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

Abstract

This invention provides a photosensitive or radiosensitive linear resin composition that exhibits excellent roughness performance and suppresses the generation of pattern defects in the formation of extremely fine patterns (e.g., line and spatial patterns with apertures of 30 nm or less, or hole patterns with apertures of 30 nm or less). The photosensitive or radiosensitive linear resin composition comprises: (A) a resin having repeating units derived from a compound represented by a specific formula (1); and (B) a compound that generates an acid upon irradiation by photosensitive rays or radiation.

Description

Technical Field

[0001] This invention relates to a photosensitive radioactive or radioactive linear resin composition, a photosensitive radioactive or radioactive linear film, a pattern forming method, a method for manufacturing electronic components, a compound, and a resin. Prior Technology

[0002] In the manufacturing process of semiconductor devices such as integrated circuits (ICs) and large-scale integrated circuits (LSIs), microfabrication is performed by using photosensitive components. As a photolithography method, one example is the formation of a resist film using a photosensitive composition, followed by exposure and development. In particular, in recent years, research has been conducted on using electron beam (EB) and extreme ultraviolet (EUV) light in addition to ArF excimer lasers during exposure, and photosensitive radioactive or radiosensitive linear resin compositions suitable for EUV exposure are being developed.

[0003] In the formation of resist patterns using EUV (wavelength 13.5 nm) or electron beams for the purpose of forming fine patterns, the requirements for various performance aspects are more stringent compared to the previous use of ArF (wavelength 193 nm) light.

[0004] Furthermore, Patent Document 1 discloses a resist composition containing a specific photoacid generating agent. For example, Patent Document 1 discloses a salt represented by a specific formula, a resin having structural units derived from the salt, and a resist composition containing the resin and the acid generating agent. Patent document 2 discloses a composition comprising a resin and a compound that produces an acid by irradiation with photosensitive rays or radiation, wherein the composition satisfies specific parameters and the compound is a specific compound. [Existing Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-99553 [Patent Document 2] International Publication No. 2020 / 158417 Summary of the Invention

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

[0007] In recent years, the miniaturization of patterns formed using EUV light or electron beams has continued to advance, requiring further improvements in aspects such as pattern roughness and defect performance.

[0008] Therefore, the objective of this invention is to provide a photosensitive or radiosensitive linear resin composition that exhibits excellent roughness performance and suppresses the generation of pattern defects in the formation of extremely fine patterns (e.g., line and spatial patterns with a diameter of 30 nm or less, or hole patterns with a diameter of 30 nm or less). Furthermore, the objective of this invention is to provide a photosensitive or radiosensitive linear film using the aforementioned photosensitive radiosensitive or radiosensitive linear resin composition, a patterning method, and a method for manufacturing electronic components. Furthermore, the objective of this invention is to provide a compound and a resin. [Methods for solving problems]

[0009] The inventors have discovered that the aforementioned problem can be solved by the following structure.

[0010] [1] A photosensitive radioactive or radiosensitive linear resin composition comprising: (A) a resin having repeating units derived from a compound represented by formula (1); and (B) Compounds that produce acids through irradiation by photochemical rays or radiation.

[0011] [Chemistry 1]

[0012] (in formula (1),) A represents a polymerizing group. L represents a divalent bonding group containing a halogen atom. R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. R 4 represents a hydrogen atom or an organic group. Let n represent an integer greater than or equal to 1, m represent an integer greater than or equal to 0, and p represent an integer greater than or equal to 0, where n, m, and p satisfy the relationship n + m ≤ 5 + 2p. When m represents an integer greater than 2, multiple R3s can be the same or different; when n represents an integer greater than 2, multiple R4s can be the same or different.

[0013] [2] As described in [1], the photosensitive radioactive or radiosensitive linear resin composition, wherein the compound represented by formula (1) is the compound represented by formula (2) below.

[0014] [Chemistry 2]

[0015] In equation (2), A has the same meaning as A in equation (1). L1 represents a single bond or a divalent linker. R1 represents a halogen atom or an organic group containing a halogen atom. R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (1).

[0016] [3] The photosensitive radioactive or radiosensitive linear resin composition as claimed in claim 2, wherein the compound represented by formula (2) is the compound represented by formula (3) below.

[0017] [Chemistry 3]

[0018] In equation (3), X represents a hydrogen atom or an organic group. R1 and R2 have the same meaning as R1 and R2 in equation (2), respectively. L2 represents a single bond or a divalent linker. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (1).

[0019] [4] As described in any one of [1] to [3], the photosensitive radioactive or radiosensitive linear resin composition, wherein the compound (B) is an onium salt. [5] As described in any one of [1] to [4], the photosensitive radioactive or radiosensitive linear resin composition, wherein the resin (A) has repeating units represented by the following formula (4).

[0020] [Chemistry 4]

[0021] In equation (4), X 11 represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group. R11 each independently represents an alkyl group, and two R11 groups can bond together to form a ring.

[0022] [6] A photosensitive radioactive or radioactive linear membrane, formed from a photosensitive radioactive or radioactive linear resin composition as described in any one of [1] to [5]. [7] A method for forming a pattern, comprising: The step of forming a photosensitive radioactive or radioactive linear film on a substrate using any one of the photosensitive radioactive or radioactive linear resin compositions as described in any one of [1] to [5]; The steps of exposing the photosensitive radioactive or radiosensitive linear film; and The step of using a developer to develop the exposed photosensitive radioactive or radiosensitive linear film to form a pattern. [8] A method for manufacturing an electronic component, comprising a pattern forming method as described in [7]. [9] A compound is represented by the following formula (2).

[0023] [Chemistry 5]

[0024] In equation (2), A represents a polymerizing group. L1 represents a single bond or a divalent organic group. R1 represents a halogen atom or an organic group containing a halogen atom. R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group. R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. R 4 represents a hydrogen atom or an organic group. Let n represent an integer greater than or equal to 1, m represent an integer greater than or equal to 0, and p represent an integer greater than or equal to 0, where n, m, and p satisfy the relationship n + m ≤ 5 + 2p. When m represents an integer greater than 2, multiple R3s can be the same or different; when n represents an integer greater than 2, multiple R4s can be the same or different.

[0025]

[10] The compounds described in [9] are compounds represented by formula (2) below, which are compounds represented by formula (3) below.

[0026] [Chemistry 6]

[0027] In formula (3), X represents a hydrogen atom or an organic group. R1 and R2 have the same meaning as R1 and R2 in equation (2). L2 represents a single bond or a divalent linker. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (2).

[0028]

[11] A resin having repeating units derived from compounds as described in [9] or

[10] . [The effects of the invention]

[0029] According to the present invention, a photosensitive or radiosensitive linear resin composition is provided that exhibits excellent roughness performance and suppresses the generation of defects in patterns during the formation of extremely fine patterns (e.g., line and spatial patterns with apertures of less than 30 nm or hole patterns with apertures of less than 30 nm). Furthermore, according to the present invention, a photosensitive radioactive or radioactive linear resin composition, a pattern forming method, a method for manufacturing electronic components, a compound, and a resin can be provided. Simple Explanation of the Diagram

[0030] none Implementation

[0031] Hereinafter, an example of a form used to implement the present invention will be described. Furthermore, in this specification, the numerical range indicated by "~" refers to the range of values ​​recorded before and after "~" as the lower and upper limits.

[0032] Unless otherwise specified, the bonding orientation of the divalent groups described in this specification is not limited. For example, in compounds represented by the general formula "XYZ" where Y is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the compound can be "X-CO-OZ" or "XO-CO-Z".

[0033] In this specification, "(meth)acrylate" is a general term encompassing both acrylic and methacrylate groups, and specifically refers to "at least one of acrylic and methacrylate groups." Similarly, "(meth)acrylic acid" refers to "at least one of acrylic acid and methacrylic acid."

[0034] The terms "photochemical rays" or "radiation" in this specification refer to, for example, the bright-line spectrum of a mercury lamp, the far-ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, and electron beams (EB). The term "light" in this specification refers to photochemical rays or radiation. Unless otherwise specified, "exposure" in this instruction manual includes not only exposure using the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, X-rays, and EUV light, but also depiction using particle beams such as electron beams and ion beams.

[0035] 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 gel permeation chromatography (GPC) 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)

[0036] 1 Å is 1×10⁻¹⁰ m.

[0037] The acid dissociation constant (pKa) referred to in this specification means the pKa in aqueous solution, specifically obtained by calculation using the software package described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification represent values ​​obtained by calculation using this software package.

[0038] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0039] On the other hand, pKa is also determined by molecular orbital calculations. One specific method is to calculate it using the free energy of H+ dissociation in the solvent based on thermodynamic cycles. (Furthermore, in this specification, water is typically used as the solvent; when pKa cannot be determined in water, dimethylsulfoxide (DMSO) is used.) Methods for calculating the H+ dissociation free energy include density functional theory (DFT), and various other methods have been reported in the literature, so this is not a limitation. Furthermore, several software programs exist that can perform DFT, such as Gaussian16.

[0040] As described in this specification, pKa refers to the value obtained by using software package 1 to calculate a database based on Hammett substituent constants and known literature values. In cases where pKa cannot be calculated by this method, it is assumed to be the value obtained by using density functional theory (DFT) and Gaussian 16.

[0041] Regarding the use of the term "group" (atomic group) in this specification, the descriptions of "substituted" and "unsubstituted" include both unsubstituted and substituted groups. For example, the term "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom.

[0042] Furthermore, this specification does not impose any particular restrictions on the type, position, or number of substituents when it mentions "may have substituents." The number of substituents may be one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, which may be selected from the following substituent T.

[0043] (Substituent T) Examples of substituents T include: halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tributoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; aceoxy groups such as acetoxy, propoxy, and benzooxy; and acetyl, benzoyl, isobutyl, propenyl, methacrylyl, and methoxyoxalyl. Acrylyl groups such as methoxalyl; alkyl mercapto groups such as methyl mercapto and tributyl mercapto; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl; alkenyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; methoxal; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonylamyl; silyl; amino; monoalkylamino; dialkylamino; arylamino; thiol; and combinations thereof.

