group.

[0046] In the general formula (a1-2), n2 represents an integer from 1 to 3, preferably 1 or 2.

[0047] The repeating unit (a1) has an acid group with a pKa of 8.0 or higher and 12.0 or lower. Preferably, the acid group with a pKa of 8.0 or higher and 12.0 or lower is covalently bonded to the atomic group constituting the repeating unit (a1). Examples of acid groups present in repeating units (a1) include phenolic hydroxyl groups and hexafluoroisopropanol groups (-C(CF3)2OH).

[0048] The pKa of the acid group of the repeating unit (a1) is preferably 8.5 or higher and 11.0 or lower, more preferably 9.0 or higher and 10.5 or lower.

[0049] Specific examples of monomers corresponding to the repeating unit (a1) along with their pKa are shown below, but the repeating unit (a1) is not limited to this. Me represents methyl.

[0050] [Chemical Formula 5]

[0051] The repeating unit (a1) is preferably represented by the above general formula (a1-1). The repeating unit (a1) is preferably represented by the general formula (a1-1), and m in the above general formula (a1-1) represents 0 or 1, more preferably m represents 0. The repeating unit (a1) is preferably represented by the above general formula (a1-1), and L1 in the above general formula (a1-1) represents a single bond.

[0052] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (a1-3).

[0053] [Chemical Formula 6]

[0054] In general formula (a1-3), Ra1 represents a hydrogen atom or an alkyl group. Ra2 represents a halogen atom, alkyl, aryl, heteroaryl, alkoxy, alkylthio, alkoxycarbonyl, or alkylcarbonyloxy. When there are complex numbers of Ra², these complex numbers of Ra² can be the same or different. L1 represents a single bond or -C(=O)O-. n3 represents an integer from 1 to 3. k2 represents an integer from 0 to 4.

[0055] In general formula (a1-3), Ra1 and Ra2 are synonyms with Ra1 and Ra2 in the aforementioned general formula (a1-1), and the specific examples and preferred ranges are also the same.

[0056] In the general formula (a1-3), n3 represents an integer from 1 to 3, preferably 1 or 2, and even more preferably 1.

[0057] In the general formula (a1-3), k2 represents an integer from 0 to 4, preferably an integer from 0 to 2, and even more preferably 0.

[0058] The repeating unit (a1) contained in resin (A) can be one type or two or more types.

[0059] The content of the repeating unit (a1) is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of the repeating unit (a1) is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, relative to all repeating units in resin (A).

[0060] (Repeating unit (a2)) The repeating unit (a2) is a repeating unit with an acid group having a pKa of less than 8.0. Preferably, the acid group with a pKa of less than 8.0 is covalently bonded to the atomic group constituting the repeating unit (a2). Examples of acid groups present in the repeating unit (a2) include carboxyl, sulfonic acid, sulfonamide, sulfonimide, and hydroxyl groups. The sulfonamide group is preferably represented by -NHSO₂R₁. R₁ represents an organic group. R₁ is preferably an alkyl or aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. The above-mentioned alkyl group preferably has a fluorine atom as a substituent. The sulfonyl imine group is preferably represented by -SO₂NHSO₂R₁. R₁ represents an organic group. R₁ is preferably an alkyl or aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. The above-mentioned alkyl group preferably has a fluorine atom as a substituent.

[0061] The pKa of the acid group of the repeating unit (a2) is preferably -8.0 or higher and 7.0 or lower, more preferably 0.0 or higher and 6.0 or lower.

[0062] The repeating unit (a2) is preferably represented by the following general formula (a2-1).

[0063] [Chemical Formula 7]

[0064] In general formula (a2-1), Ra5 represents a hydrogen atom or an alkyl group. L3 represents a linker group consisting of a single bond or at least one of the groups selected from alkyl, cycloalkyl, and aryl groups. p represents an integer from 1 to 3.

[0065] In general formula (a2-1), Ra5 is synonymous with Ra1 in the aforementioned general formula (a1-1), and the specific examples and preferred ranges are also the same. As L3, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The cycloalkyl group of L3 is preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 5 to 15 carbon atoms, and even more preferably a cycloalkyl group with 6 to 10 carbon atoms. The aryl group of L3 is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 10 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. In the general formula (a2-1), p preferably represents 1 or 2, and more preferably 1.

[0066] Specific examples of the monomer corresponding to the repeating unit (a2) along with its pKa are shown below, but the repeating unit (a2) is not limited to this.

[0067] [Chemical Formula 8]

[0068] The repeating unit (a2) contained in resin (A) can be one type or two or more types.

[0069] The content of the repeating unit (a2) is not particularly limited, but it is preferably 1 mol% or more, more preferably 3 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of the repeating unit (a2) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, relative to all repeating units in resin (A).

[0070] (Repeating unit (a3)) The repeating unit (a3) ​​is a repeating unit containing at least one fluorine atom and not having an acid group with a pKa of less than 12.0. The repeating unit (a3) ​​does not have an acid group, or even if it does have an acid group, the pKa of the acid group is greater than 12.0. The repeating unit (a3) ​​preferably comprises an alkyl or aryl group having at least one fluorine atom as a substituent. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

[0071] The repeating unit (a3) ​​preferably comprises an alkyl group having 3 or more fluorine atoms as substituents, more preferably comprises an alkyl group having 3 to 15 fluorine atoms as substituents, and even more preferably comprises an alkyl group having 3 to 10 fluorine atoms as substituents.

[0072] The repeating unit (a3) ​​is preferably represented by the following general formula (a3-1).

[0073] [Chemical Formula 9]

[0074] In general formula (a3-1), Ra3 represents a hydrogen atom or an alkyl group. Ra4 represents an alkyl group having three or more fluorine atoms as substituents.

[0075] In general formula (a3-1), Ra3 is synonymous with Ra1 in the aforementioned general formula (a1-1), and the specific examples and preferred ranges are also the same. In general formula (a3-1), Ra4 represents an alkyl group having 3 or more fluorine atoms as substituents, more preferably an alkyl group having 3 to 15 fluorine atoms as substituents, and even more preferably an alkyl group having 3 to 10 fluorine atoms as substituents. The alkyl group of Ra4 is preferably an alkyl group with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or 2-ethylhexyl, and more preferably an alkyl group with 1 to 10 carbon atoms.

[0076] Specific examples of monomers corresponding to the repeating unit (a3) ​​include acid groups along with their pKa as shown below, but the repeating unit (a3) ​​is not limited to this.

[0077] [Chemical Formula 10]

[0078] The repeating unit (a3) ​​contained in resin (A) can be one type or two or more types.

[0079] The content of the repeating unit (a3) ​​is not particularly limited, but it is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of the repeating unit (a3) ​​is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, relative to all repeating units in resin (A).

[0080] In addition to repeating units (a1), (a2), and (a3), resin (A) may further contain other repeating units. The content of other repeating units, relative to all repeating units in resin (A), is preferably 40 mol% or less, and more preferably 30 mol% or less. Resin (A) preferably does not contain repeating units that have groups that decompose under the action of acid and increase polarity. Also, resin (A) preferably does not contain repeating units that produce acid when exposed to photochemical rays or radiation.

[0081] Resin (A) can be synthesized using conventional methods (such as free radical polymerization). The weight average molecular weight of resin (A) is preferably below 100,000, more preferably 1,000 to 50,000, further preferably 3,000 to 40,000, and especially preferably 4,000 to 30,000. The dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.

[0082] The dissolution rate of the resin (A) film made solely of resin in an alkaline developing solution is preferably 0.002 nm / s or more, more preferably 0.005 nm / s or more, and even more preferably 0.01 nm / s or more. The upper limit of the above dissolution rate is preferably 100 nm / s or less. The resin (A) film made solely of resin dissolves at a rate of over 0.002 nm / s in alkaline developing solution, thus exhibiting excellent developability and further improving LWR performance, making it superior. The dissolution rate of a resin-based film in an alkaline developer can be adjusted by the ratio of the content of repeating units (a1), (a2), and (a3), as well as their molecular weight.

[0083] The method for calculating the dissolution rate of a film made solely of resin in an alkaline developer is as follows. The resin was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether (mass ratio 8 / 2) to prepare a concentration of 3% by mass. The prepared resin solution was coated onto a 6-inch Si wafer pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resin film with a thickness of 100 nm. The film thickness reduction rate when the resin film was immersed in a 2.38% (mass) aqueous solution of tetramethylammonium hydroxide at 23°C was calculated using a Litho Tech Japan Corporation photoresist developer analyzer (RDA-790EB). In this manner, the dissolution rate of the resin-only film in an alkaline developer was calculated.

[0084] The content of resin (A) in the composition of the present invention is not particularly limited, but it is preferably 0.1 to 40.0% by mass, more preferably 1.0 to 30.0% by mass, and even more preferably 5.0 to 20.0% by mass, relative to the total solid content of the composition of the present invention. The resin (A) contained in the composition of the present invention may be one type or two or more types.

[0085] [(B) Component] The composition of the present invention contains component (B) which contains repeating units (b1) having phenolic hydroxyl groups and repeating units (b2) having groups that decompose under the action of acid and increase in polarity, and does not contain resins that produce acid by irradiation with photochemical rays or radiation. Component (B) is also known as "resin (B)".

[0086] (Repeating unit (b1)) The repeating unit (b1) is a repeating unit with a phenolic hydroxyl group. The repeating unit (b1) preferably has a structure in which a hydroxyl group is bonded to an aromatic hydrocarbon ring with 6 to 20 carbon atoms. The repeating unit (b1) is preferably a repeating unit represented by the following general formula (b1-1).

[0087] [Chemical Formula 11]

[0088] In general formula (b1-1), A a1 represents a hydrogen atom, alkyl, cycloalkyl, halogen atom, or cyano group. R 21 represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl, or aryloxycarbonyl group; when there are multiple R 21 groups, they can be the same or different. When there are multiple R 21 groups, they can form a ring together. Preferably, R 21 is a hydrogen atom. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0089] Specific examples of the repeating unit (b1) are shown below, but are not limited to this. In the formula, a represents an integer from 1 to 3.

[0090] [Chemical Formula 12]

[0091] [Chemical Formula 13]

[0092] [Chemical Formula 14]

[0093] [Chemical Formula 15]

[0094] As the repeating unit (b1), it is preferably the repeating unit shown below. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer from 1 to 3.

[0095] [Chemical Formula 16]

[0096] [Chemical Formula 17]

[0097] The content of the repeating unit (b1) is not particularly limited, but it is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (B). Furthermore, the content of the repeating unit (b1) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, relative to all repeating units in resin (B).

[0098] (Repeating unit (b2)) The repeating unit (b2) is a repeating unit that has a group that decomposes and increases in polarity through the action of acid (also called an "acid-decomposable group"). The repeating unit (b2) is also called a "repeating unit with an acid-decomposable group". Resin (B) is an acid-degradable resin. In the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern can be formed better, and when an organic developer is used as the developer, a negative pattern can be formed better. As a repeating unit (b2), in addition to repeating units with acid-degradable groups described later, it is preferred to be a repeating unit with acid-degradable groups containing unsaturated bonds.