[0044] [Photosensitive or radiosensitive linear resin composition] The photosensitive or radiosensitive linear resin composition of the present invention comprises: (A) a resin having repeating units derived from a compound represented by the following formula (1); and (B) a compound that produces an acid by irradiation with photosensitive rays or radiation.

[0045] [Chemistry 7]

[0046] In equation (1), A represents a polymerizing group. L represents a divalent bonding group containing a halogen atom. R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. R 4 represents a hydrogen atom or an organic group. Let n represent an integer greater than or equal to 1, m represent an integer greater than or equal to 0, and p represent an integer greater than or equal to 0, where n, m, and p satisfy the relationship n + m ≤ 5 + 2p. When m represents an integer greater than 2, multiple R3s can be the same or different; when n represents an integer greater than 2, multiple R4s can be the same or different.

[0047] Furthermore, in the photosensitive or radiosensitive linear resin composition of the present invention, the compound (B) that generates acid by irradiation with photosensitive rays or radiation can be the same compound (C) described later.

[0048] While the mechanism by which the present invention is solved using the aforementioned configuration may not be clear, the inventors have considered the following. In other words, the inventors first conducted a detailed study on the morphology of halogen atoms, which are particularly absorbent by EUV or electron beams and are expected to contribute to achieving the goal of forming extremely fine patterns (e.g., line and spatial patterns of less than 30 nm or pore patterns of less than 30 nm), in the resin of a photosensitive or radiosensitive linear resin composition (hereinafter also referred to as "composition"). The results showed that, in order to form good patterns, it is important that the resin and other components (such as acid generators or acid diffusion control agents) have high compatibility in the photosensitive or radiosensitive linear film (typically a photoresist film) formed by the composition. For example, in resins with hydroxyl-substituted aromatic rings, further substitution of halogen atoms on the aromatic rings to introduce halogen atoms into the resin morphology results in insufficient roughness performance during the formation of extremely fine patterns, and pattern defects are also easily generated. This is believed to be because, due to the formation of a structure within the resin where hydroxyl and halogen atoms are located close to each other, the resins tend to aggregate easily through this structure, leading to insufficient mixing (compatibility) between the resin and other components in the resist film. More specifically, due to insufficient compatibility between the resin and other components, it is believed that components other than the resin (such as acid generators or acid diffusion control agents) tend to aggregate easily, resulting in pattern defects. Furthermore, it is believed that in the exposed areas, the reaction between the acid generated by the acid generator and the resin tends to become incomplete, resulting in insufficient roughness performance.

[0049] On the other hand, in this invention, the halogen atom in L of the formula (1) exists to some extent separately from the group represented by OR 4, which is a substituent in the aromatic ring. The detailed reasons are not yet clear, but compared with the described form, it is speculated that even if the repeating unit derived from the compound represented by the formula (1) is in a state with halogen atoms, it is a state in which resins are not easily aggregated. Therefore, it is believed that the resin in the resist film has high compatibility with components other than resin, and is not prone to agglomeration of components other than resin (such as acid generators or acid diffusion control agents), thus suppressing defects in the resist. In addition, in the exposed part, for example, the reaction between the acid generated by the acid generator and the resin can be carried out easily and fully, thus obtaining sufficient roughness performance.

[0050] [Components of photosensitive or radiosensitive linear resins] The following provides a detailed description of the components that may be included in photosensitive or radiosensitive linear resin compositions. The photosensitive or radiosensitive linear resin composition of the present invention is typically a photoresist composition, which can be a positive or negative photoresist composition. Additionally, it can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development. The composition of the present invention is typically a chemically amplified photoresist composition.

[0051] <(A) Resin> The photosensitive or radiosensitive linear resin composition (hereinafter also referred to as the "composition") contains resin (A). Resin (A) is typically an acid-degradable resin, that is, a resin whose polarity increases by the action of acid, thereby increasing its solubility in alkaline developing solutions and decreasing its solubility in organic solvents. Resin (A) has a group that decomposes under the action of acid to generate a polar group (in other words, a structure in which the polar group is protected by a detaching group that is removed by the action of acid). This group (structure) is also called an acid-decomposable group. Resins with acid-decomposable groups (i.e., resins containing repeating units with acid-decomposable groups) become more polar due to the action of acid and have increased solubility relative to alkaline developing solutions, while their solubility relative to organic solvents decreases.

[0052] (Derived from the repeating unit of the compound represented by formula (1)) Resin (A) has repeating units derived from the compound represented by the following formula (1) (hereinafter also referred to as "repeating unit (a1)").

[0053] [Chemistry 8]

[0054] In equation (1), A represents a polymerizing group. L represents a divalent bonding group containing a halogen atom. R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. R 4 represents a hydrogen atom or an organic group. Let n represent an integer greater than or equal to 1, m represent an integer greater than or equal to 0, and p represent an integer greater than or equal to 0, where n, m, and p satisfy the relationship n + m ≤ 5 + 2p. When m represents an integer greater than 2, multiple R3s can be the same or different; when n represents an integer greater than 2, multiple R4s can be the same or different.

[0055] There is no particular limitation on the positional relationship between L and OR 4. When p is 0, it is preferable that L and OR 4 are located in the intermediate or opposite position. The polymerizable group of A is not particularly limited, for example, vinyl groups that may have substituents can be listed, preferably the group represented by the following formula (A).

[0056] [Chemistry 9]

[0057] In formula (A), X represents a hydrogen atom or an organic group. * indicates the location of the bond.

[0058] As an organic group, there are no particular limitations; examples include alkyl, alkenyl, cycloalkyl, aryl, alkoxy, etc. The alkyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably methyl or ethyl, and more preferably methyl. There are no particular limitations on the alkenyl group; examples include alkenyl groups with 2 to 12 carbon atoms that are either straight-chain or branched-chain, with vinyl groups being preferred. There is no particular limitation on the cycloalkyl group, and examples of cycloalkyl groups with 3 to 20 carbon atoms are possible. Preferred examples are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracene. The alkoxy group is not particularly limited, and examples include linear or branched alkoxy groups with 1 to 12 carbon atoms, preferably alkoxy groups with 1 to 6 carbon atoms, and more preferably alkoxy groups with 1 to 3 carbon atoms. Alkyl, alkenyl, cycloalkyl, aryl, and alkoxy groups may have substituents.

[0059] L represents a divalent bonding group containing a halogen atom. Examples of divalent linkages containing halogen atoms include: -COO-, -CO-, -O-, alkyl, cycloalkyl, aryl, and linkages formed by the linkage of multiple of these. The alkyl group is not particularly limited and can be either straight-chain or branched-chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3. The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 10, more preferably 3 to 6. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbons, and more preferably an aryl group with 6 to 10 carbons. alkyl, cycloalkyl, and aryl groups may have substituents. As a preferred embodiment, the alkyl, cycloalkyl, or aryl groups may have halogen atoms, hydroxyl groups, amino groups, thiols, or organic groups. Examples of organic groups, listed below, are those that are R2 in formula (2). These groups may further have substituents. A divalent linker of L containing halogen atoms has at least one halogen atom, or may have multiple halogen atoms.

[0060] R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. As an organic group, there are no particular limitations; examples include alkyl, alkenyl, cycloalkyl, aryl, etc. The alkyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably methyl or ethyl, and more preferably methyl. There are no particular limitations on the alkenyl group; examples include alkenyl groups with 2 to 12 carbon atoms that are either straight-chain or branched-chain, with vinyl groups being preferred. There is no particular limitation on the cycloalkyl group, and examples of cycloalkyl groups with 3 to 20 carbon atoms are possible. Preferred examples are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracene. Alkyl, alkenyl, cycloalkyl, and aryl groups may have substituents.

[0061] The organic group that serves as R4 is the same as the organic group that serves as R3 in formula (1), and the preferred range is also the same. R4 is preferably a hydrogen atom. The aromatic ring in formula (1) may further have substituents.

[0062] There is no specific upper limit for n, which is usually 5. A value of 1 to 3 is preferred, and 1 to 2 is even better. There is no specific upper limit for m, which is usually 5. The preferred value for m is 0~3, and even better is 0~2. There is no specific upper limit for p, which is usually 3. The preferred value for p is 0~3, and even better is 0~2.

[0063] The compound represented by formula (1) is preferably the compound represented by formula (2) below.

[0064] [Chemistry 10]

[0065] In equation (2), A has the same meaning as A in the above formula (1). L1 represents a single bond or a divalent linker. R1 represents a halogen atom or an organic group having a halogen atom. R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (1). When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

[0066] L1 represents a single bond or a divalent linker. Examples of divalent linking groups include: -COO-, -CO-, -O-, alkylene, cycloalkylene, arylene, and linking groups formed by multiple linkages of these. There are no particular limitations on the alkyl groups; they can be either straight-chain or branched-chain. 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. The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 10, more preferably 3 to 6. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbons, and more preferably an aryl group with 6 to 10 carbons. alkyl, cycloalkyl, and aryl groups may have substituents. L1 is preferred as a divalent linker.

[0067] R1 represents a halogen atom or an organic group having a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. As an organic group containing halogen atoms, there is no particular limitation; examples include alkyl, cycloalkyl, aryl, alkoxy, etc. The alkyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. There is no particular limitation on the cycloalkyl group, and examples of cycloalkyl groups with 3 to 20 carbon atoms are possible. Preferred examples are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracene. The alkoxy group is not particularly limited, and examples include linear or branched alkoxy groups with 1 to 12 carbon atoms, preferably alkoxy groups with 1 to 6 carbon atoms, and more preferably alkoxy groups with 1 to 3 carbon atoms.

[0068] Alkyl, cycloalkyl, aryl, and alkoxy groups may have substituents. As a preferred embodiment, the substituents are not particularly limited, but are preferably halogen atoms, hydroxyl groups, or alkoxy carbonyl groups. The alkyl group in the alkoxycarbonyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. The alkoxycarbonyl group may further have substituents. The substituents are not particularly limited, and for example, halogen atoms are preferred. The organic group containing halogen atoms as R1 has at least one halogen atom, or may have multiple halogen atoms.

[0069] R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. As an organic group, there are no particular limitations; examples include alkyl, cycloalkyl, aryl, alkoxy, etc. The alkyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. There is no particular limitation on the cycloalkyl group, and examples of cycloalkyl groups with 3 to 20 carbon atoms are possible. Preferred examples are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracene. The alkoxy group is not particularly limited, and examples include linear or branched alkoxy groups with 1 to 12 carbon atoms, preferably alkoxy groups with 1 to 6 carbon atoms, and more preferably alkoxy groups with 1 to 3 carbon atoms.

[0070] Alkyl, cycloalkyl, aryl, and alkoxy groups may have substituents. As a preferred embodiment, the substituents are not particularly limited, but are preferably halogen atoms, hydroxyl groups, or alkoxy carbonyl groups. The alkyl group in the alkoxycarbonyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. The alkoxycarbonyl group may further have substituents. The substituents are not particularly limited, and for example, halogen atoms are preferred. R2 is preferably a hydrogen atom, a halogen atom, or an organic group. R4 is preferably a hydrogen atom. The aromatic ring in formula (2) may further have substituents.

[0071] The compound represented by formula (2) is preferably the compound represented by formula (3) below.

[0072] [Chemistry 11]

[0073] In equation (3), X represents a hydrogen atom or an organic group. R1 and R2 have the same meaning as R1 and R2 in equation (2). L2 represents a single bond or a divalent linker. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (1). When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

[0074] X represents a hydrogen atom or an organic group. The organogroup of X is the same as the organogroup of X in formula (A), and the preferred range is also the same.

[0075] L2 represents a single bond or a divalent linker. Examples of divalent linking groups include: -COO-, -CO-, -O-, alkylene, cycloalkylene, arylene, and linking groups formed by multiple linkages of these. There are no particular limitations on the alkyl groups; they can be either straight-chain or branched-chain. 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. The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 10, more preferably 3 to 6. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbons, and more preferably an aryl group with 6 to 10 carbons. alkyl, cycloalkyl, and aryl groups may have substituents. L2 is preferably a single bond or an extended alkyl group. R2 is preferably a hydrogen atom, a halogen atom, or an organic group. R4 is preferably a hydrogen atom. The aromatic ring in formula (3) may further have substituents.

[0076] The following examples illustrate compounds represented by formula (1), but the present invention is not limited to these.

[0077] [Chemistry 12]

[0078] [Chemistry 13]

[0079] In resin (A), the repeating unit (a1) can be used alone or in more than two types.

[0080] In resin (A), the content of repeating unit (a1) relative to all repeating units of resin (A) is preferably 5 mol% to 70 mol%, more preferably 5 mol% to 55 mol%, and even more preferably 5 mol% to 30 mol%.

[0081] (Repeating unit (a2) with acid-decomposing groups) Resin (A) may contain repeating units with acid-degradable groups (also called "repeating units (a2)").

[0082] The acid-decomposable group is preferably a structure protected by a polar group that is removed by the acid (removed group). Examples of polar groups include: carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimido groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imido groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imido groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imido groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups (typically, groups dissociated in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), as well as alcoholic hydroxyl groups.

[0083] Furthermore, the term "alcoholic hydroxyl group" refers to hydroxyl groups other than those bonded to a hydrocarbon group and directly bonded to an aromatic ring (phenolic hydroxyl groups). This excludes aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) that are substituted at the α-position with electron-withdrawing groups such as fluorine atoms. Preferably, an alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 or higher and 20 or lower.

[0084] 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.

[0085] As a group that is released due to the action of an acid (released group), for example, the groups represented by formulas (Y1) to (Y4) can be listed. Equation (Y1): -C(Rx 1)(Rx 2)(Rx 3) Formula (Y2):-C(=O)OC(Rx 1)(Rx 2)(Rx 3) Formula (Y3):-C(R 3 6)(R 3 7)(OR 3 8) Equation (Y4): -C(Rn)(H)(Ar)

[0086] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched-chain), alkenyl (straight-chain or branched-chain), cycloalkyl (monocyclic or polycyclic), or aryl (monocyclic or polycyclic). Wherein, Rx 1 to Rx 3 preferably represent straight-chain or branched-chain alkyl groups independently, and Rx 1 to Rx 3 more preferably represent straight-chain alkyl groups independently. Two bonds between Rx 1 and Rx 3 can form a single ring or multiple rings. The alkyl group Rx 1 to Rx 3 is not particularly limited, and alkyl groups having 1 to 20 carbon atoms can be listed, with alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl being preferred. There are no particular limitations on the alkenyl group that is Rx 1 to Rx 3. Alkenyl groups with 2 to 20 carbon atoms can be listed, with vinyl, propenyl, isopropenyl and other alkenyl groups with 2 to 4 carbon atoms being preferred. There is no particular limitation on the cycloalkyl group Rx 1 to Rx 3. Examples of cycloalkyl groups with 3 to 20 carbon atoms are included. Preferred are 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 14 carbon atoms, such as phenyl, naphthyl and anthracene. Alkyl, alkenyl, cycloalkyl, and aryl groups may have substituents.

[0087] The cycloalkyl group formed by the two bonds of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms. Regarding the cycloalkyl groups formed by the two bonds of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. Cycloalkyl groups formed by two bonds of Rx1 to Rx3 may have substituents.

[0088] In formula (Y3), R36 to R38 independently represent hydrogen atoms or monovalent organogroups. R37 and R38 can bond to each other to form a ring. Examples of monovalent organogroups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R36 is also preferably a hydrogen atom.

[0089] As for equation (Y3), it is preferred to use the basis represented by the following equation (Y3-1).

[0090] [Chemistry 14]

[0091] Here, L1 and L2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group composed of these (e.g., a group composed of an alkyl group and an aryl group). M represents a single bond or a 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 that may contain heteroatoms, or a group composed of these (e.g., a group composed of alkyl and cycloalkyl groups). One of the alkyl and cycloalkyl groups, such as the methylene group, may be substituted by a heteroatom such as an oxygen atom or a group with a heteroatom such as a carbonyl group. Furthermore, it is preferable that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group formed by combining alkyl and aryl. At least two of Q, M, and L1 can be bonded to form a ring (preferably a 5-membered or 6-membered ring). Regarding the refinement of the pattern, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tributyl or adamantyl. In these forms, due to the higher Tg (glass transition temperature) or activation energy, fogging can be suppressed in addition to ensuring film strength.

[0092] In formula (Y4), Ar represents an aromatic cycloalkyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can also bond to each other to form a non-aromatic ring. Ar is preferably an aryl group.

[0093] Resin (A) is preferably acetal in structure. The acid-degradable group is preferably an acetal structure. An acetal structure is a structure in which polar groups such as carboxyl groups, phenolic hydroxyl groups, and fluorinated alcohol groups are protected by the group represented by the above formula (Y3).

[0094] As a repeating unit with an acid-decomposable group, it is preferably the repeating unit represented by formula (A).

[0095] [Chemistry 15]

[0096] L1 represents a divalent linker, R1~R3 ​​represent hydrogen atoms or monovalent substituents independently, and R4 represents a group that decomposes and is released by the action of an acid. L1 represents a divalent linker. Examples of divalent linkers include -CO-, -O-, -S, -SO-, -SO2-, hydrocarbon groups (e.g., alkyl, cycloalkyl, alkenyl, aryl, etc.), and linkers formed by the linkage of multiple of these. Among these, -CO- and aryl are preferred as L1. 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.

[0097] R1 through R3 each independently represent a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include alkyl groups, cycloalkyl groups, or halogen atoms. Alkyl groups can be straight-chain or branched-chain. 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. The cycloalkyl group can be monocyclic or polycyclic. The preferred number of carbon atoms in the cycloalkyl group is 3 to 8. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0098] R 4 represents a radical that is released by the action of an acid (a released radical). Among them, as the detached basis, the basis represented by the above equations (Y1) to (Y4) can be listed, and the basis represented by the above equation (Y3) is preferred.

[0099] When each of the groups has a substituent, 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.

[0100] As a repeating unit with an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (AI).

[0101] [Chemistry 16]

[0102] In general formula (AI), Xa 1 represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linker. Rx 1 to Rx 3 independently represent alkyl (straight-chain or branched-chain), alkenyl (straight-chain or branched-chain), cycloalkyl (monocyclic or polycyclic), or aryl (monocyclic or polycyclic). Where all Rx 1 to Rx 3 are alkyl (straight-chain or branched-chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl. Two of Rx 1 to Rx 3 can also be bonded together to form a cycloalkyl group (monocyclic or polycyclic).

[0103] As represented by Xa 1, alkyl groups such as methyl or -CH 2-R 1 1 can be listed. R 1 1 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, such as alkyl groups with 5 or fewer carbon atoms and acetyl groups with 5 or fewer carbon atoms, preferably alkyl groups with 3 or fewer carbon atoms, and more preferably methyl groups. As Xa 1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0104] Examples of divalent linkers 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, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0105] The alkyl group Rx 1 to Rx 3 is not particularly limited, and alkyl groups having 1 to 20 carbon atoms can be listed, with alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl being preferred. There are no particular limitations on the alkenyl group that is Rx 1 to Rx 3. Alkenyl groups with 2 to 20 carbon atoms can be listed, with vinyl, propenyl, isopropenyl and other alkenyl groups with 2 to 4 carbon atoms being preferred. There is no particular limitation on the cycloalkyl group Rx 1 to Rx 3. Examples of cycloalkyl groups with 3 to 20 carbon atoms are included. Preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group of Rx 1 to Rx 3, but it is preferred to be an aryl group with 6 to 14 carbons, such as phenyl, naphthyl, or anthracene.

[0106] The cycloalkyl group formed by the two bonds of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, it is also preferably a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Among them, a monocyclic cycloalkyl group with 5 to 6 carbon atoms is preferred. Regarding the cycloalkyl groups formed by the two bonds of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. The repeating unit represented by the general formula (AI) is preferably in the following state: Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 are bonded to form the cycloalkyl group.

[0107] When each of the groups has a substituent, 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.

[0108] As the repeating unit represented by the general formula (AI), it is preferably an acid-degradable (meth)acrylate trialkyl ester repeating unit (Xa 1 represents a hydrogen atom or methyl and T represents a single bond repeating unit).