[0099] Acid-degradable groups refer to groups that decompose to produce polar groups under the action of acids. Preferably, acid-degradable groups have a structure that protects the polar groups with groups that can be released by acid (release groups). That is, resin (B) has repeating units, which contain groups that decompose to produce polar groups under the action of acids. Resins with these repeating units exhibit increased polarity under the action of acids, thus increasing their solubility relative to alkaline developers and decreasing their solubility relative to organic solvents. As a polar group, it is preferably a base-soluble group, such as carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonimino, (alkylsulfonyl)(alkylcarbonyl) imino, (alkylsulfonyl)(alkylcarbonyl) imino, bis(alkylcarbonyl) imino, bis(alkylcarbonyl) imino, bis(alkylsulfonyl) imino, bis(alkylsulfonyl) imino, tri(alkylcarbonyl) imino and tri(alkylsulfonyl) imino, etc., as well as alcoholic hydroxyl groups. Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0100] As a group that is released by the action of an acid, for example, groups represented by formulas (Y1) to (Y4) can be cited. Equation (Y1): -C(Rx 1)(Rx 2)(Rx 3) Formula (Y2):-C(=O)OC(Rx 1)(Rx 2)(Rx 3) Equation (Y3): -C(R 36)(R 37)(OR 38) Equation (Y4): -C(Rn)(H)(Ar)

[0101] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched), or aryl (monocyclic or polycyclic). Furthermore, when all Rx1 to Rx3 are alkyl (straight-chain or branched), at least two of Rx1 to Rx3 are preferably methyl. Preferably, Rx 1 to Rx 3 each independently represent a straight-chain or branched alkyl group, and more preferably, Rx 1 to Rx 3 each independently represent a straight-chain alkyl group. Two of Rx 1 to Rx 3 can be bonded together to form a single ring or multiple rings. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 5 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The ring formed by the two bonds in Rx 1 to Rx 3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms. In cycloalkyl groups formed by two bonds in Rx1 to Rx3, one of the methyl groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene. In these cycloalkyl groups, one or more ethyl groups constituting the cycloalkane ring may be replaced by vinylidenes. The group represented by formula (Y1) or formula (Y2) is preferably Rx1 being methyl or ethyl, and Rx2 and Rx3 being bonded to form the above-mentioned cycloalkyl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the alkyl, cycloalkyl, alkenyl, aryl groups represented by R x1 to R x3 and the ring formed by two bonds of R x1 to R x3 preferably further have fluorine or iodine atoms as substituents.

[0102] In formula (Y3), R36 to R38 independently represent a hydrogen atom or a monovalent organogroup. R37 and R38 can bond together to form a ring. Examples of monovalent organogroups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R36 is preferably a hydrogen atom. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may contain heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more methyl groups may be replaced by heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. R 38 can bond with another substituent in the main chain of the repeating unit to form a ring. The group formed by R 38 bonding with another substituent in the main chain of the repeating unit is preferably an elongated alkyl group such as an elongated methyl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the monovalent organic groups represented by R 36 to R 38 and the ring formed by the mutual bonding of R 37 and R 38 preferably further have fluorine or iodine atoms as substituents.

[0103] As for formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0104] [Chemical Formula 18]

[0105] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining these (e.g., groups formed by combining alkyl and aryl). M represents a single-bonded or divalent linker. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group composed of these groups (e.g., a group composed of alkyl and cycloalkyl groups). Alkyl and cycloalkyl groups, for example, in which one of the methyl groups can be replaced by heteroatoms such as oxygen atoms, or groups containing heteroatoms such as carbonyl groups. Furthermore, it is preferable that one of L1 and L2 is a hydrogen atom, and the other is a group composed of alkyl, cycloalkyl, aryl, or alkylene and aryl groups. At least two of Q, M, and L1 can be bonded to form a loop (preferably a 5- or 6-membered loop). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tributyl and adamantyl. In this isostate sample, the glass transition temperature (Tg) and activation energy are increased, thus ensuring film strength and suppressing fogging.

[0106] When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the alkyl, cycloalkyl, aryl, and groups formed by combining these, represented by L1 and L2, preferably further have fluorine or iodine atoms as substituents. Preferably, the alkyl, cycloalkyl, aryl, and aralkyl groups mentioned above contain heteroatoms such as oxygen atoms in addition to fluorine and iodine atoms. Specifically, for example, a methyl group of the alkyl, cycloalkyl, aryl, and aralkyl groups can be replaced by a heteroatom such as an oxygen atom, or a group containing heteroatoms such as a carbonyl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the heteroatom represented by Q is preferably selected from the group consisting of alkyl, cycloalkyl, aryl, amino, ammonium, mercapto, cyano, aldehyde, and groups composed of these heteroatoms.

[0107] In formula (Y4), Ar represents an aromatic cycloalkyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is preferably an aryl group. When the photoresist composition of the present invention is, for example, a photoresist composition for EUV exposure, the aromatic cycloalkanes represented by Ar and the alkyl, cycloalkyl and aryl groups represented by Rn are preferably substituents having fluorine or iodine atoms.

[0108] From the viewpoint of excellent acid decomposition properties of repeating units, in the release group protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring is preferably not a halogen atom such as a fluorine atom as a substituent.

[0109] In addition, the group that is removed by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0110] As a repeating unit with an acid-decomposable group, it is also preferred to be a repeating unit represented by formula (A).

[0111] [Chemical Formula 19]

[0112] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, or an aryl group that may have a fluorine or iodine atom; and R2 represents a detached group that can have a fluorine or iodine atom after being removed by the action of an acid. At least one of L1, R1, and R2 has a fluorine or iodine atom. Examples of divalent linking groups represented by L1, which may have fluorine or iodine atoms, include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have fluorine or iodine atoms (e.g., alkylene, cycloalkylene, alkenylene, and arylene), and linking groups formed by multiple such groups. Preferably, L1 is -CO-, arylene, or -arylene-alkylene-with fluorine or iodine atoms, and more preferably -CO-, or -arylene-alkylene-with fluorine or iodine atoms. As an enfrylene group, enfrylene is preferred. The alkyl group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferred to be 1 to 10, and more preferably 1 to 3. There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0113] The alkyl group represented by R 1 can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine and iodine atoms contained in the alkyl group represented by R1, which has fluorine or iodine atoms, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by R 1 may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0114] As a detaching radical represented by R 2, which may have fluorine or iodine atoms, examples can be given by detaching radicals represented by the above formulas (Y1) to (Y4) that have fluorine or iodine atoms.

[0115] As a repeating unit with an acid-decomposable group, it is also preferred to be the repeating unit represented by formula (AI).

[0116] [Chemical Formula 20]

[0117] In formula (AI), Xa 1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linker. Rx 1 to Rx 3 independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic or polycyclic). Preferably, when all Rx 1 to Rx 3 are alkyl (linear or branched), at least two of Rx 1 to Rx 3 are methyl groups. Two of Rx 1 to Rx 3 can bond together to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0118] As represented by Xa 1, an alkyl group that can have substituents, examples include methyl or a group represented by -CH 2-R 11. R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organogroup. As represented by R 11, examples include alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acetyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom; preferably, it is an alkyl group with 3 or fewer carbon atoms, and more preferably, it is a methyl group. As Xa 1, it is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0119] Examples of divalent linking groups for T include alkyl groups, aromatic cycloyl groups, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkyl or cycloalkyl group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0120] The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The cycloalkyl group formed by two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. Also preferably, it is a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Cycloalkyl groups formed by two bonds in Rx1 to Rx3, for example, wherein one of the methyl groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene. Furthermore, in such cycloalkyl groups, one or more of the ethyl groups constituting the cycloalkane ring can be replaced by vinylidenes. The repeating unit represented by formula (AI), for example, preferably Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl state.

[0121] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0122] As the repeating unit represented by formula (AI), it is preferably an acid-degradable (meth)acrylate trialkyl ester repeating unit (Xa 1 represents a hydrogen atom or methyl group, and T represents a single bond repeating unit).

[0123] Specific examples of repeating units having acid-decomposable groups are shown below, but are not limited to these. Furthermore, in the formula, Xa1 and Rx represent hydrogen atoms or substituents (preferably straight-chain or branched alkyl groups having 1 to 6 carbon atoms, CF3, F, or CH2OH). Rxa and Rxb each independently represent substituents (preferably alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, or heteroaryl groups having 1 to 12 carbon atoms). Z represents a substituent. p represents an integer greater than or equal to 0.

[0124] [Chemical Formula 21]

[0125] [Chemical Formula 22]

[0126] [Chemical Formula 23]

[0127] [Chemical Formula 24]

[0128] [Chemical Formula 25]

[0129] Resin (B), as a repeating unit with an acid-degradable group, may have repeating units containing an acid-degradable group with an unsaturated bond. As a repeating unit having an acid-decomposable group containing unsaturated bonds, it is preferably a repeating unit represented by formula (B).

[0130] [Chemical Formula 26]

[0131] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group that may have substituents. L represents a single bond or a divalent linker that may have substituents. Ry 1 to Ry 3 independently represent a straight-chain or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. At least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 can bond together to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0132] As represented by Xb, an alkyl group that can have substituents, examples include methyl or a group represented by -CH2-R11. R11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, and an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably an alkyl group with 3 or fewer carbon atoms, and more preferably a methyl group. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group are preferred.

[0133] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In these formulas, Rt represents an alkyl group, an cycloalkyl group, or an aromatic cycloalkyl group, preferably an aromatic cycloalkyl group. The L group is preferably -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO-. Rt may have halogen atoms, hydroxyl groups, alkoxy groups, or other substituents.

[0134] The alkyl group of Ry 1 to Ry 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups of Ry 1 to Ry 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Ry 1 to Ry 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Ry 1 to Ry 3 is preferably vinyl. The acetylenic group of Ry1 to Ry3 is preferably acetylenic. The cycloalkenyl groups of Ry 1 to Ry 3 are preferably those containing double bonds as part of a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. The cycloalkyl group formed by two bonds in Ry 1 to Ry 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups formed by two bonds in Ry 1 to Ry 3, for example, wherein one of the methyl groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as -SO 2- or -SO 3-, vinylidene, or a combination thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethyl groups constituting the cycloalkane or cycloalkene ring can be replaced by vinylidene groups. The repeating unit represented by formula (B), for example, preferably Ry 1 is methyl, ethyl, vinyl, allyl, or aryl, and Ry 2 and Ry 3 are bonded to form the above-mentioned cycloalkyl or cycloalkenyl state.

[0135] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0136] As the repeating unit represented by formula (B), it is preferably an acid-degradable (meth)acrylate tertiary ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -CO- group repeating unit), an acid-degradable hydroxystyrene tertiary alkyl ether repeating unit (Xb represents a hydrogen atom or methyl, and L represents a phenyl repeating unit), or an acid-degradable styrene carboxylic acid tertiary ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -Rt-CO- group (Rt is an aromatic group) repeating unit).

[0137] The content of repeating units containing acid-degradable groups with unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (B). Furthermore, as an upper limit, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (B).

[0138] Specific examples of repeating units containing acid-degrading groups with unsaturated bonds are shown below, but are not limited to this. Furthermore, in the formula, Xb and L1 represent any of the substituents and linkers as described above, Ar represents an aromatic group, R represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acetoxy, cyano, nitro, amino, halogen atom, ester (-OCOR''' or -COOR''', R'''' is an alkyl or fluorinated alkyl with 1 to 20 carbon atoms), or a carboxyl group, etc., R' represents a straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl, alkenyl, alkynyl, or monocyclic or polycyclic aryl, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as -SO2- or -SO3-, vinylidene, or a combination thereof, and n, m, and l represent integers greater than or equal to 0.

[0139] [Chemical Formula 27]

[0140] [Chemical Formula 28]

[0141] [Chemical Formula 29]

[0142] [Chemical Formula 30]

[0143] The content of repeating units (repeating unit (b2)) having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (B). Furthermore, as an upper limit, it is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to all repeating units in resin (B).

[0144] In addition to repeating units (b1) and (b2), resin (B) may also contain other repeating units. Among them, resin (B) does not contain repeating units that produce acid by exposure to photochemical rays or radiation.

[0145] Resin (B) may contain at least one repeating unit selected from the group consisting of group A below and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of repeating units of the following (20) to (24). (20) The repeating unit with acid groups, described later. (21) The repeating unit described later, which does not have any of the acid-decomposing groups or acid groups, but has a fluorine atom, a bromine atom, or an iodine atom. (22) Repeating units having lactone, sulcinolone, or carbonate groups, as described later. (23) Repeating units, as described later, represented by equation (V-1) or equation (V-2) below. (24) Repeating units used to reduce the motion of the main chain Furthermore, the repeating units represented by equations (A) to (E) described later are equivalent to (24) repeating units used to reduce the mobility of the main chain. Group B: A group consisting of repeating units of the following (30) to (32). (30) The repeating unit described below, having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble group. (31) The repeating unit described later, which has an alicyclic hydrocarbon structure and does not exhibit acid decomposition properties. (32) The repeating unit described later, represented by formula (III), which does not have either a hydroxyl or a cyano group.

[0146] Resin (B) may have at least one repeating unit selected from the group consisting of Group A above. When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for EUV exposure, resin (B) preferably has at least one repeating unit selected from the group consisting of Group A above. Resin (B) may contain at least one of fluorine atoms and iodine atoms. When the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (B) preferably contains at least one of fluorine atoms and iodine atoms. When resin (B) contains both fluorine atoms and iodine atoms, resin (B) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (B) may contain both repeating units containing fluorine atoms and repeating units containing iodine atoms. Resin (B) may have repeating units containing aromatic groups. When the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (B) is preferably a resin having repeating units containing aromatic groups. Resin (B) may have at least one repeating unit selected from the group consisting of the above-described group B. When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, resin (B) preferably has at least one repeating unit selected from the group consisting of the above-described group B. Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (B) is preferably free of either fluorine atoms or silicon atoms. When the photoresist composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for ArF, resin (B) is preferably free of aromatic groups.

[0147] (Repeating units with acid groups) In addition to repeating units (b1) and (b2), resin (B) may also have repeating units containing acid groups. As an acid group, it is preferable to have an acid group with a pKa of 13 or less. The acid dissociation constant of the above-mentioned acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (B) contains acid groups with a pKa of 13 or less, the content of acid groups in resin (B) is not particularly limited, and is generally 0.2 to 6.0 mmol / g. Preferably, it is 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the content of acid groups is within the above range, development will proceed well, resulting in excellent pattern shape and resolution. As an acid group, for example, it is preferably a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In the aforementioned hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms can be replaced by groups other than fluorine atoms (such as alkoxycarbonyl groups). As an acid group, -C(CF3)(OH)-CF2- is also preferred. Furthermore, one or more fluorine atoms can be replaced by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group is preferably a repeating unit that is different from repeating units having a structure in which a polar group is protected by a group that is removed by the action of the acid described above, and repeating units having lactone, sulcinolone or carbonate groups as described later. Repeating units with acid groups can have fluorine or iodine atoms.

[0148] The following repeating units can be cited as examples of repeating units having acid groups.

[0149] [Chemical Formula 31]

[0150] The content of repeating units with acid groups is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in resin (B). Furthermore, as an upper limit, it is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (B).

[0151] (A repeating unit that does not have an acid-decomposing group or any of the acid groups, but has a fluorine atom, a bromine atom or an iodine atom) In addition to the aforementioned <repeating units with acid-decomposable groups> and <repeating units with acid groups>, resin (B) may also have repeating units (hereinafter also referred to as unit X) that do not have either acid-decomposable groups or acid groups but have fluorine, bromine, or iodine atoms. The <repeating units with fluorine, bromine, or iodine atoms that do not have either acid-decomposable groups or acid groups> mentioned here are preferably other types of repeating units belonging to group A, different from the <repeating units with lactone, sulopentalide, or carbonate groups> described later.

[0152] As unit X, it is preferably a repeating unit represented by equation (C).

[0153] [Chemical Formula 32]

[0154] L 5 represents a single bond or an ester group. R 9 represents a hydrogen atom, or an alkyl group that may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group that may have 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 group composed of these combinations.

[0155] The following are examples of repeating units having fluorine or iodine atoms.

[0156] [Chemical Formula 33]

[0157] The content of unit X, relative to all repeating units in resin (B), is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (B), it is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

[0158] In the repeating units of resin (B), the total content of repeating units containing at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and especially preferably 40 mol% or more, relative to all repeating units of resin (B). There is no particular upper limit; for example, it may be 100 mol% or less relative to all repeating units of resin (B). Furthermore, as repeating units containing at least one of fluorine, bromine, and iodine atoms, examples include: repeating units having fluorine, bromine, or iodine atoms and having an acid-decomposing group; repeating units having fluorine, bromine, or iodine atoms and having an acid group; and repeating units having fluorine, bromine, or iodine atoms.

[0159] (Repeating units with lactone, sulcinolone, or carbonate groups) Resin (B) may have at least one repeating unit (hereinafter also referred to as "unit Y") selected from the group consisting of lactone groups, sulcinolone groups and carbonate groups. Unit Y is also preferably free of acid groups such as hydroxyl and hexafluoropropanol groups.

[0160] As a lactone or sulfonyl group, it is sufficient to have a lactone or sulfonyl structure. The lactone or sulfonyl structure is preferably a 5-7 membered ring lactone or 5-7 membered ring sulfonyl structure. More preferably, it is a bicyclic or spirocyclic structure formed by ring condensation of other ring structures on the 5-7 membered ring lactone structure, or a bicyclic or spirocyclic structure formed by ring condensation of other ring structures on the 5-7 membered ring sulfonyl structure. Resin (B) preferably has repeating units containing lactone or sulfonolactone groups, which are formed by removing one or more hydrogen atoms from the ring-member atoms of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or a sulfonolactone structure represented by any one of the following formulas (SL1-1) to (SL1-3). The lactone or sulfonolactone groups can be directly bonded to the main chain. For example, the ring-member atoms of the lactone or sulfonolactone groups can also constitute the main chain of resin (B).

[0161] [Chemical Formula 34]

[0162] The aforementioned lactone or sulopentalide structures can also have substituents (Rb 2). Preferred substituents (Rb 2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n 2 represents an integer from 0 to 4. When n 2 is 2 or more, the plurality of Rb 2 groups can be different, and the plurality of Rb 2 groups can also bond together to form a ring.

[0163] As a repeating unit having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3), for example, a repeating unit represented by the following formula (AI) can be cited.

[0164] [Chemical Formula 35]

[0165] In formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that can be present in the alkyl group of Rb 0 include hydroxyl groups and halogen atoms. Examples of halogen atoms that can be represented by Rb 0 include fluorine, chlorine, bromine, and iodine. Rb 0 is preferably represented by hydrogen or methyl. Ab represents a single bond, an alkyl group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linker formed by combinations of these. Preferably, Ab is a single bond or a linker represented by -Ab 1-CO 2-. Ab 1 is a straight-chain or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group, preferably methyl, ethyl, cyclohexyl, adamantyl, or norbornenyl. V represents a group formed by removing a hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or a group formed by removing a hydrogen atom from a ring member atom of a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3).

[0166] When an optical isomer exists in a repeating unit containing a lactone group or a sulcinolone group, any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90% or higher, and more preferably 95% or higher.

[0167] As a carbonate group, a cyclic carbonate group is preferred. As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following formula (A-1).

[0168] [Chemical Formula 36]

[0169] In formula (A-1), RA1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl). n represents an integer greater than or equal to 0. RA2 represents a substituent. When n is 2 or more, the multiple RA2 groups can be the same or different. A represents a single bond or a divalent linking group. As the aforementioned divalent linking group, it is preferably an alkyl group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these. Z represents a group that forms a monocyclic or polycyclic atom together with the group represented by -O-CO-O- in the formula.

[0170] The following example illustrates unit Y. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0171] [Chemical Formula 37]

[0172] [Chemical Formula 38]

[0173] The content of unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in resin (B). Furthermore, as an upper limit, it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and especially preferably 60 mol% or less, relative to all repeating units in resin (B).

[0174] (Repeating units represented by equation (V-1) or equation (V-2) below) Resin (B) may have repeating units represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formulas (V-1) and (V-2) are preferably different from the repeating units described above.

[0175] [Chemical Formula 39]

[0176] In the formula, R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acetoxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group with 1 to 6 carbon atoms), or carboxyl group. As an alkyl group, it is preferred to be a straight-chain, branched, or cyclic alkyl group with 1 to 10 carbon atoms. n 3 represents an integer from 0 to 6. n 4 represents an integer from 0 to 4. X 4 is a methyl group, an oxygen atom, or a sulfur atom. The following examples illustrate repeating units represented by equations (V-1) or (V-2). As a 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.

[0177] (Repetitive units used to reduce the mobility of the main chain) From the viewpoint of suppressing excessive diffusion of the generated acid or pattern breakdown during development, resin (B) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and most preferably greater than 125°C. Furthermore, from the viewpoint of having a good dissolution rate in the developer, Tg is preferably below 400°C, and more preferably below 350°C. Furthermore, in this specification, the glass transition temperature (Tg) of polymers such as resin (B) (hereinafter also referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of the homopolymer consisting only of each repeating unit contained in the polymer is calculated separately using the Bicerano method. Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Then, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these is taken as the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). When calculating Tg using the Bicerano method, the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.) can be used.

[0178] To increase the Tg of resin (B) (preferably, to make Tg exceed 90°C), it is preferable to reduce the mobility of the main chain of resin (B). Methods for reducing the mobility of the main chain of resin (B) include the following methods (a) to (e). (a) Introducing large-volume substituents into the main chain (b) Introducing multiple substituents into the main chain (c) Introducing substituents near the main chain to induce interactions between resins (B). (d) Formation of the main chain in the ring structure (e) Linking ring structures to the main chain Furthermore, resin (B) is preferably a repeating unit with a Tg of 130°C or higher, which is a homopolymer. Furthermore, there are no particular restrictions on the types of repeating units whose Tg of the homopolymer is above 130°C, as long as the repeating unit whose Tg of the homopolymer is above 130°C as calculated using the Bicerano method is acceptable. In addition, the repeating units represented by equations (A) to (E) described later, depending on the type of functional groups therein, are equivalent to repeating units whose Tg of the homopolymer is above 130°C.

[0179] As one example of a specific implementation of (a) above, a method of introducing a repeating unit represented by formula (A) into resin (B) can be cited.

[0180] [Chemical Formula 40]

[0181] In formula (A), RA represents a group containing a polycyclic structure. Rx represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and these multiple ring structures may or may not be fused. As a specific example of a repeating unit represented by formula (A), the repeating unit described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954 can be cited.

[0182] As one example of a specific implementation of (b) above, a method of introducing repeating units represented by formula (B) into resin (B) can be cited.