[0109] As a preferred embodiment, resin (A) contains repeating units represented by the following formula (4).

[0110] [Chemistry 17]

[0111] In equation (4), X 11 represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group. R11 each independently represents an alkyl group, and two R11 groups can bond together to form a ring.

[0112] Examples of halogen atoms that are X 11 include: fluorine, chlorine, bromine, and iodine. There are no particular limitations on the organic groups that can be used as X 11, and examples include: alkyl, cycloalkyl, aryl, etc. The alkyl group is not particularly limited, and examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, preferably methyl or ethyl, and more preferably methyl. There is no particular limitation on the cycloalkyl group, and examples of cycloalkyl groups with 3 to 20 carbon atoms are possible. Preferred examples are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracene. Alkyl, cycloalkyl, and aryl groups may include -O-, -COO-, and alkyl groups. Alkyl, cycloalkyl, and aryl groups may have substituents. There are no particular limitations on the substituents, but halogen atoms are preferred.

[0113] There is no particular limitation on the alkyl group used in R11. Examples of linear or branched alkyl groups are given. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 10. Alkyl groups may have substituents. There are no particular limitations on the substituents, but preferred examples include: alkoxy groups (1 to 4 carbon atoms), acetyl groups (e.g., acetyl), hydroxyl groups, halogen atoms, etc.

[0114] Two R11 atoms can bond together to form a ring. Specifically, two R11 atoms can bond together to form a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group formed by two R11 bonds is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred. Regarding the cycloalkyl group formed by two R11 bonds, for example, one of the methylene groups constituting the ring may be substituted by a heteroatom such as an oxygen atom or a group with a heteroatom such as a carbonyl group.

[0115] Resin (A) may contain only one repeating unit with an acid-degradable group, or it may contain two or more repeating units.

[0116] The content of repeating units with acid-degradable groups in resin (A) relative to all repeating units of resin (A) (total if there are multiple repeating units with acid-degradable groups) is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol.

[0117] The total content of repeating units (a1) and repeating units (a2) contained in resin (A) relative to all repeating units of resin (A) (the total of these if there are multiple repeating units (a1) and repeating units (a2) respectively) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol%. Furthermore, when resin (A) has only repeating units (a1) and repeating units (a2), the total amount of repeating units (a1) and repeating units (a2) contained in resin (A) is 100 mol.

[0118] (Repeating unit (a3)) The resin (A) preferably further comprises repeating units (a3) ​​having acid groups, which are different from the repeating units (a1).

[0119] The acid group in the repeating unit (a3) ​​is preferably selected from at least one group in the group consisting of carboxylic acid group, sulfonic acid group, phenolic hydroxyl group and fluorinated alkyl alcohol group, and more preferably phenolic hydroxyl group or fluorinated alkyl alcohol group.

[0120] • Repeating units with phenolic hydroxyl groups The repeating unit having phenolic hydroxyl groups is preferably the repeating unit represented by the following general formula (B2).

[0121] [Chemistry 18]

[0122] In general formula (B2), X represents a hydrogen atom, an alkyl group, or a halogen atom. The alkyl group can be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The substituents of the alkyl group are preferably hydroxyl or halogen atoms. Where the alkyl group has substituents, it is preferable to have only hydroxyl and / or halogen atoms as substituents. The alkyl group is preferably -CH3.

[0123] In general formula (B2), X 4 represents a single bond, -COO-, or -CONR 64-, and R 64 represents a hydrogen atom or an alkyl group (which can be straight-chain or branched-chain. Preferably, it has 1 to 5 carbon atoms). The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit.

[0124] In general formula (B2), L4 represents a single bond or an alkyl group (which can be straight-chain or branched-chain. Preferably, it has 1 to 20 carbon atoms).

[0125] In general formula (B2), Ar 4 represents an (n+1) valence aromatic cyclic group. The aromatic cyclic group is preferably a phenyl cyclic group, naphthyl cyclic group, or anthracene cyclic group with 6 to 18 carbon atoms, or a heterocyclic cyclic group containing heterocycles such as thiophene cyclic group, furan cyclic group, pyrrole cyclic group, benzothiophene cyclic group, benzofuran cyclic group, benzopyrrole cyclic group, triazine cyclic group, imidazole cyclic group, benzimidazole cyclic group, triazole cyclic group, thiadiazole cyclic group, and thiazolium cyclic group; more preferably a phenyl cyclic group.

[0126] In general formula (B2), n represents an integer from 1 to 5. The (n+1) valence aromatic ring group may further have substituents.

[0127] Substituents that may be present as the alkyl group of R 64, the alkyl group of L 4, and the (n+1) valent aromatic ring group of Ar 4 include, for example, halogen atoms (preferably fluorine atoms), alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl. Additionally, substituents that may be present as the (n+1) valent aromatic ring group of Ar 4 include, for example, alkyl groups (which may be straight-chain or branched-chain; preferably having 1 to 20 carbon atoms).

[0128] The following are specific examples of repeating units having phenolic hydroxyl groups, but the invention is not limited thereto. In the formula, a represents 1 or 2.

[0129] [Chemistry 19]

[0130] [Chemistry 20]

[0131] [Chemistry 21]

[0132] Furthermore, the repeating unit is preferably the repeating unit specifically described below. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer from 1 to 3.

[0133] [Chemistry 22]

[0134] • Repeating units with fluorinated alkyl alcohol groups As a repeating unit having a fluorinated alkyl alcohol group, it is preferred to have a repeating unit having a hexafluoroisopropanol group.

[0135] Hereinafter, examples are given of repeating units that correspond to repeating units having fluorinated alkyl alcohol groups, but the present invention is not limited to these repeating units.

[0136] [Chemistry 23]

[0137] [Chemistry 24]

[0138] Specific examples of monomers that correspond to repeating units (a3) ​​having acid groups other than phenolic hydroxyl groups and fluorinated alkyl alcohol groups are given, but the present invention is not limited thereto.

[0139] [Chemistry 25]

[0140] When resin (A) has repeating unit (a3), the content of repeating unit relative to all repeating units of resin (A) is preferably 1 mol% to 30 mol%, more preferably 5 mol% to 25 mol%, and even more preferably 5 mol% to 20 mol. The repeating unit (a3) ​​can be used alone or in more than one form.

[0141] (Repeating unit with polar groups (a4)) Resin (A) may further contain repeating units with polar groups that are different from repeating units (a1) (also referred to as "repeating units (a4)").

[0142] The polar group of the repeating unit (a4) is preferably selected from at least one group selected from the group consisting of ester, sulfonate, sulfonamide, carbonate, carbamate, alcoholic hydroxyl (except for the fluorinated alkyl alcohol group in the repeating unit (a2)), urethane, sulfonyl, ketone, amide, sulfonamide, cyano, nitro and ether, more preferably selected from at least one group selected from the group consisting of lactone, sulfonolactone, sultam, alcoholic hydroxyl (except for the fluorinated alkyl alcohol group in the repeating unit (a2)) and cyclic carbonate, and further preferably lactone or sulfonolactone, especially lactone. That is, the repeating unit (a4) preferably has a lactone structure or a sulfonolactone structure, and more preferably has a lactone structure.

[0143] As a lactone structure or a sulfonolactone structure, it is acceptable as long as it has a lactone ring or a sulfonolactone ring, preferably a lactone structure having a 5-membered to 7-membered ring or a sulfonolactone structure having a 5-membered to 7-membered ring. Preferably, it is a lactone structure formed by condensing other rings into a 5-membered to 7-membered lactone ring to form a bicyclic or spirocyclic structure. Also preferably, it is a sulfonyl lactone structure formed by condensing other rings into a 5-membered to 7-membered sulfonyl lactone ring to form a bicyclic or spirocyclic structure.

[0144] The resin (A) preferably comprises repeating units having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-22), or a sulfonyl lactone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). Moreover, the lactone structure or sulfonyl lactone structure can be directly bonded to the main chain. Among them, the preferred structures are the lactone structures shown in general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), or general formula (LC1-22), or the sulcinolone structure shown in general formula (SL1-1).

[0145] [Chemistry 26]

[0146] The lactone or sulopentalide structure may or may not have a substituent (Rb 2). Preferably, the substituent (Rb 2) is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, or a cyano group, and more preferably an alkyl group having 1 to 4 carbon atoms or a cyano group. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple substituents (Rb 2) may be the same or different. Furthermore, the multiple substituents (Rb 2) may also bond together to form a ring.

[0147] As a repeating unit having a lactone structure or a sulfonyl lactone structure, it is preferably a repeating unit represented by the following general formula (LS1).

[0148] [Chemistry 27]

[0149] In the general formula (LS1), A LS represents an ester bond (represented by the group -COO-) or an amide bond (represented by the group -CONH-).

[0150] t is the number of repetitions in the structure represented by -R LS2-R LS3-, and is an integer from 0 to 5, preferably 0 or 1, and even more preferably 0. When t is 0, (-R LS2-R LS3-)t becomes a single bond.

[0151] R LS2 represents an alkyl group, an cycloalkyl group, or a combination thereof. In the presence of multiple R LS2s, the multiple R LS2s may be the same or different. The alkyl or cycloalkyl groups of R LS2 may have substituents.

[0152] R LS3 represents a single bond, ether bond, ester bond, amide bond, carbamate bond, or urea bond. In the presence of multiple R LS3s, each R LS3 may be identical or different. Among them, R LS3 is preferably an ether bond or an ester bond, and more preferably an ester bond.

[0153] R LS4 represents a monovalent organic group having a lactone or sulfonyl lactone structure. In any of the structures represented by general formulas (LC1-1) to (LC1-22) and general formulas (SL1-1) to (SL1-3), it is preferably a group formed by removing a hydrogen atom from a carbon atom constituting a lactone or sulfonyl lactone structure. Furthermore, the carbon atom from which a hydrogen atom has been removed is preferably not a carbon atom constituting a substituent (Rb2).

[0154] R LS1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl).