[0183] [Chemical Formula 41]

[0184] In formula (B), Rb1 to Rb4 independently represent hydrogen atoms or organic groups, and at least two of Rb1 to Rb4 represent organic groups. When at least one of the organic groups is a group that is directly linked to the main chain of the ring structure and the repeating unit, there are no particular restrictions on the types of other organic groups. Furthermore, when none of the organic groups are directly linked to the main chain of the ring structure and repeating unit, at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms. As a specific example of a repeating unit represented by equation (B), the repeating unit described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954 can be cited.

[0185] As one example of a specific implementation of (c) above, a method of introducing repeating units represented by formula (C) into resin (B) can be given.

[0186] [Chemical Formula 42]

[0187] In formula (C), Rc1 to Rc4 independently represent hydrogen atoms or organic groups, and at least one of Rc1 to Rc4 is a group containing hydrogen atoms with hydrogen bonding in the main chain carbon with a number of atoms up to 3. In order to induce the interaction between the main chains of resin (B), it is preferable to have hydrogen atoms with hydrogen bonding in the number of atoms up to 2 (closer to the main chain). As a specific example of a repeating unit represented by formula (C), the repeating unit described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954 can be cited.

[0188] As one example of a specific implementation of (d) above, a method of introducing a repeating unit represented by formula (D) into resin (B) can be cited.

[0189] [Chemical Formula 43]

[0190] In formula (D), "Cyclic" represents a group whose main chain is formed in a cyclic structure. There is no particular restriction on the number of atoms constituting the ring. As a specific example of a repeating unit represented by formula (D), the repeating unit described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954 can be cited.

[0191] As one example of a specific implementation of (e) above, a method of introducing repeating units represented by formula (E) into resin (B) can be given.

[0192] [Chemical Formula 44]

[0193] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups that can have substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in a cyclic group. As a specific example of a repeating unit represented by formula (E), the repeating unit described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954 can be cited.

[0194] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble groups) Resin (B) may have repeating units containing at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups. Examples of repeating units having lactone, sulfonyl, or carbonate groups in resin (B) include those described in the section on <Repeating Units Having Lactone, Sulfolactone, or Carbonate Groups> above. A preferred content is also as described in the section on <Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups> above.

[0195] Resin (B) may have repeating units containing hydroxyl or cyano groups. This can improve substrate adhesion and developer affinity. The repeating unit having a hydroxyl or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl or cyano group. The repeating unit having a hydroxyl or cyano group is preferably free of acid-degradable groups. Examples of repeating units having a hydroxyl or cyano group include those described in paragraphs

[0081] to

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

[0196] Resin (B) may have repeating units containing base-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonimide groups, disulfonimide groups, and aliphatic alcohol groups substituted with electron-withdrawing groups at the α-position (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units with alkali-soluble groups in the resin (B), the resolving power in contact hole applications can be increased. Examples of repeating units with alkali-soluble groups include those described in paragraphs

[0085] and

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

[0197] (A repeating unit with an alicyclic hydrocarbon structure that does not exhibit acid decomposition properties) Resin (B) may contain repeating units with an alicyclic hydrocarbon structure that do not exhibit acid-degradable properties. This reduces the leaching of low-molecular-weight components from the photoresist film into the immersion bath during immersion exposure. Examples of repeating units with an alicyclic hydrocarbon structure that do not exhibit acid-degradable properties include, for example, repeating units derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0198] (A repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group) Resin (B) may have repeating units represented by formula (III) that do not have either hydroxyl or cyano groups.

[0199] [Chemical Formula 45]

[0200] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH₂-O-Ra₂ group. In the formula, Ra₂ represents a hydrogen atom, an alkyl group, or a acetyl group. As a repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group, the repeating unit described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-098921 can be cited.

[0201] (Other repeating units) Furthermore, resin (B) may have other repeating units besides the repeating units described above. For example, resin (B) may have repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. The following are specific examples of repeating units other than the repeating units mentioned above.

[0202] [Chemical Formula 46]

[0203] In addition to the repeating units mentioned above, resin (B) may also have various repeating units to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist profile, resolution, heat resistance, and sensitivity.

[0204] As resin (B), it is preferable that all repeating units are composed of repeating units derived from compounds having vinyl unsaturated bonds, especially when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF. In particular, it is also preferable that all repeating units are composed of (meth)acrylate repeating units. When all repeating units are composed of (meth)acrylate repeating units, it is permissible to use any of the following: all repeating units are methacrylate repeating units, all repeating units are acrylate repeating units, or all repeating units are composed of both methacrylate and acrylate repeating units. Preferably, the acrylate repeating units constitute 50 moles or less of all repeating units.

[0205] Resin (B) can be synthesized using conventional methods (e.g., free radical polymerization). Using the GPC method with polystyrene equivalents, the weight average molecular weight of resin (B) is preferably below 30,000, more preferably 1,000 to 30,000, further preferably 3,000 to 30,000, and especially preferably 5,000 to 15,000. The dispersion (molecular weight distribution) of resin (B) is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, and especially preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and photoresist shape, and the smoother the sidewalls and the better the roughness of the photoresist pattern.

[0206] In the photoresist composition of the present invention, the content of resin (B) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, relative to the total solid content of the photoresist composition of the present invention. Resin (B) can be used in one or more ways.

[0207] [(C) Component] The composition of the present invention contains component (C), which is a compound that produces acid by irradiation with photochemical rays or radiation (photoacid generator). Component (C) is also known as "compound (C)" or "photoacid generator".

[0208] As photoacid generators, compounds that generate organic acids by irradiation with photochemical rays or radiation are preferred. Examples include strontium salts, monazine salts, diazonium salts, phosphonium salts, acetylene sulfonate compounds, oxime sulfonate compounds, diazonium disulfonate compounds, diazonium disulfonate compounds, and o-nitrobenzyl sulfonate compounds.

[0209] As a photoacid generator, a known compound that generates acid by irradiation with photochemical rays or radiation can be used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0086] to

[0094] of U.S. Patent Application Publication 2015 / 0004544A1, and paragraphs

[0323] to

[0402] of U.S. Patent Application Publication 2016 / 0237190A1 can be used.

[0210] As a photoacid generator, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferred.

[0211] [Chemical Formula 47]

[0212] In the above general formula (ZI), R 201, R 202 and R 203 each independently represent an organic group. The number of carbon atoms in the organic groups of R 201, R 202, and R 203 is generally 1 to 30, and preferably 1 to 20. Furthermore, two of R 201 to R 203 can bond to form a ring structure, which may contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbonyl groups. Examples of groups formed by the bonding of two of R 201 to R 203 include alkyl groups (e.g., butyl, pentyl) and -CH 2-CH 2-O-CH 2-CH 2-. Z- indicates anion (preferably a non-nucleophilic anion).

[0213] As preferred examples of cations in general formula (ZI), examples include the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Furthermore, the photoacid generator can be a compound having a plurality of structures represented by the general formula (ZI). For example, it can be a compound having at least one of R 201 to R 203 of a compound represented by the general formula (ZI) and at least one of R 201 to R 203 of another compound represented by the general formula (ZI) by a single bond or a linker group.

[0214] First, the compound (ZI-1) will be described. Compound (ZI-1) is an aryl strontium compound in which at least one of R 201 to R 203 of the above general formula (ZI) is an aryl group, that is, a compound in which aryl strontium is a cation. Aryl strontium compounds can have all R 201 to R 203 being aryl, or a portion of R 201 to R 203 being aryl, with the remainder being alkyl or cycloalkyl. Examples of aryl strontium compounds include, for example, triaryl strontium compounds, diarylalkyl strontium compounds, aryldialkyl strontium compounds, diarylcycloalkyl strontium compounds, and aryldicycloalkyl strontium compounds.

[0215] The aryl group contained in the aryl strontium compound is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure with an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl strontium compound has two or more aryl groups, the two or more aryl groups can be the same or different. The alkyl or cycloalkyl group of the aryl strontium compound is preferably a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tributyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0216] The aryl, alkyl, and cycloalkyl groups of R 201 to R 203 may also independently have alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl, or phenylthio group as substituents.

[0217] Next, the compound (ZI-2) will be described. In the compound (ZI-2) system formula (ZI), R 201 to R 203 independently represent compounds with an organic group that does not have an aromatic ring. The aromatic ring referred to here also includes aromatic rings containing heteroatoms. As R 201~R 203, the non-aromatic organic group is usually 1~30 carbons, preferably 1~20. R 201 to R 203 are each preferably alkyl, cycloalkyl, allyl or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0218] The alkyl and cycloalkyl groups of R 201 to R 203 are preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl). R 201~R 203 can be further substituted with halogen atoms, alkoxy groups (e.g., carbon 1~5), hydroxyl groups, cyano groups or nitro groups.

[0219] Next, the compound (ZI-3) will be described.

[0220] [Chemical Formula 48]

[0221] In general formula (ZI-3), M represents an alkyl, cycloalkyl, or aryl group. When a ring structure is formed, the ring structure may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond. R6c and R7c independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R6c and R7c can bond together to form a ring. Rx and Ry independently represent an alkyl, cycloalkyl, or alkenyl group. Rx and Ry can bond together to form a ring. Furthermore, at least two of M, R6c, and R7c can bond together to form a ring structure, which may also include a carbon-carbon double bond. Z- represents an anion.

[0222] In general formula (ZI-3), the alkyl and cycloalkyl represented by M are preferably straight-chain alkyl with 1 to 15 carbons (preferably 1 to 10 carbons), branched alkyl with 3 to 15 carbons (preferably 3 to 10 carbons), or cycloalkyl with 3 to 15 carbons (preferably 1 to 10 carbons). Specifically, examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tributyl, cyclopropyl, cyclobutyl, cyclohexyl, and norbornyl. The aryl group represented by M is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure with an oxygen atom or a sulfur atom. Examples of heterocyclic structures include furan rings, thiophene rings, benzofuran rings, and benzothiophene rings.

[0223] The M mentioned above can further have substituents. For example, benzyl can be used as M. Furthermore, when M has a ring structure, the aforementioned ring structure may include at least one of oxygen atom, sulfur atom, ester bond, amide bond and carbon-carbon double bond.

[0224] As for the alkyl, cycloalkyl, and aryl groups represented by R6c and R7c, examples can be made that are the same as M above, and their preferred forms are also the same. Furthermore, R6c and R7c can be bonded together to form a ring. Halogen atoms represented by R6c and R7c include, for example, fluorine, chlorine, bromine and iodine atoms.

[0225] As for the alkyl and cycloalkyl groups represented by Rx and Ry, examples can be made that are the same as M above, and their preferred forms are also the same. The alkenyl groups represented by Rx and Ry are preferably allyl or vinyl. The aforementioned Rx and Ry may further have substituents. For example, 2-oxoalkyl or alkoxycarbonylalkyl groups can be used as Rx and Ry. As represented by Rx and Ry, 2-oxoalkyl groups, for example, those with 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically, 2-oxopropyl and 2-oxobutyl, etc. As the alkoxycarbonyl alkyl group represented by Rx and Ry, examples include those with 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Furthermore, Rx and Ry can be bonded to form a ring. The ring structure formed by the mutual bonding of Rx and Ry can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds or carbon-carbon double bonds.

[0226] In the general formula (ZI-3), M and R 6c can bond to form a ring structure, and the formed ring structure can contain carbon-carbon double bonds.

[0227] Among them, the above-mentioned compound (ZI-3) is preferably compound (ZI-3A). Compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and has a benzoylmethyl strontium salt structure.

[0228] [Chemical Formula 49]

[0229] In the general formula (ZI-3A), R1c to R5c independently represent hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio. As R6c and R7c, they have the same meaning as R6c and R7c in the above general formula (ZI-3), and their preferred state is also the same. As Rx and Ry, they have the same meaning as Rx and Ry in the above general formula (ZI-3), and their preferred state is also the same.

[0230] Any two or more of R1c to R5c, and Rx and Ry can each bond to form a ring structure, which can independently contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbon-carbon double bonds. Furthermore, R5c and R6c, and R5c and Rx can each bond to form a ring structure, which can each independently contain carbon-carbon double bonds. Also, R6c and R7c can each bond to form a ring structure. Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings composed of two or more such rings. Examples of ring structures include 3 to 10-membered rings, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0231] Examples of groups formed by the bonding of any two or more of R1c to R5c, R6c and R7c, and Rx and Ry include butylyl and pentenylyl. The group formed by the bond between R5c and R6c, and between R5c and Rx, is preferably a single bond or an alkyl group. Examples of alkyl groups include alkylmethyl and alkylethyl groups. Zc - represents an anion.

[0232] Next, compound (ZI-4) will be described. The compound (ZI-4) is represented by the following general formula (ZI-4).

[0233] [Chemical Formula 50]

[0234] In the general formula (ZI-4), l represents an integer from 0 to 2. r represents an integer from 0 to 8. R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have substituents. When there are multiple R 14 groups, each independently represents an alkyl, cycloalkyl, alkoxy, alkylsulfonyl, cycloalkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have substituents. R 15 can independently represent alkyl, cycloalkyl, or naphthyl groups. These groups may have substituents. Two R 15 groups can bond together to form a ring. When two R 15 groups bond together to form a ring, the ring skeleton may contain heteroatoms such as oxygen or nitrogen atoms. In one state, it is preferred that the two R 15 groups are alkyl groups and bond together to form a ring structure. Z - indicates anion.

[0235] In general formula (ZI-4), the alkyl groups of R13, R14, and R15 are straight-chain or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. Methyl, ethyl, n-butyl, or tributyl are more preferably used as alkyl groups.

[0236] Next, the general formulas (ZII) and (ZIII) will be explained. In general formulas (ZII) and (ZIII), R 204 to R 207 independently represent aryl, alkyl, or cycloalkyl groups, respectively. The aryl group in R 204 to R 207 is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group in R 204 to R 207 can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of skeletons for aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As for the alkyl and cycloalkyl groups of R 204 to R 207, they are preferably straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), or cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0237] The aryl, alkyl, and cycloalkyl groups of R 204 to R 207 may each have substituents independently. Examples of substituents that may be present in the aryl, alkyl, and cycloalkyl groups of R 204 to R 207 include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Z - indicates anion.

[0238] The Z- in general formula (ZI), Z- in general formula (ZII), Z- in general formula (ZI-3), Zc- in general formula (ZI-3A), and Z- in general formula (ZI-4) are preferably the anions represented by the following general formula (3).

[0239] [Chemical Formula 51]

[0240] In general formula (3), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0241] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferably that Xf in both cases is a fluorine atom.

[0242] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are multiple R4s and R5s, R4s and R5s may be the same or different. The alkyl groups represented by R4 and R5 may have substituents, preferably having 1 to 4 carbon atoms. R4 and R5 are preferably hydrogen atoms. Specific examples and preferred forms of alkyl groups substituted with at least one fluorine atom are the same as specific examples and preferred forms of Xf in general formula (3).

[0243] L represents a binary linking basis. When there are multiple Ls, each L can be the same or different. Examples of divalent linking groups include -COO- (-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- are preferred, and more preferably -COO-, -OCO-, -CONH-, -SO 2-, -COO-alkylene-, or -OCO-alkylene-.

[0244] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Preferably, these are alicyclic groups with a large volumetric structure, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0245] The aryl group can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene. The heterocyclic group can be monocyclic or polycyclic. Polycyclic heterocyclic groups can further suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Examples of lactone and sulfonyl lactone rings include the lactone and sulfonyl lactone structures illustrated in the aforementioned resins. The heterocycle in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0246] The aforementioned cyclic organic group may have substituents. Examples of such substituents include alkyl groups (which may be either linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms constituting the cyclic organic group (carbons that contribute to ring formation) may also be carbonyl carbons.

[0247] The preferred anions represented by general formula (3) are 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)qW, and SO₃-CF₂-CH(CF₃)-OCO-(L)q'-W. Here, L, q, and W are the same as in general formula (3). q' represents an integer from 0 to 10.

[0248] In one state sample, Z- in general formula (ZI), Z- in general formula (ZII), Z- in general formula (ZI-3), Zc- in general formula (ZI-3A), and Z- in general formula (ZI-4) are preferably anions represented by the following general formula (4).

[0249] [Chemical Formula 52]

[0250] In general formula (4), XB1 and XB2 represent, independently, a hydrogen atom or a monovalent organic group without a fluorine atom. XB1 and XB2 are preferably hydrogen atoms. XB3 and XB4 each independently represent a hydrogen atom or a monovalent organogroup. Preferably, at least one of XB3 and XB4 is a fluorine atom or a monovalent organogroup having a fluorine atom; more preferably, both XB3 and XB4 are fluorine atoms or monovalent organogroups having a fluorine atom. Further preferably, both XB3 and XB4 are alkyl groups substituted with fluorine atoms. L, q, and W are the same as in general formula (3).

[0251] Z- in general formula (ZI), Z- in general formula (ZII), Z- in general formula (ZI-3), Zc- in general formula (ZI-3A), and Z- in general formula (ZI-4) can be benzenesulfonic acid anions, preferably benzenesulfonic acid anions substituted with branched alkyl or cycloalkyl groups.

[0252] Z- in general formula (ZI), Z- in general formula (ZII), Z- in general formula (ZI-3), Zc- in general formula (ZI-3A), and Z- in general formula (ZI-4) are preferably aromatic sulfonic acid anions represented by the following general formula (SA1).

[0253] [Chemical Formula 53]

[0254] In formula (SA1), Ar represents an aryl group, which can be further substituented with groups other than sulfonic acid anions and -(DB) groups. Examples of substituents that can be further added include fluorine atoms and hydroxyl groups.

[0255] n represents an integer greater than or equal to 0. Preferably, n is 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0256] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, urethane groups, urethane groups, sulfonate groups, ester groups, and groups composed of two or more of these.

[0257] B represents a hydrocarbon group.

[0258] Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably isopropyl or cyclohexyl.

[0259] Preferred examples of thionium cations in general formula (ZI) and iodonium cations in general formula (ZII) are shown below.

[0260] [Chemical Formula 54]

[0261] Preferred examples of the anions Z- in general formula (ZI), general formula (ZII), general formula (ZI-3), general formula (ZI-3A), and general formula (ZI-4) are shown below.

[0262] [Chemical Formula 55]

[0263] [Chemical Formula 56]

[0264] The above-mentioned cations and anions can be combined in any way to be used as photoacid generators.

[0265] The aforementioned cations or anions may have lactone groups. As the lactone group, any group can be used as long as it has a lactone structure, but it is preferred to have a 5-7 membered ring lactone structure, and even more preferably, the 5-7 membered ring lactone structure has other ring structures formed by ring condensation in the form of a bicyclic or spirocyclic structure. More preferably, it is a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). As the lactone structure, it is preferred to be a group represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

[0266] [Chemical Formula 57]

[0267] The lactone moiety can have substituents (Rb 2). Preferred substituents (Rb 2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n 2 represents an integer from 0 to 4. When n 2 is 2 or more, the multiple Rb 2 groups can be different, and the multiple Rb 2 groups can also bond together to form a ring.

[0268] The pKa of the acid generated by the above-mentioned photoacid generator is preferably -10 or higher and 5 or lower, and more preferably -5 or higher and 1 or lower.

[0269] Photoacid generators can be in the form of low-molecular-weight compounds or as a part embedded in a polymer. Alternatively, they can be in both the form of low-molecular-weight compounds and as a part embedded in a polymer. Photoacid generators are preferably in the form of low molecular weight compounds. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Photoacid generators can be used alone or in combination with two or more.

[0270] Compound (C) is preferably selected from at least one of the group consisting of compounds (I) to (II).

[0271] (Compound (I)) Compound (I) is a compound having one or more structural sites X and one or more structural sites Y, and is a compound that produces an acid by exposure to photochemical rays or radiation, comprising the first acidic site derived from structural site X and the second acidic site derived from structural site Y. Structural site X: Composed of anionic site A1- and cationic site M1+, and formed by irradiation with photochemical rays or radiation, forming the first acidic site represented by HA1. Structural site Y: Composed of anionic site A2- and cationic site M2+, and formed by irradiation with photochemical rays or radiation, forming a second acidic site represented by HA2. The above compound (I) satisfies the following condition I.

[0272] Condition I: In the above compound (1), the compound PI obtained by replacing the above cation M1+ in the above structural site X and the above cation M2+ in the above structural site Y with H+ has an acid dissociation constant a1 derived from the acidic site represented by HA1 obtained by replacing the above cation M1+ in the above structural site X with H+ and an acid dissociation constant a2 derived from the acidic site represented by HA2 obtained by replacing the above cation M2+ in the above structural site Y with H+, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0273] The following will provide a more detailed explanation of condition I. When compound (I) is, for example, a compound that produces an acid having a first acidic site derived from the above-described structural site X and a second acidic site derived from the above-described structural site Y, compound PI is equivalent to "a compound having HA 1 and HA 2". The acid dissociation constants a1 and a2 of compound PI, more specifically, refer to the pKa of compound PI when it becomes a "compound having A1- and HA2", given that the acid dissociation constant of compound PI has been determined, and the pKa of the aforementioned "compound having A1- and HA2" when it becomes a "compound having A1- and A2-".

[0274] When compound (I) is, for example, a compound that produces an acid having two first acidic sites derived from the above-mentioned structural site X and one second acidic site derived from the above-mentioned structural site Y, compound PI is equivalent to "a compound having two HA 1 and one HA 2". Having determined the acid dissociation constant of compound PI, the acid dissociation constant when compound PI is a "compound having one A1-, one HA1, and one HA2", and the acid dissociation constant when the "compound having one A1-, one HA1, and one HA2" becomes a "compound having two A1- and one HA2", are equivalent to the aforementioned acid dissociation constant a1. When the "compound having two A1- and one HA2" becomes a "compound having two A1- and A2-", the acid dissociation constant is equivalent to acid dissociation constant a2. That is, in the case of compound PI, when there are multiple acid dissociation constants for the acidic site represented by HA1 obtained by replacing the cation site M1+ derived from the above structural site X with H+, the value of acid dissociation constant a2 is greater than the maximum value among the multiple acid dissociation constants a1. Furthermore, when the acid dissociation constant of compound PI is defined as "a compound having one Al-, one HA1, and one HA2", and the acid dissociation constant of "a compound having one Al-, one HA1, and one HA2" is defined as "ab", the relationship between aa and ab satisfies aa <ab。

[0275] The acid dissociation constants a1 and a2 can be determined using the methods described above for determining the acid dissociation constants. The compound PI mentioned above is equivalent to the acid produced when compound (I) is irradiated with photochemical rays or radiation. When compound (I) has two or more structural sites X, the structural sites X may be the same or different. Furthermore, two or more of the above-mentioned A1- and two or more of the above-mentioned M1+ may be the same or different. In compound (I), the above-mentioned A1- and A2-, as well as the above-mentioned M1+ and M2+, may be the same or different, but the above-mentioned A1- and A2- are preferably different.