[0155] Hereinafter, examples are given of monomers having repeating units that are selected from at least one of the group consisting of lactone and sulcolone structures. In the examples below, the methyl group bonded to the vinyl group may be substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[0156] [Chemistry 28]

[0157] [Chemistry 29]

[0158] [Chemistry 30]

[0159] As a repeating unit (a4), it is also preferred to be a repeating unit having a carbonate group. The carbonate group in the repeating unit having a carbonate group is preferably contained in a cyclic carbonate group. The repeating unit having a carbonate group is preferably the repeating unit represented by the general formula (A4).

[0160] [Chemistry 31]

[0161] In general formula (A4), RA 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl). n represents an integer greater than or equal to 0 (preferably 0 to 3). RA 2 represents a substituent. When n is 2 or more, there can be multiple RA 2s, which can be the same or different. A represents a single bond or a divalent linker. The divalent linker is preferably an alkyl group (preferably with 1 to 4 carbon atoms), a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxylic acid group, or a divalent group formed by combining these. Z represents a group of atoms that, together with the radical represented by -O-CO-O- in the formula, form a monocyclic or polycyclic atom. The monocyclic or polycyclic group formed by Z together with the group represented by -O-CO-O- in the formula is preferably a 5-membered cyclic carbonate group, and more preferably a cyclic carbonate structure represented by the following general formula (CC1-1). That is, A in the general formula (A4) is preferably a basic bond formed by removing a hydrogen atom from the ring member atom of the cyclic carbonate structure represented by the following general formula (CC1-1).

[0162] [Chemistry 32]

[0163] The cyclic carbonate structure in the general formula (CC1-1) may also have substituents (Rb 2). Preferred substituents (Rb 2) include, for example, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxylic acid groups, halogen atoms (preferably fluorine atoms), hydroxyl groups, and cyano groups. n3 represents an integer of 0 or 1.

[0164] Resin (A) may also contain repeating units having polar groups other than the aforementioned lactone, sulopentalide, or carbonate groups. Preferably, the repeating unit having a polar group other than the aforementioned lactone, sulopentalide, or carbonate group is a repeating unit having an alicyclic hydrocarbon structure substituted with the aforementioned polar group. Preferably, the alicyclic hydrocarbon structure substituted with a polar group is cyclohexyl, adamantyl, or norbornyl.

[0165] The following are specific examples of monomers that correspond to repeating units having the polar groups, but the present invention is not limited to these specific examples.

[0166] [Chemistry 33]

[0167] Resin (A) is also preferably a repeating unit (a4) as the repeating unit described in paragraphs

[0370] to

[0433] of the specification of U.S. Patent Application Publication No. 2016 / 0070167A1.

[0168] When resin (A) contains repeating units (a4), the type of repeating units (a4) contained in resin (A) may be one or more.

[0169] When resin (A) contains repeating units (a4), the content of repeating units (a4) contained in resin (A) (or the total content when there are multiple repeating units (a4)) is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 45 mol%, and even more preferably 10 mol% to 30 mol% relative to all repeating units in resin (A).

[0170] (Other repeating units) In addition, resin (A) may also contain repeating units (a5) represented by the following formula (D).

[0171] [Chemistry 34]

[0172] In formula (D), "Cyclic" represents a base whose main chain is formed in a ring structure. There is no particular restriction on the number of atoms constituting the ring.

[0173] As a repeating unit represented by equation (D), the following repeating units can be listed for example.

[0174] [Chemistry 35]

[0175] In the formula, R independently represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acetoxy, cyano, nitro, amino, halogen atom, ester group (-OCOR'' or -COOR'': R'' is an alkyl or fluorinated alkyl group with 1 to 20 carbon atoms), or carboxylic acid group. Furthermore, the alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to a carbon atom in the group represented by R may be replaced by a fluorine or iodine atom. In the formula, R' independently represents an alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acetoxy, cyano, nitro, amino, halogen atom, ester group (-OCOR'' or -COOR'': R'' is an alkyl or fluorinated alkyl group with 1 to 20 carbon atoms), or carboxylic acid group. Furthermore, the alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced by a fluorine or iodine atom. m represents an integer greater than or equal to 0. There is no particular upper limit to m, but it is usually less than 2 and even more often less than 1.

[0176] When resin (A) contains the repeating unit (repeating unit (a5)) represented by formula (D), the content of the repeating unit is preferably 1 mol% to 50 mol% relative to all repeating units of resin (A), more preferably 3 mol% to 40 mol%, and even more preferably 5 mol% to 30 mol%.

[0177] In addition, resin (A) may also contain repeating units (a6) represented by the following formula (E).

[0178] [Chemistry 36]

[0179] 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" is 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.

[0180] As a repeating unit represented by equation (E), the following repeating units can be listed for example.

[0181] [Chemistry 37]

[0182] In the formula, R independently 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 group with 1 to 20 carbon atoms), or carboxylic acid group. Furthermore, the alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may also have substituents. Additionally, the hydrogen atom bonded to a carbon atom in the group represented by R may be replaced by a fluorine or iodine atom. R' can independently represent 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 group with 1 to 20 carbon atoms), or carboxylic acid group. Furthermore, the alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may also have substituents. Additionally, the hydrogen atom bonded to a carbon atom in the group represented by R' can be replaced by a fluorine or iodine atom. m represents an integer greater than or equal to 0. There is no particular upper limit to m, but it is usually less than 2 and even more often less than 1. In addition, in equations (E-2), (E-4), (E-6), (E-8), and (E-12), the two Rs can be bonded to each other to form a ring.

[0183] In the case where the resin (A) includes the repeating unit (a6) represented by formula (E), the content of the repeating unit relative to all the repeating units of the resin (A) is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 40 mol%, and even more preferably 5 mol% to 30 mol.

[0184] Resin (A) may contain repeating units other than those described above, as a different repeating unit from repeating unit (a1), without impairing the effects of the present invention. For example, it may contain repeating units having photoacid generating groups.

[0185] The repeating unit having a photoacid generating group is not particularly limited, but it is preferably the repeating unit represented by the general formula (A7) (repeat unit (a7)).

[0186] [Chemistry 38]

[0187] In general formula (A7), the two Xf atoms independently represent a hydrogen atom, a fluorine atom, or an alkyl group substituted with at least one fluorine atom (preferably CF3). At least one of the two Xf atoms is preferably not a hydrogen atom. The alkyl group can be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group preferably has only fluorine atoms as substituents.

[0188] In general formula (A7), R1 and R2 independently represent hydrogen atoms, fluorine atoms, or alkyl groups, respectively. When multiple R1 and R2 exist, they may be the same or different. The alkyl group can be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The substituents of the alkyl group are preferably fluorine atoms. Where the alkyl group has substituents, it is preferable that it has only fluorine atoms as substituents.

[0189] In general formula (A7), L represents a divalent linker, and when there are multiple Ls, they can be the same or different. Examples of divalent linkages of L include -COO-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene, cycloalkylene, alkenylene, and linkages formed by linking multiple of these, preferably linkages with a total carbon number of 12 or less.

[0190] In the general formula (A7), x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0191] In general formula (A7), X7 represents a hydrogen atom, an alkyl group, or a halogen atom. When X 7 represents an alkyl group, examples of linear or branched alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, isopropyl or n-propyl, more preferably methyl or ethyl, and even more preferably methyl. As a substituent when the alkyl group has a substituent, the substituents described in substituent T can be listed. When X 7 represents a halogen atom, the halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred choice.

[0192] In general formula (A7), M+ represents a cation. For example, the same cation as M+ in general formula (PA-1) described later can be used for details of M+.

[0193] When resin (A) has repeating unit (a7), the content of repeating unit relative to all repeating units of resin (A) is preferably 1 mol% to 40 mol%, more preferably 1 mol% to 25 mol%, and even more preferably 1 mol% to 15 mol. The repeating unit (a7) can be used alone or in more than one form.

[0194] Resin (A) can be synthesized by conventional methods (e.g., free radical polymerization). Using the GPC method, the weight-average molecular weight of resin (A), converted to polystyrene, is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 4,500 to 15,000. Setting the weight-average molecular weight of resin (A) to 1,000 to 200,000 can prevent the deterioration of heat resistance and dry etching resistance, thereby preventing the deterioration of developability and the deterioration of film-forming properties due to increased viscosity. The dispersion (molecular weight distribution) of resin (A) is typically 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and resist shape, and consequently the smoother the sidewalls of the resist pattern and the better the roughness performance.

[0195] In the composition of the present invention, the content of resin (A) in all solid components is preferably 10.0% to 99.9% by mass, more preferably 20.0% to 99.0% by mass. In addition, as a preferred embodiment, in the composition of the present invention, the content of resin (A) in all solid components is preferably 25.0% to 99.9% by mass, more preferably 60.0% to 99.0% by mass. In addition, one type of resin (A) may be used, or two or more types may be used.

[0196] Without impairing the effects of the invention, the composition of the invention may contain resin (A') that does not have repeating unit (a1) in addition to resin (A). As for resin (A'), there is no particular limitation as long as it does not have repeating units (a1), for example, resins that do not have repeating units (a1) in resin (A) can be listed. When the composition of the present invention contains resin (A'), the ratio of the content of resin (A) to the content of resin (A') in the composition of the present invention is preferably 9:1 to 8:2 by mass.

[0197] [The compound represented by formula (2)] The present invention also relates to a compound represented by the following formula (2).

[0198] [Chemistry 39]

[0199] In equation (2), A represents a polymerizing group. L1 represents a single bond or a divalent organic group. R1 represents a halogen atom or an organic group having a halogen atom. R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group. R 3 represents a halogen atom, an amino group, a thiol group, or an organic group. R 4 represents a hydrogen atom or an organic group. Let n represent an integer greater than or equal to 1, m represent an integer greater than or equal to 0, and p represent an integer greater than or equal to 0, where n, m, and p satisfy the relationship n + m ≤ 5 + 2p. When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

[0200] A, L1, R1, R2, R3, R4, n, m, and p have the same meaning as A, L1, R1, R2, R3, R4, n, m, and p in formula (2) of the resin (A) contained in the composition of the present invention.

[0201] The compound represented by formula (2) is preferably the compound represented by formula (3) below.

[0202] [Chemistry 40]

[0203] In equation (3), X represents a hydrogen atom or an organic group. R1 and R2 have the same meaning as R1 and R2 in equation (2). L2 represents a single bond or a divalent linker. R3, R4, n, m, and p have the same meaning as R3, R4, n, m, and p in equation (2). When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

[0204] X and L2 have the same meaning as X and L2 in formula (3) of the resin (A) contained in the composition of the present invention. The compound represented by formula (2) can be synthesized by the following method. As an example, the M-70 will be used for illustration, as will be discussed later. First, 4-tert-butoxybenzaldehyde was dissolved in tetrahydrofuran, and then trifluoromethyltrimethylsilane and tetrabutylammonium fluoride were added and stirred. Methacrylic anhydride was further added to the resulting solution, and the mixture was heated and stirred, followed by separation, purification, and concentration to obtain an intermediate. This intermediate was then heated and stirred in acetone with 4M hydrochloric acid water, followed by separation, concentration, crystallization, and drying to synthesize M-70. Compounds other than M-70 can also be synthesized in the same way.

[0205] In addition, the present invention also relates to a resin having repeating units derived from the compound represented by formula (2) or the repeating units derived from the compound represented by formula (3). As a resin, examples of resins (A) contained in the composition of the present invention include resins having repeating units derived from compounds represented by formula (2) or from compounds represented by formula (3).

[0206] <(B) Compounds that produce acids through irradiation by photochemical rays or radiation> The composition of this invention contains a compound that produces acid by irradiation with photochemical rays or radiation (also known as a photoacid generator, or photoacid generator (B)). The photoacid generator is a compound that produces acid by exposure (preferably exposure to EUV light). Photoacid generators can be in the form of low-molecular-weight compounds or in the form incorporated into a polymer. Alternatively, both low-molecular-weight compound forms and forms incorporated into a polymer can be used. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. When the photoacid generator is incorporated into part of the polymer, it can be incorporated into part of resin (A) or into a resin different from resin (A). In this invention, the photoacid generator is preferably in the form of a low molecular weight compound. There are no particular limitations on photoacid generators, but they are preferably compounds that generate organic acids by EUV light irradiation, and even more preferably photoacid generators that have fluorine or iodine atoms in their molecules. Examples of such organic acids include: sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine, bis(alkyl sulfonyl) imine, and tri(alkyl sulfonyl) methyl acid, etc.

[0207] In this invention, the strength of the acid generated by the photoacid generator (B) is not particularly limited. For example, the pKa of the generated acid is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and even more preferably -5.00 to 0.00.

[0208] There is no particular limitation on the volume of acid generated by the photoacid generator, but in terms of suppressing the diffusion of acid generated by exposure to non-exposed areas and ensuring good resolution, it is preferably 240 Å 3 or more, more preferably 305 Å 3 or more, even more preferably 350 Å 3 or more, and especially preferably 400 Å 3 or more. Furthermore, in terms of sensitivity or solubility in the coating solvent, the volume of acid generated by the photoacid generator is preferably 1500 Å 3 or less, more preferably 1000 Å 3 or less, and even more preferably 700 Å 3 or less. The volume value was determined using the "WinMOPAC" manufactured by Fujitsu Inc. In calculating the volume value, firstly, the chemical structure of each acid was input; secondly, this structure was used as the initial structure, and the most stable stereoconformation of each acid was determined using molecular force field calculations based on molecular mechanics (MM)3. Then, molecular orbital calculations were performed on these most stable stereoconformations using the parameterized model number (PM)3 method to calculate the "accessible volume" of each acid.

[0209] The structure of the acid generated by the photoacid generator is not particularly limited. However, in terms of suppressing acid diffusion and improving resolution, it is preferable that the acid generated by the photoacid generator has a strong interaction with the resin (A). In this respect, when the acid generated by the photoacid generator is an organic acid, it is preferable that it has polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonyl sulfonyl imine groups, disulfonyl imine groups, and trisulfonyl methyl acid groups. Examples of polar groups include: ether, ester, acetamino, acetyl, sulfonyl, sulfonyloxy, sulfonylamine, thioether, thioester, urea, carbonate, carbamate, hydroxyl, and mercapto. There is no particular limitation on the number of polar groups in the generated acid, but it is preferable to have one or more, more preferably two or more. In terms of suppressing excessive development, the number of polar groups is preferably less than six, more preferably less than four.

[0210] The photoacid generator is preferably a photoacid generator that produces the acids shown in the examples below. Furthermore, the calculated volume (in ų) is indicated for some examples.

[0211] [Chemistry 41]

[0212] [Chemistry 42]

[0213] [Chemistry 43]

[0214] As a photoacid generator, there are no particular limitations. It can be a non-anionic photoacid generator without anionic and cationic structures, or it can be a photoacid generator with anionic and cationic structures, such as the so-called onium salt. In terms of further advantages of the present invention, the photoacid generator is preferably an onium salt.

[0215] The photoacid generator is preferably one in which a halogen atom is present in the cation portion. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0216] (Compounds represented by the general formula (PA-1)) The photoacid generator is preferably a compound represented by the general formula (PA-1).

[0217] [Chemistry 44]

[0218] In the general formula (PA-1), A1 and A2 independently represent -SO2-RP or -CO-RP, respectively. RP represents an organic group. The two RPs in the general formula (PA-1) can be the same or different. In the general formula (PA-1), the number of carbons of the two RPs present is preferably 1 to 25, and more preferably 1 to 15, respectively. In the general formula (PA-1), the number of atoms other than hydrogen atoms in the two RPs is preferably 2 to 30, more preferably 4 to 20, each independently. RP is preferably represented by the general formula (RF). -L RF-R RF(RF)

[0219] In the general formula (RF), L RF represents a single bond or a divalent linker. Examples of divalent linkers include: -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkyl groups (which can be linear or branched, preferably with 1 to 6 carbon atoms), cycloalkyl groups (preferably with 3 to 15 carbon atoms), alkenyl groups (which can be linear or branched, preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. Furthermore, these divalent linking groups may preferably have substituents that are halogen atoms, and more preferably fluorine atoms, where possible. For example, the alkylene group (including alkylene groups that may be included in a combination of multiple divalent linking groups) is also preferably a perfluoroalkylene group. The divalent linker is preferably -extrinyl-COO- or -extrinyl-SO2-. -extrinyl-COO- and -extrinyl-SO2- are preferably associated with the N-side.

[0220] In the general formula (RF), R RF represents cycloalkyl or alkyl. When R and RF are cycloalkyl groups, the cycloalkyl group can be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 15 carbon atoms, and more preferably 5 to 10 carbon atoms. Examples of cycloalkyl groups include norbornel, decalinyl, and adamantyl. The cycloalkyl group may preferably have alkyl substituents (which may be straight-chain or branched, preferably with 1 to 5 carbon atoms). The cycloalkyl group is also preferably free of other substituents. One or more carbon atoms that are members of the cycloalkyl group may also be substituted by carbonyl carbon atoms and / or heteroatoms. For example, the carbon atom (-CH<) bonded to L RF in the cycloalkyl group may also be substituted by a nitrogen atom (-N<). When R and RF are alkyl groups, the alkyl group can be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The alkyl group may preferably have substituents that are cycloalkyl, fluorine, or cyano. The alkyl group is also preferably free of substituents other than these. Examples of cycloalkyl groups that are said to be substituents can be similarly illustrated in the case where R and RF are cycloalkyl groups. When the alkyl group has a fluorine atom as a substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as a substituent, some or all of the alkyl group is preferably a perfluoromethyl group.

[0221] In the general formula (PA-1), the two RPs contained in "A1-N-A2" can be bonded to each other to form a loop.

[0222] In the general formula (PA-1), M+ represents a cation. The cation of M+ is preferably an organic cation. The organic cation is preferably a cation represented by the general formula (ZaI) (cation (ZaI)) or a cation represented by the general formula (ZaII) (cation (ZaII)).

[0223] [Chemistry 45]

[0224] In the general formula (ZaI), R 201, R 202 and R 203 each independently represent an organic group. The number of carbon atoms in the organic groups R 201, R 202, and R 203 is typically 1 to 30, preferably 1 to 20. Furthermore, two of R 201 to R 203 can bond to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group. 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-.

[0225] Examples of cations in the general formula (ZaI) include, for example, the cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b).

[0226] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is an aryl strontium cation of the general formula (ZaI) in which at least one of R 201 to R 203 is aryl. The aryl strontium cation can be entirely composed of aryl groups from R201 to R203, or a portion of R201 to R203 can be aryl groups, with the remainder being alkyl or cycloalkyl groups. Additionally, one of R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 can bond together to form a ring structure, which may also contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group. Examples of groups formed by the bonding of two of R 201 to R 203 include alkyl groups (e.g., butyl, pentyl, or -CH 2-CH 2-O-CH 2-CH 2-) formed by substituting one or more methylene groups with an oxygen atom, a sulfur atom, an ester group, an amino group, and / or a carbonyl group. Examples of aryl strontium cations include: triaryl strontium cations, diarylalkyl strontium cations, aryldialkyl strontium cations, diarylcycloalkyl strontium cations, and aryldicycloalkyl strontium cations.

[0227] The aryl group in the aryl strontium cation is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be a heterocyclic structure containing oxygen, nitrogen, or sulfur atoms. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl strontium cation has two or more aryl groups, these two or more aryl groups can be the same or different. The aryl strontium cation preferably has a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, such as methyl, ethyl, propyl, n-butyl, dibutyl, tributyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0228] The aryl, alkyl, and cycloalkyl groups of R 201 to R 203 may have substituents. The aryl, alkyl, and cycloalkyl groups in R 201 to R 203 may have no particular limitation on the substituents, but are preferably alkyl (e.g., 1 to 15 carbons), cycloalkyl (e.g., 3 to 15 carbons), aryl (e.g., 6 to 14 carbons), alkoxy (e.g., 1 to 15 carbons), cycloalkylalkoxy (e.g., 1 to 15 carbons), halogen atom, hydroxyl or phenylthio. The substituent may further have substituents where possible; for example, the alkyl group may have a halogen atom as a substituent and become a trifluoromethyl or other halogenated alkyl group.