[0276] In the aforementioned compound PI, the absolute value of the difference between the acid dissociation constant a1 (which is the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. Furthermore, there is no particular upper limit to the absolute value of the difference between the acid dissociation constant a1 (which is the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2; for example, it may be 16 or less.

[0277] In the above-mentioned compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. Furthermore, as a lower limit value of the acid dissociation constant a2, it is preferably -4.0 or more.

[0278] In the above-mentioned compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. Furthermore, as a lower limit value of the acid dissociation constant a1, it is preferably -20.0 or more.

[0279] Anionic sites A1- and A2- are structural sites containing negatively charged atoms or groups of atoms. For example, structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below can be cited. The anionic site A1- is preferably an acidic site that can form an acid dissociation constant, and more preferably any one of formulas (AA-1) to (AA-3), and even more preferably any one of formulas (AA-1) and (AA-3). Furthermore, the anionic site A2- is preferably an acidic site that can form an acid dissociation constant larger than that of the anionic site A1-, more preferably any one of formulas (BB-1) to (BB-6), and even more preferably any one of formulas (BB-1) and (BB-4). Furthermore, in the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), RA represents a monovalent organic group. There are no particular limitations on the monovalent organic group represented by RA; for example, cyano, trifluoromethyl, and methanesulfonyl can be cited.

[0280] [Chemical Formula 58]

[0281] [Chemical Formula 59]

[0282] The cation sites M1+ and M2+ are structural sites containing positively charged atoms or groups of atoms. For example, an organic cation with a monovalent charge can be cited. Furthermore, as an organic cation, for example, the organic cation represented by M+ mentioned above can be cited.

[0283] (Compound (II)) Compound (II) is a compound having two or more of the above-described structural sites X and one or more of the above-described structural sites Z, and is a compound that produces an acid comprising two or more first acidic sites derived from the above-described structural sites X and the above-described structural sites Z by irradiation with photochemical rays or radiation. Structural site Z: The site that can neutralize the nonionic nature of acids.

[0284] In compound (II), the definitions of structural site X, A1- and M1+ are synonymous with those in compound (I) above, and are also the same in preferred form.

[0285] In the above compound (II), in compound PII formed by replacing the above-mentioned cation M 1 + in the above-mentioned structural site X with H +, the preferred range of the acid dissociation constant a1 derived from the acidic site represented by HA 1 formed by replacing the above-mentioned cation M 1 + in the above-mentioned structural site X with H + is the same as the acid dissociation constant a1 in the above-mentioned compound PI. Furthermore, for example, when compound (II) is a compound that produces an acid having two acidic sites derived from the first acidic site X and the acidic site Z, compound PII is equivalent to "a compound having two HA 1s". Having determined the acid dissociation constant of compound PII, the acid dissociation constant when compound PII is "a compound having one A 1 - and one HA 1" and the acid dissociation constant when "a compound having one A 1 - and one HA 1" becomes "a compound having two A 1 -s" are equivalent to the acid dissociation constant a1.

[0286] The acid dissociation constant a1 can be determined using the method described above for determining the acid dissociation constant. The above compound PII is equivalent to the acid produced when compound (II) is irradiated with photochemical rays or radiation. Furthermore, the two or more structural parts X mentioned above may be the same or different. Similarly, the two or more A1- and the two or more M1+ mentioned above may be the same or different.

[0287] There are no particular limitations on the nonionicity of the acid in structural site Z, but it is preferable to have a site containing a group that can electrostatically interact with a proton or a functional group with electrons. Examples of functional groups capable of electrostatic interaction with protons or possessing electrons include, for instance, functional groups with macrocyclic structures such as cyclic polyethers, or functional groups containing nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation. Nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation refer, for example, nitrogen atoms having a partial structure as shown in the following formula.

[0288] [Chemical Formula 60]

[0289] Examples of partial structures that are functional groups capable of electrostatically interacting with protons or having electrons include crown ether structures, azacrown ether structures, first- to third-order amine structures, pyridine structures, imidazole structures, and pyrazine structures, with first- to third-order amine structures being preferred.

[0290] Examples of sites other than cations that compounds (I) and (II) may have are given.

[0291] [Chemical Formula 61]

[0292] [Chemical Formula 62]

[0293] Specific examples of compound (C) are shown below, but are not limited to these.

[0294] [Chemical Formula 63]

[0295] [Chemical Formula 64]

[0296] In the composition of the present invention, the content of component (C) (photoacid generator) (total when multiple components are present) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, further preferably 1 to 20% by mass, and especially preferably 1 to 15% by mass, based on the total solid content of the composition of the present invention. As a photoacid generator, when the composition contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (the total of multiple types if present) is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.

[0297] <Acid diffusion control agent> The composition of this invention may contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher, which captures the acid generated from photoacid generators during exposure and inhibits the reaction of acid-decomposing resin in the unexposed area caused by excess generated acid. There are no particular limitations on the types of acid diffusion control agents. For example, basic compounds (CA), low molecular weight compounds (CB) with nitrogen atoms and groups that can be removed by the action of acid, and compounds (CC) whose acid diffusion control ability is reduced or disappears by irradiation with photochemical rays or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids relative to photoacid generators, and basic compounds (CE) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation. As a specific example of a basic compound (CA), for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; as a specific example of a basic compound (CE) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation, those described in paragraphs

[0137] to

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

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

[0156] to

[0163] of International Publication No. 2020 / 066824. As a specific example of an onium salt compound (CD) that is a relatively weak acid relative to a photoacid generator, one can cite, for example, the one described in paragraphs

[0305] to

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

[0298] In addition to the above, for example, well-known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 may be used as acid diffusion control agents.

[0299] When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (the total of multiple types if present) relative to the total solid content of the composition of the present invention is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass. In the composition of this invention, an acid diffusion control agent may be used alone or in combination with two or more.

[0300] <Hydrophobic resin> The composition of the present invention may further include a hydrophobic resin (also referred to as "hydrophobic resin (D)") that is different from resin (A). Hydrophobic resin (D) is preferably designed to be present on the surface of the photoresist film. However, unlike surfactants, it does not necessarily have to have hydrophilic groups in its molecules and can also help to uniformly mix polar and non-polar substances. As an example of the effects of adding hydrophobic resin (D), it can be seen that it controls the static and dynamic contact angle of the photoresist film surface with respect to water, and suppresses gas escape.

[0301] From the viewpoint of surface-biased membrane formation, the hydrophobic resin (D) preferably has one or more of the following structures: fluorine atoms, silicon atoms, and CH3 moieties contained in the side chain portion of the resin; more preferably, it has two or more of these. The aforementioned hydrophobic resin (D) preferably has a hydrocarbon group having five or more carbon atoms. These groups can exist in the main chain of the resin or can be substituted in the side chain. As a hydrophobic resin (D), the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306 can be cited.

[0302] When the composition of the present invention contains hydrophobic resin (D), the content of hydrophobic resin (D) is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention.

[0303] <surfactants> The composition of this invention may contain surfactants. When surfactants are present, patterns with better adhesion and fewer development defects can be formed. Fluorine-based and / or silicone-based surfactants are preferred. As fluorine-based and / or silicon-based surfactants, examples include the surfactants disclosed in paragraphs

[0218] and

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

[0304] Surfactants can be used alone or in combination with two or more.

[0305] When the composition of the present invention contains a surfactant, the content of the surfactant, relative to the total solid content of the composition of the present invention, is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0306] Solvent The composition of the present invention preferably contains a solvent. The solvent preferably comprises at least one of components (M1) and (M2), wherein component (M1) is a propylene glycol monoalkyl ether carboxylic acid ester, and component (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones, and alkyl carbonates. Furthermore, the solvent may further comprise components other than (M1) and (M2).

[0307] From the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern, it is preferable to combine the above-mentioned solvent and the above-mentioned resin. Since the above-mentioned resin has a good balance of solubility, boiling point and viscosity, the above-mentioned solvent can suppress uneven film thickness of the photoresist film and the generation of precipitates during spin coating. Details of the ingredients (M1) and (M2) are described in paragraphs

[0218] to

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

[0308] When 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% by mass relative to the total amount of solvent.

[0309] The solvent content in the composition of the present invention is preferably set such that the solid component concentration is 0.5-30% by mass, more preferably 1-20% by mass. This further improves the coatability of the composition of the present invention.

[0310] <Other Additives> The composition of the present invention may further contain a solubility-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility relative to the developer (e.g., a phenolic compound with a molecular weight of less than 1000, or an alicyclic or aliphatic compound containing a carboxyl group).

[0311] The aforementioned "dissolution-inhibiting compounds" refer to compounds with a molecular weight of less than 3000 that have reduced solubility in organic developing solutions due to acid decomposition.

[0312] The composition of the present invention is suitable for use as a photosensitive composition for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons at the same sensitivity. Therefore, "photon shot noise," which probabilistically deviates from the expected photon count, has a greater impact, leading to deterioration of line edge roughness (LER) and bridging defects. To reduce photon shot noise, increasing the exposure to increase the number of incident photons is one method, but this must be balanced with the requirement for high sensitivity.

[0313] When the value of A, calculated by the following formula (1), is high, the absorption efficiency of EUV light and electron beam of the photoresist film formed by the photoresist composition is higher, which can effectively reduce photon shot noise. The value of A represents the absorption efficiency of EUV light and electron beam of the photoresist film by mass ratio. Formula (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) The A value is preferably above 0.120. There is no particular upper limit, but when the A value is too large, the transmittance of EUV light and electron beam in the photoresist film will decrease, the optical image contour in the photoresist film will deteriorate, and it will be difficult to obtain a good pattern shape. Therefore, it is preferably below 0.240, and more preferably below 0.220.

[0314] Furthermore, in formula (1), [H] represents the molar ratio of hydrogen atoms from the total solids component of the photosensitive or radiosensitive linear resin composition to all atoms of the total solids component, [C] represents the molar ratio of carbon atoms from the total solids component of the photosensitive or radiosensitive linear resin composition to all atoms of the total solids component, [N] represents the molar ratio of nitrogen atoms from the total solids component of the photosensitive or radiosensitive linear resin composition to all atoms of the total solids component, and [O] represents the molar ratio of nitrogen atoms from the total solids component of the photosensitive or radiosensitive linear resin composition to all atoms of the total solids component. The molar ratio of oxygen atoms in the total solids component relative to all atoms in the total solids component in the composition, [F] represents the molar ratio of fluorine atoms in the total solids component relative to all atoms in the total solids component derived from photosensitive or radiosensitive linear resin compositions, [S] represents the molar ratio of sulfur atoms in the total solids component relative to all atoms in the total solids component derived from photosensitive or radiosensitive linear resin compositions, and [I] represents the molar ratio of iodine atoms in the total solids component relative to all atoms in the total solids component derived from photosensitive or radiosensitive linear resin compositions. For example, when the photoresist composition contains an acid-degrading resin, a photoacid generator, an acid diffusion control agent, and a solvent, the aforementioned acid-degrading resin, photoacid generator, and acid diffusion control agent are equivalent to the solid components. That is, all the atoms of the total solid components are equivalent to the sum of all atoms originating from the aforementioned resin, all atoms originating from the aforementioned photoacid generator, and all atoms originating from the aforementioned acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms originating from the total solids to all atoms in the total solids. If we are to explain based on the above example, then [H] represents the molar ratio of the sum of hydrogen atoms originating from the acid-degrading resin, the photoacid generator, and the acid diffusion control agent to the sum of all atoms originating from the acid-degrading resin, the photoacid generator, and the acid diffusion control agent.