[0229] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is a cation in formula (ZaI) where R 201 to R 203 each independently represent an organic group without an aromatic ring. Here, the term "aromatic ring" also includes aromatic rings containing heteroatoms. The organic groups that do not have an aromatic ring, which are R 201 to R 203, generally have 1 to 30 carbons, and preferably 1 to 20 carbons. R 201 to R 203 are preferably alkyl, cycloalkyl, allyl or vinyl, more preferably straight-chain or branched 2-oxoalkyl, 2-oxocycloalkyl or alkoxycarbonylmethyl, and even more preferably straight-chain or branched 2-oxoalkyl.

[0230] Examples of alkyl and cycloalkyl groups as R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), as well as cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). R 201~R 203 can also be further substituted by halogen atoms, alkoxy groups (e.g., carbon 1~5), hydroxyl groups, cyano groups or nitro groups.

[0231] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is the cation represented by the following general formula (ZaI-3b).

[0232] [Chemistry 46]

[0233] In the general formula (ZaI-3b), R1c to R5c independently represent hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio. R6c and R7c independently represent a hydrogen atom, an alkyl group (such as a third butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, respectively. Rx and Ry independently represent alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl, respectively.

[0234] Any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry can be bonded to form a ring, which can also independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds. Examples of the rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensation rings formed by combining two or more of these rings. The rings can be 3-membered to 10-membered, preferably 4-membered to 8-membered, and more preferably 5-membered or 6-membered.

[0235] The group can be formed by bonding any two or more of R1c to R5c, R6c and R7c, and Rx and Ry, for example, alkyl groups such as butylyl and pentylyl. The methylene group in the alkyl group may be substituted with a heteroatom such as an oxygen atom. The groups formed by the bonds of R5c and R6c, and R5c and Rx, are preferably single bonds or alkyl groups. Examples of alkyl groups include methylene and ethyl groups.

[0236] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is the cation represented by the following general formula (ZaI-4b).

[0237] [Chemistry 47]

[0238] In the general formula (ZaI-4b), l represents an integer from 0 to 2. r represents an integer from 0 to 8. R13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be the cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may also have substituents. R14 represents a hydroxyl, alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl, or a group having a cycloalkyl group (which may be the cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may also have substituents. In the presence of multiple R14 groups, each group independently represents the hydroxyl group, etc. R1 and R5 independently represent alkyl, cycloalkyl, or naphthyl groups. These groups may also have substituents. Two R15 groups may bond together to form a ring. When two R15 groups are bonded together to form a ring, the ring skeleton may also contain heteroatoms such as oxygen or nitrogen atoms. In one configuration, it is preferred that the two R15 groups are alkyl groups and are bonded together to form a ring structure.

[0239] In the general formula (ZaI-4b), the alkyl groups of R13, R14, and R15 are straight-chain or branched-chain. The number of carbon atoms in the alkyl group is preferably 1 to 10. More preferably, the alkyl group is methyl, ethyl, n-butyl, or tributyl, etc.

[0240] Next, the general formula (ZaII) will be explained. In the general formula (ZaII), R 204 and R 205 independently represent aryl, alkyl, or cycloalkyl groups, respectively. The aryl group in R 204 and R 205 is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group in R 204 and R 205 may also be an aryl group containing a heterocycle with an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic aryl groups include: pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. The alkyl and cycloalkyl groups in R 204 and R 205 are preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0241] The aryl, alkyl, and cycloalkyl groups in R 204 and R 205 may each have substituents independently. Examples of substituents that may be present in the aryl, alkyl, and cycloalkyl groups in R 204 and R 205 include: alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 15 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0242] (Other photoacid generating agents) Other photoacid generating agents besides those described can also be used in the composition of this invention. Other photoacid generators include, for example, compounds represented by "M + Z - (M + represents cation, Z - represents anion)" (onium salts).

[0243] In compounds represented by "M +Z -", M + represents a cation, and can be listed as the same cation as in the general formula (PA-1). In compounds represented by "M +Z -", Z - represents an anion, preferably an anion with a significantly low ability to induce nucleophilic reactions. Examples of such anions include: sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylate anions), and tri(alkylsulfonyl)methylated anions.

[0244] The aliphatic portion of the aliphatic sulfonate anion and the aliphatic carboxylate anion can be alkyl or cycloalkyl, preferably a straight-chain or branched alkyl with 1 to 30 carbon atoms, or a cycloalkyl with 3 to 30 carbon atoms.

[0245] The aromatic cyclic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group with 6 to 14 carbon atoms, such as phenyl, tolyl and naphthyl.

[0246] Substituents that may be present in the listed alkyl, cycloalkyl, and aryl groups include, for example: nitro, halogen atoms such as fluorine atoms, carboxylic acid groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably with 1 to 15 carbon atoms), cycloalkyl groups (preferably with 3 to 15 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably with 2 to 7 carbon atoms), acetyl groups (preferably with 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably with 2 to 7 carbon atoms), and alkylthio groups. The compounds are: alkyl sulfonyl (preferably with 1 to 15 carbon atoms), alkyliminosulfonyl (preferably with 1 to 15 carbon atoms), aryloxysulfonyl (preferably with 6 to 20 carbon atoms), alkylaryloxysulfonyl (preferably with 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl (preferably with 10 to 20 carbon atoms), alkoxyalkoxy (preferably with 5 to 20 carbon atoms), and cycloalkylalkoxyalkoxy (preferably with 8 to 20 carbon atoms).

[0247] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group with 7 to 12 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl.

[0248] The alkyl group in the tri(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include, for example, halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, preferably fluorine atoms or alkyl groups substituted with fluorine atoms. Multiple sulfonate anions can be bonded to each other via linking groups. In addition, multiple tri(alkylsulfonyl)methyl anions can be bonded to each other via linking groups.

[0249] Other non-nucleophilic anions include, for example, phosphorus fluoride (e.g., PF6-), boron fluoride (e.g., BF4-), and antimony fluoride (e.g., SbF6-).

[0250] The non-nucleophilic anion is preferably an aliphatic sulfonate anion with at least an α-position fluorine atom substitution, an aromatic sulfonate anion with a fluorine atom or a fluorine-containing alkyl group substitution, or a tri(alkylsulfonyl)methylation anion with an alkyl group substituted with a fluorine atom. More preferably, it is a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion with a fluorine atom, and even more preferably, a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion.

[0251] In terms of acid strength, to improve sensitivity, it is preferable that the pKa of the acid produced is below -1.

[0252] In addition, non-nucleophilic anions are preferably represented by the following general formula (AN1).

[0253] [Chemistry 48]

[0254] In the formula, Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R1 and R2 independently represent hydrogen atoms, fluorine atoms, or alkyl groups, respectively. When multiple R1 and R2 exist, they can be the same or different. L represents a divalent linkage base. When there are multiple Ls, they can be the same or different. A represents a cyclic organic group. x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0255] A more detailed explanation of the general formula (AN1) is provided. The alkyl group substituted with a fluorine atom in Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with a fluorine atom in Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of Xf include: fluorine atom, CF3, C2F5, C3F7, C4F9, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, etc., wherein, fluorine atom or CF3 is preferred. It is especially preferred that both Xf are fluorine atoms.

[0256] The alkyl groups of R1 and R2 may have substituents (preferably fluorine atoms), and the substituents preferably have 1 to 4 carbon atoms. The substituents are preferably perfluoroalkyl groups having 1 to 4 carbon atoms. Examples of substituent alkyl groups in R1 and R2 include: CF3, C2F5, C3F7, C4F9, C5F11, C6F13, C7F15, C8F17, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, etc., with CF3 being preferred. R1 and R2 are preferably fluorine atoms or CF3.

[0257] x is preferably an integer from 1 to 10, and more preferably from 1 to 5. y is preferably an integer between 0 and 4, and more preferably 0. z is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3. Examples of divalent linkers for L include: -COO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene, cycloalkylene, alkenylene, and linkers formed by linking multiple of these, preferably linkers with a total carbon number of 12 or less. Among these, -COO-, -CO-, or -O- are preferred, and -COO- is even more preferred.

[0258] The cyclic organic group of A is not particularly limited as long as it has a cyclic structure. Examples include alicyclic groups, aromatic cyclic groups, and heterocyclic groups (including not only those with aromaticity but also those without aromaticity). The alicyclic group can be monocyclic or polycyclic, preferably a monocyclic cycloalkyl group such as cyclopentyl, cyclohexyl, and cyclooctyl. Other preferred polycyclic cycloalkyl groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Specifically, in terms of suppressing diffusion in the film during the post-exposure heating step and increasing the Mask Error Enhancement Factor (MEEF), alicyclic groups with a large volume structure having 7 or more carbon atoms, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, are preferred. Examples of aromatic cyclic groups include benzene rings, naphthalene rings, phenanthrene rings, and anthracene rings. Examples of heterocyclic groups include those derived from furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Preferably, the group is derived from a furan ring, thiophene ring, or pyridine ring.

[0259] In addition, as a cyclic organic group, lactone structures can also be listed. As specific examples, lactone structures represented by the general formulas (LC1-1) to (LC1-22) can be listed.

[0260] The cyclic organic group may also have substituents. Examples of substituents include: alkyl groups (which may be linear or branched, or contain a cyclic structure; preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic or polycyclic, and when polycyclic, may be 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, etc. Furthermore, the carbon atoms constituting the cyclic organic group (carbons that contribute to ring formation) may also be carbonyl carbons.

[0261] Alternatively, photoacid generators can also be betaine compounds with a structure having a cationic portion and an anionic portion linked by covalent bonds.

[0262] As a photoacid generator, paragraphs

[0368] to

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

[0240] to

[0262] of Japanese Patent Application Publication No. 2013-228681 (corresponding to

[0339] of U.S. Patent Application Publication No. 2015 / 004533) are cited and incorporated into the description of this case.

[0263] Furthermore, as preferred specific examples, the following compounds can be listed. In the following compounds, the anions and cations can be interchanged arbitrarily.