[0315] The A value can be calculated by determining the atomic ratio when the structure and content of the total solid components in the photoresist composition are known. Furthermore, even when the constituent components are unknown, the atomic ratio can be calculated using analytical methods such as elemental analysis for photoresist films obtained by evaporating the solvent components of the photoresist composition.

[0316] <Second-state sample of photosensitive or radiosensitive linear resin composition> The photosensitive radioactive or radiosensitive linear resin composition of the present invention can be in the following state (also referred to as "the composition of the second state"). Second state sample: a photosensitive radioactive or radiosensitive linear resin composition, containing at least (AX), (B) and (C) below. (AX) contains repeating units (ax1) with an acid group having a pKa of 8.0 or higher and 12.0 or lower. Repeating units (a2) with acid groups having a pKa less than 8.0, and A repeating unit (a3) ​​containing at least one fluorine atom and no acid group with a pKa below 12.0, wherein the resin film made solely of resin has a dissolution rate of 0.002 nm / s or higher in an alkaline developing solution. (B) Contains repeating units (b1) having phenolic hydroxyl groups, and Repeating unit (b2) with groups that decompose under acidic conditions and have increased polarity. Furthermore, the resin does not contain repeating units that produce acid through exposure to photochemical rays or radiation. (C) Compounds that produce acids through exposure to photochemical rays or radiation.

[0317] The composition of the second state is the same as that of the aforementioned composition of the present invention, except that it includes component (AX) in place of component (A). (AX) component is also known as resin (AX). The dissolution rate of the resin (AX) film made solely of resin in an alkaline developer is 0.002 nm / s or higher, preferably 0.005 nm / s or higher, and more preferably 0.01 nm / s or higher. The upper limit of the above dissolution rate is preferably 100 nm / s or lower. The method for calculating the dissolution rate of a film made solely of resin in an alkaline developer is as described above. The resin (AX) film, made solely of resin, dissolves at a rate of over 0.002 nm / s in alkaline developing solution, thus exhibiting excellent developability and further improving LWR performance, making it superior. The dissolution rate of a resin-based film in an alkaline developer can be adjusted by the ratio of the content of repeating units (a1), (a2), and (a3), as well as their molecular weight.

[0318] The resin (AX) is the same as the aforementioned resin (A) except that it contains the repeating unit (ax1) instead of the repeating unit (a1). The structure of the repeating unit (ax1) of the resin (AX) is not particularly limited, but is preferably represented by the above general formula (a1-1) or (a1-2). The description, specific examples and preferred scope of the repeating unit (ax1) of the resin (AX) are the same as those described for the aforementioned repeating unit (a1).

[0319] <Methods for forming photosensitive or radiosensitive linear films and patterns> The present invention also relates to a photosensitive radioactive or radioactive linear film formed from the components of the present invention (hereinafter, "the components of the present invention" also includes the aforementioned "second-state components"). The photosensitive radioactive or radioactive linear film of the present invention is preferably a photoresist film. There is no particular limitation on the order of the pattern forming method using the components of the present invention, but it is preferred to include the following processes. Process 1: A process of forming a photoresist film on a substrate using the components of the present invention. Process 2: The process of exposing the photoresist film. Process 3: The process of developing the exposed photoresist film using a developing solution. The steps of each of the above processes will be described in detail below.

[0320] (Process 1: Photoresist film formation process) Process 1 is a process of forming a photoresist film on a substrate using the components of the present invention.

[0321] As a method for forming a photoresist film on a substrate using the composition of the present invention, for example, a method of coating the composition of the present invention onto a substrate can be cited. Furthermore, it is preferable to filter the components of the present invention with a filter as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0322] The components of this invention can be applied to a substrate (e.g., a silicon or silicon dioxide coating) for manufacturing integrated circuit elements by a suitable coating method such as a spin coater or a coating machine. The preferred coating method is spin coating using a spin coater. The preferred rotation speed for spin coating using a spin coater is 1000-3000 rpm (rotation per minute). After coating the composition of this invention, the substrate can be dried to form a photoresist film. Furthermore, various substrate films (inorganic films, organic films, anti-reflective films) can be formed on the underside of the photoresist film, as needed.

[0323] As a drying method, for example, drying by heating can be cited. Heating can be carried out using the equipment provided in a conventional exposure machine and / or developing machine, or it can be carried out using a hot plate. The heating temperature is preferably 80~150°C, more preferably 80~140°C, and even more preferably 80~130°C. The heating time is preferably 30~1000 seconds, more preferably 60~800 seconds, and even more preferably 60~600 seconds.

[0324] There is no particular limitation on the thickness of the photoresist film, but from the viewpoint of forming finer patterns with higher precision, a thickness of 10 to 120 nm is preferred. Specifically, when using EUV exposure, the thickness of the photoresist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the thickness of the photoresist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0325] In addition, a topcoat composition can be used to form a topcoat on the top layer of the photoresist film. The composition of the top coating is preferably not mixed with the photoresist film and can be uniformly coated on the upper layer of the photoresist film. The top coating is not particularly limited and can be formed by previously known methods, for example, the top coating can be formed according to paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the photoresist film. Specific examples of alkaline compounds that can be contained in the top coating include alkaline compounds that can be contained in the composition of the present invention. The top coating is preferably a compound containing at least one group or bond selected from the group consisting of ether, thioether, hydroxyl, thiol, carbonyl and ester bonds.

[0326] (Process 2: Exposure Process) Process 2 is a process for exposing the photoresist film. One method of exposure is to irradiate the formed photoresist film with photochemical rays or radiation through a prescribed mask. Examples of photochemical rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Far ultraviolet light with wavelengths below 250 nm, more preferably below 220 nm, and especially preferably 1-200 nm can be cited. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0327] It is preferable to bake (heat) after exposure and before development. Baking promotes the reaction of the exposed part, thereby improving sensitivity and pattern shape. The preferred heating temperature is 80~150℃, more preferably 80~140℃, and even more preferably 80~130℃. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using the equipment found in conventional exposure machines and / or developing machines, or it can be done using hot plates, etc. This process is also known as post-exposure baking.

[0328] (Process 3: Development Process) Process 3 uses a developer to develop the exposed photoresist film to form a pattern. The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as an organic developer).

[0329] Examples of development methods include, for instance, immersing the substrate in a tank filled with developer for a certain period of time (immersion method), using surface tension to cause developer to accumulate on the substrate surface and leave it to stand for a certain period of time to perform development (puddle method), spraying developer onto the substrate surface (spraying method), and continuously spraying developer from a nozzle on a substrate rotating at a certain speed while scanning at a certain speed (dynamic distribution method). Furthermore, after the developing process, a process can also be implemented where the developing process is stopped while the solvent is being replaced with another solvent. The development time is only the time required for the resin in the unexposed areas to fully dissolve, and there are no particular restrictions. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The optimal temperature for the developer is 0~50℃, and more preferably 15~35℃.

[0330] Alkaline developer is preferably an alkaline aqueous solution containing an alkali. There are no particular limitations on the type of alkaline aqueous solution; examples include alkaline aqueous solutions containing quaternary ammonium salts (represented by tetramethylammonium hydroxide), inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, or cyclic amines. Among these, an aqueous solution of a quaternary ammonium salt (represented by tetramethylammonium hydroxide, TMAH) is preferred. Appropriate amounts of alcohols, surfactants, etc., can be added to the alkaline developer. The alkali concentration of the alkaline developer is typically preferred to be 0.1% to 20% by mass. The pH of the alkaline developer is typically preferred to be 10.0 to 15.0.

[0331] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0332] The solvents described above can be mixed in multiple ways, or mixed with solvents other than those described above, or with water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and most preferably substantially water-free. The content of organic solvent relative to the organic developer, relative to the total amount of developer, is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and especially preferably 95% by mass or more and 100% by mass or less.

[0333] (Other processes) The above-mentioned pattern formation method preferably includes a cleaning process with rinsing solution after process 3.

[0334] As a rinsing solution used in the rinsing process following development with an alkaline developer, pure water can be cited as an example. Furthermore, an appropriate amount of surfactant can be added to the pure water. An appropriate amount of surfactant can also be added to the rinsing solution.

[0335] The rinsing solution used in the rinsing process after the developing process using an organic developer is not particularly restricted, as long as it does not dissolve the pattern. Solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0336] There are no particular limitations on the rinsing process. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion), and spraying rinsing liquid onto the surface of the substrate (spraying). Furthermore, the pattern forming method can include a post-bake process after the washing process. This process removes residual developer and washing solution between and inside the pattern through baking. Additionally, this process also anneals the photoresist pattern and improves its surface roughness. The post-wash heating process is typically performed at 40–250°C (preferably 90–200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0337] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the lower film and substrate) and form a pattern on the substrate. There are no particular limitations on the processing method of the substrate (or the lower film and the substrate), but it is preferable to use the pattern formed in process 3 as a mask and form the pattern on the substrate (or the lower film and the substrate) by dry etching. Dry etching is preferably oxygen plasma etching.

[0338] The various materials used in the composition and pattern forming method of the present invention (e.g., solvents, developers, rinsing solutions, compositions for forming antireflective films, compositions for forming topcoats, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular limitation on the lower limit, but it is preferably 0 ppt or more. Examples of metallic impurities include, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0339] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. Details of filtration using a filter are described in paragraph

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

[0340] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials for various materials, filtering the raw materials for various materials with filters, and using TEFLON (registered trademark) to form a lining in the apparatus to carry out distillation under conditions that suppress contamination as much as possible.

[0341] In addition to filtration, impurities can also be removed using adsorption materials, or a combination of filtration and adsorption materials can be used. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the metal content in the cleaning solution used to clean the manufacturing apparatus. The metal content in the used cleaning solution is preferably less than 100 parts per trillion (ppt), more preferably less than 10 ppt, and even more preferably less than 1 ppt. There is no particular lower limit, but it is preferably 0 ppt or more.

[0342] Conductive compounds can be added to organic processing solutions such as rinsing solutions to prevent malfunctions in the solution piping and various components (filters, O-rings, and tubing) caused by static electricity and subsequent electrostatic discharge. There are no particular limitations on the conductive compounds; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining better developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There are no particular limitations on the lower limit, but it is preferably 0.01% by mass or more. For example, SUS (stainless steel) or various pipes coated with anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used for chemical fluid piping. Similarly, for filters and O-rings, anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can also be used.

[0343] Manufacturing Methods of Electronic Devices This specification also relates to a method for manufacturing an electronic device that includes the above-described pattern forming method, and to an electronic device manufactured by the method. As a preferred embodiment of the electronic device described in this specification, it may be embodied in electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.). [Example]

[0344] The present invention will be described in more detail below based on embodiments. The materials, amounts, ratios, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0345] The various components used in the photoresist compositions of the embodiments and comparative examples are shown below.

[0346] <Resin(A)> As resin (A), AP-1 to AP-13 were used. Furthermore, in the comparative example, RAP-1 to RAP-4 were used as resins other than resin (A). For convenience, RAP-1 to RAP-4 are also listed in the resin (A) column in Table 3 below. AP-1 to AP-13 and RAP-1 to RAP-4 are those containing the repeating units shown in Table 1 according to the molar ratio shown in Table 1 below. Each repeating unit is shown by the structure of the corresponding monomer. Although the repeating unit formed by the corresponding monomer MX contained in RAP-2 is not equivalent to repeating unit (a1), it is recorded in the repeating unit (a1) column for convenience. Table 1 also shows the dissolution rates of individual films made solely of resin in alkaline developer (denoted as "VA" in Table 1). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the content of repeating units was determined by 13C-NMR (nuclear magnetic resonance).

[0347] (Dissolution rate (VA) of a film made solely of resin in an alkaline developer) Each resin was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (mass ratio of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 8 / 2) to prepare a film at a concentration of 3% by mass. The prepared resin solution was coated onto a 6-inch Si wafer pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resin film with a thickness of 100 nm. The film thickness reduction rate when the resin film was immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C was calculated using a Litho Tech Japan Corporation photoresist developer analyzer (RDA-790EB). The dissolution rate (VA) of the resin-only film in an alkaline developer was calculated in the same manner. The VA is recorded in Table 1.

[0348] [Table 1]

[0349] The corresponding monomer structures and pKa shown in Table 1 are as follows.

[0350] [Chemical Formula 65]

[0351] [Chemical Formula 66]

[0352] [Chemical Formula 67]

[0353] <Resin (B): Acid-degradable resin> MP-1 to MP-5 were used as resins (B). Table 2 shows the content (moles%), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit contained in each resin. The content of repeating units is the ratio (molar ratio) of each repeating unit contained in each resin to all repeating units. In Table 2, the content of repeating units for each resin corresponds to the order in which the repeating units are recorded in the structural formulas of each resin as shown below. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the content of repeating units was determined by 13C-NMR (nuclear magnetic resonance).

[0354] [Chemical Formula 68]

[0355] [Table 2]

[0356] <Compound (C): Photoacid Generator> As compound (C), C-1 to C-2 were used.

[0357] [Chemical Formula 69]

[0358] <Acid diffusion control agent> Q-1 to Q-3 were used as acid diffusion control agents.

[0359] [Chemical Formula 70]

[0360] <surfactants> The surfactants used are shown below. W-1: MEGAFAC R08 (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.; fluorine and silicon-based surfactant).

[0361] Solvent The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane) S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) S-3: Ethyl lactate S-4: γ-Butyrolactone

[0362] <Preparation of Photoresist Composition> Dissolve the components shown in Table 3 in the solvents shown in Table 3 to prepare a solution with the solid component concentrations shown in Table 3, and filter it through a polyethylene filter with a pore size of 0.02 μm to prepare a photoresist composition. Furthermore, the term "solid component" refers to all components other than the solvent. The obtained photoresist composition was used in the examples and comparative examples. Table 3 shows the content (mass%) of each component relative to the total solids content in the photoresist composition. Furthermore, regarding solvents, the types of compounds used and their proportions (mass ratios) are listed. When using surfactants, the addition amount is set to 0.1% by mass relative to the total solids content in the photoresist composition.

[0363] [Table 3]

[0364] <Pattern Formation Method (1): EB Exposure, Alkaline Development (Positive Type)> The prepared photoresist composition was coated onto a 6-inch Si wafer pretreated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and then dried at 100°C for 60 seconds on a hot plate to obtain a photoresist film with a thickness of 100 nm. Furthermore, the same result can be obtained even if the Si wafer is replaced with a chromium substrate. The photoresist-coated wafer obtained above was patterned using an electron beam lithography apparatus (Hitachi, Ltd. HL750, accelerating voltage 50keV). At this time, a 1:1 line-space pattern was formed. After electron beam lithography, the wafer was heated at 100°C for 60 seconds on a hot plate, developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 30 seconds, rinsed with pure water, then rotated at 4000 rpm for 30 seconds, and finally heated at 95°C for 60 seconds to obtain a 1:1 line-space pattern with a linewidth of 50 nm.

[0365] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). The exposure (electron beam irradiation) when resolving a 1:1 line with a linewidth of 50 nm and a photoresist pattern in space was used as the sensitivity (Eopt). The resolution (nm) is defined as the minimum linewidth at which the line and space (line:space = 1:1) are separated and resolved at the exposure levels of the above sensitivity.

[0366] [LWR (Initial)] Using a length-measuring scanning electron microscope (SEM (Hitachi, S-9380II)), a line-space pattern (line:space = 1:1) with a linewidth of 50 nm, as resolved by the above method, was observed from above. The linewidth of the pattern was observed at any point (160 points), and its standard deviation (σ) was calculated. 3σ (nm) was used as the LWR value to evaluate the measurement deviation of the linewidth. This value was set as "LWR (initial)". The smaller the value, the better the LWR performance.

[0367] [LWR (after elapsed time)] As for the photoresist components, except for those photoresist components that have been stored at 23°C for 6 months, the LWR value was calculated in the same manner as the "LWR (initial)" mentioned above. This value is taken as "LWR (after time)".

[0368] [PED Stability] Under exposure conditions of 50nm linewidth and 50nm spatial width for a 1:1 line and a spatial pattern with a linewidth of 50nm, the linewidth dimensions (L0h) after rapid PEB processing following exposure and after PEB processing one hour after exposure (L2h) were measured, and the linewidth change rate was calculated using the following formula. Furthermore, the PEB processing involved heating at 100°C for 60 seconds. Linewidth change rate (%) = 100 x (L2h - L0h) nm / 50 nm A smaller value indicates better performance and serves as an indicator of PED stability. Furthermore, in practical applications, a value of B or higher is preferred, with A being even better. A: Line width variation rate is less than 2%. B: Line width variation rate is 2% or more but less than 5%. C: Line width variation rate is 5% or more but less than 10% D: Line width variation rate is above 10%

[0369] <Pattern Formation Method (2): EUV Exposure, Alkaline Development (Positive Type)> The prepared photoresist composition was coated onto a 6-inch Si wafer pretreated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and then dried at 100°C for 60 seconds on a hot plate to obtain a photoresist film with a thickness of 100 nm. Using an EUV exposure apparatus (Exitech; Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36), and with an exposure mask (line / space = 1 / 1), a wafer with a photoresist film configured as described above was patterned and exposed. After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, and then immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds. The wafer was then rinsed with water for 30 seconds. Afterward, the wafer was rotated at 4000 rpm for 30 seconds and then baked at 95°C for 60 seconds to dry it. In this manner, a photoresist pattern with a line and space pattern (line / space = 1 / 1) with a linewidth of 50 nm was obtained.

[0370] <Performance Evaluation> The LWR (initial) and PED stability were evaluated using the same method as those described above.

[0371] [Table 4]

[0372] As shown in Table 4, the photoresist compositions used in Examples 1-29 exhibit excellent resolution, LWR performance, and PED stability. Regarding LWR performance, both the "LWR (initial)" when the photoresist composition is used immediately after preparation and the "LWR (after time)" when the photoresist composition is used after being stored at 23°C for 6 months after preparation are excellent. [Industrial Applicability]

[0373] According to the present invention, a photosensitive or radiosensitive linear resin composition with excellent LWR performance and PED stability can be provided. Furthermore, according to the present invention, it is possible to provide a photosensitive or radiosensitive linear film using the above-described photosensitive or radiosensitive linear resin composition, a pattern forming method, and a manufacturing method for electronic components.

[0374] Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2022-008250, filed on January 21, 2022, the contents of which are incorporated herein by reference.

[0375] none

[0376] none

Claims

1. A photosensitive or radiosensitive linear resin composition comprising at least the following (A), (B) and (C): (A) a resin comprising repeating units (a1) having an acid group with a pKa of 8.0 or more and 12.0 or less, repeating units (a2) having an acid group with a pKa less than 8.0, and repeating units (a3) ​​having at least one fluorine atom and not having an acid group with a pKa of 12.0 or less; (B) a resin comprising repeating units (b1) having a phenolic hydroxyl group, and repeating units (b2) having a group that decomposes under the action of acid and increases in polarity, and not containing repeating units that generate acid by irradiation with photosensitive rays or radiation; (C) an ionic photoacid generator. In the above general formula, Ra1 represents a hydrogen atom or an alkyl group; Ra2 represents a halogen atom, alkyl group, aryl group, heteroaryl group, alkoxy group, alkylthio group, alkoxycarbonyl group, or alkylcarbonyloxy group. When there are multiple Ra2s, they can be the same or different. L1 represents a single bond or -C(=O)O-; m represents an integer from 0 to 2; n1 represents an integer greater than 1 and less than (5+2m); k1 represents an integer greater than 0 and less than (5+2m-n1).

2. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, In the general formula (a1-1), m represents 0 or 1.

3. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, In this general formula (a1-1), L1 represents a single bond.

4. The photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 3, wherein, The repeating unit (a3) ​​contains an alkyl group having three or more fluorine atoms as substituents.

5. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 3, wherein, The repeating unit (a3) ​​is represented by the following general formula (a3-1): In general formula (a3-1), Ra3 represents a hydrogen atom or an alkyl group; Ra4 represents an alkyl group having three or more fluorine atoms as substituents.

6. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 3, wherein, The pKa of the acid group in the repeating unit (a2) is greater than 0.0 and less than 6.

0.

7. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 3, wherein, The repeating unit (a2) is represented by the following general formula (a2-1): In general formula (a2-1), Ra5 represents a hydrogen atom or an alkyl group; L3 represents a linking group consisting of a single bond or at least one of the groups selected from the group consisting of alkyl, cycloalkyl and aryl groups; p represents an integer from 1 to 3.

8. A photosensitive or radiosensitive linear resin composition, comprising at least the following (AX), (B) and (C): (AX) comprising repeating units (ax1) having an acid group with a pKa of 8.0 or more and 12.0 or less, repeating units (a2) having an acid group with a pKa less than 8.0, and repeating units (a3) ​​having at least one fluorine atom and not having an acid group with a pKa of 12.0 or less, wherein the film made of the resin has a dissolution rate of 0.002 nm / s or more in an alkaline developing solution; (B) comprising repeating units (b1) having phenolic hydroxyl groups, and repeating units (b2) having groups that decompose under the action of acid and increase in polarity, and not containing repeating units that generate acid by irradiation with photosensitive rays or radiation; (C) ionic photoacid generator. In the above general formula, Ra1 represents a hydrogen atom or an alkyl group. Ra2 represents a halogen atom, alkyl, aryl, heteroaryl, alkoxy, alkylthio, alkoxycarbonyl, or alkylcarbonyloxy; when there are multiple Ra2s, they can be the same or different; L1 represents a single bond or -C(=O)O-; m represents an integer from 0 to 2; n1 represents an integer greater than 1 and less than (5+2m); k1 represents an integer greater than 0 and less than (5+2m-n1).

9. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 8, wherein, The (AX) film, made solely of resin, dissolves at a rate of over 0.01 nm / s in an alkaline developer.

10. A photosensitive radioactive or radiosensitive linear film formed from a photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 9.

11. A pattern forming method comprising: a process of forming a photosensitive radioactive or radioactive linear resin composition on a substrate from any one of claims 1 to 9; a process of exposing the photosensitive radioactive or radioactive linear film; and a process of developing the exposed photosensitive radioactive or radioactive linear film using a developing solution.

12. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 11.