[0264] [Chemistry 49]

[0265] [Transformation 50]

[0266] [Chemistry 51]

[0267] [Chemistry 52]

[0268] [Chemistry 53]

[0269] [Chemistry 54]

[0270] [Chemistry 55]

[0271] [Chemistry 56]

[0272] The content of the photoacid generator in the composition of the present invention is not particularly limited. However, for the purpose of enhancing the effects of the present invention, it is preferably 5.0% by mass or more, more preferably 9.0% by mass or more, and even more preferably 15.0% by mass or more, relative to the total solid content of the composition. Furthermore, the content is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 70.0% by mass or less. A photoacid generator can be used alone or in combination with two or more.

[0273] <(C) Compounds whose acid-scavenging ability decreases due to decomposition by photochemical rays or radiation> The composition of the present invention may include (C) a compound whose acid-capturing ability is reduced by irradiation with photochemical rays or radiation (also referred to as compound (C), photodegradable quencher, or photodegradable quencher (C)) as an acid diffusion control agent. Compound (C) functions as a quencher that captures the acid produced during exposure by the photoacid generator (B) and the like, and inhibits the reaction of the resin (A) in the unexposed portion caused by the excess generated acid.

[0274] Compound (C) is a compound that produces an acid that is relatively weak compared to the acid produced by the photoacid generator (B). That is, compound (C) is a compound that produces an acid with a pKa greater than that produced by the photoacid generator (B). The difference between the pKa of the acid produced by compound (C) and the pKa of the acid produced by photoacid generator (B) (the value obtained by subtracting the pKa of the acid produced by photoacid generator (B) from the pKa of the acid produced by free compound (C)) is preferably 1.00 or more, preferably 1.00 to 10.00, more preferably 1.00 to 5.00, and even more preferably 1.00 to 3.00. Furthermore, the pKa of the acid produced by compound (C) varies depending on the type of photoacid generator (B) used, for example, preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and even more preferably -1.00 to 5.00.

[0275] Compound (C) can be either a nonionic compound or an ionic compound. As a preferred embodiment, the ionic compound (C) contains a halogen atom in its anionic portion. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine is preferred.

[0276] As a preferred method, as compound (C), a compound that produces an acid that is relatively weak relative to the acid produced by the photoacid generator (B) can be selected from the compounds listed as photoacid generators (B) (preferably compounds represented by the general formula (PA-1) or onium salts represented by M+Z-).

[0277] The ionic compound (C) is also preferably one that contains halogen atoms in the cation portion.

[0278] The ionic compound (C) is preferably a compound represented by the following general formulas (C1) to (C3).

[0279] (Compounds represented by the general formula (C1))

[0280] [Chemistry 57]

[0281] In general formula (C1), R C1 represents cycloalkyl or aryl. L C1 represents a single bond, an extended alkyl group, an extended cycloalkyl group, -O-, -C(=O)-, or a divalent linkage group composed of these. MC+ represents an organic cation.

[0282] In general formula (C1), R C1 represents cycloalkyl or aryl. When R C1 represents a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 5 to 10 carbon atoms. The cycloalkyl group can be monocyclic or polycyclic. Examples of cycloalkyl groups include norbornel, decalinyl, and adamantyl, with adamantyl being preferred.

[0283] When R C1 represents an aryl group, the aryl group is preferably an aryl group with 6 to 15 carbon atoms. Examples of aryl groups include phenyl and naphthyl, with phenyl being the preferred choice.

[0284] R C1 can have substituents. As a preferred approach, when R C1 has a substituent, examples of substituents include fluorine atoms, groups having fluorine atoms, hydroxyl groups, alkyl groups, and halogen atoms other than fluorine atoms. The alkyl group having a fluorine atom is preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 5 carbon atoms. Specifically, trifluoromethyl, pentafluoroethyl, and nonafluorobutyl are examples, with trifluoromethyl being the most preferred. As a fluorinated cycloalkyl group, a fluorinated cycloalkyl group having 3 to 15 carbon atoms is preferred. Specifically, examples include fluorinated cyclohexyl, fluorinated cyclopentyl, and fluorinated adamantyl, with fluorinated cyclohexyl being preferred. Examples of alkyl groups include chain-like or branched alkyl groups having 1 to 5 carbon atoms. Halogen atoms other than fluorine atoms include chlorine, bromine, and iodine.

[0285] As a preferred method, at least one of R C1 and L C1 is substituted with a fluorine atom or a group having a fluorine atom. As a preferred embodiment, R C1 is preferably a polycyclic cycloalkyl or aryl group substituted with a fluorine atom or a group having a fluorine atom.

[0286] In general formula (C1), L C1 represents a single bond, an extended alkyl group, an extended cycloalkyl group, -O-, -C(=O)-, or a divalent linker consisting of these.

[0287] When L C1 represents an alkyl group, examples of alkyl groups with 1 to 20 carbon atoms can be listed, either in a chain or branched form. Examples of chain-like or branched alkyl groups having 1 to 20 carbon atoms include: methylene, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, etc., with methylene, ethyl, n-propyl, or n-butyl being preferred.

[0288] When L C1 represents an extended cycloalkyl group, examples of monocyclic or polycyclic extended cycloalkyl groups with 3 to 20 carbon atoms can be listed. Examples of cycloalkyl groups that are monocyclic or polycyclic with 3 to 20 carbon atoms include adamantyl, cyclohexyl, cyclopentyl, cycloheptyl, and norbornyl, with adamantyl, cyclohexyl, and norbornyl being preferred.

[0289] L C1 can have substituents. As a preferred approach, the substituents for L C1 when it has substituents can be listed as substituents for R C1 when it has substituents.

[0290] L C1 is preferably a single bond or an extended alkyl group, and more preferably a single bond or an extended n-butyl group.

[0291] In general formula (C1), MC+ represents an organic cation. MC+ is preferably a cation represented by the following general formula (ZcI) or general formula (ZcII).

[0292] [Chem.58]

[0293] In the general formula (ZcI), RCO1, RCO2, and RCO3 each independently represent an organic group.

[0294] [Chemistry 59]

[0295] In the general formula (ZcII), RCO4 and RCO5 independently represent aryl, alkyl, or cycloalkyl groups, respectively.

[0296] In the general formula (ZcI), RCO1, RCO2, and RCO3 each independently represent an organic group. The number of carbon atoms in the organic groups of RCO1, RCO2, and RCO3 is typically 1 to 30, preferably 1 to 20. Furthermore, two of the RCO1 to RCO3 groups can bond to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group. Examples of groups formed by the bonding of two of the RCO1 to RCO3 groups include alkyl groups (e.g., butyl, pentyl) and -CH2-CH2-O-CH2-CH2-.

[0297] There is no particular limitation on the cation in the general formula (ZcI). For example, the cations (ZaI-1), (ZaI-2), (ZaI-3b) represented by the general formula (ZaI-3b) and (ZaI-4b) represented by the general formula (ZaI-4b) can be listed.

[0298] In the general formula (ZcII), RCO4 and RCO5 independently represent aryl, alkyl, or cycloalkyl groups, respectively. The aryl group in RCO4 and RCO5 is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group in RCO4 and RCO5 may also be an aryl group containing a heterocycle with an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic aryl groups include: pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. The alkyl and cycloalkyl groups of R C04 and R C05 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, or pentyl), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0299] The aryl, alkyl, and cycloalkyl groups of RCO4 and RCO5 may each have substituents independently. Examples of substituents that may be present in the aryl, alkyl, and cycloalkyl groups of RCO4 and RCO5 include: alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 15 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0300] (Compounds represented by the general formula (C2))

[0301] [Transformation 60]

[0302] In general formula (C2), R C2 represents cycloalkyl or aryl. L C2 represents a single bond, an alkyl group, a cycloalkyl group, -O-, -C(=O)-, or a divalent linker consisting of these. MC+ represents an organic cation.

[0303] In general formula (C2), R C2 represents cycloalkyl or aryl. When R C2 represents a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 5 to 10 carbon atoms. The cycloalkyl group can be monocyclic or polycyclic. Examples of cycloalkyl groups include norbornel, decalinyl, and adamantyl, with adamantyl being preferred.

[0304] When aryl is represented by R C2, it is preferably an aryl group with 6 to 15 carbon atoms. Examples of aryl groups include phenyl and naphthyl, with phenyl being the preferred choice.

[0305] R C2 can also have substituents. As a preferred embodiment, as a substituent when R C2 has a substituent, examples of substituents when R C1 has a substituent in the general formula (C1) of the preferred embodiment can be listed.

[0306] R C2 is preferably a polycyclic cycloalkyl group, a polycyclic cycloalkyl group substituted with a fluorine atom or a fluorine-containing group, or an aryl group substituted with a fluorine atom or a fluorine-containing group, more preferably an adamantyl group or a phenyl group substituted with a fluorine atom or a fluorine-containing group.

[0307] In general formula (C2), L C2 represents a single bond, an extended alkyl group, an extended cycloalkyl group, -O-, -C(=O)-, or a divalent linkage group composed of these.

[0308] When L C2 represents an alkyl group, alkyl groups with 1 to 20 carbon atoms can be listed as either chain-like or branched. Examples of chain-like or branched alkyl groups having 1 to 20 carbon atoms include: methylene, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, etc., with methylene, ethyl, n-propyl, or n-butyl being preferred.

[0309] When L C2 represents an extended cycloalkyl group, examples of monocyclic or polycyclic extended cycloalkyl groups with 3 to 20 carbon atoms can be listed. Examples of cycloalkyl groups that are monocyclic or polycyclic with 3 to 20 carbon atoms include adamantyl, cyclohexyl, cyclopentyl, cycloheptyl, and norbornyl, with adamantyl, cyclohexyl, and norbornyl being preferred.

[0310] L C2 can have substituents. As a preferred embodiment, the substituents when L C2 has substituents can be listed as substituents when R C2 has substituents as the preferred embodiment.

[0311] When R C2 represents an aryl group, L C2 is preferably a single bond. When R C2 represents a cycloalkyl group, L C2 is preferably an alkyl group, -O-, -C(=O)-, or a divalent linker group formed by combining these, more preferably an alkyl group, -O-, -C(=O)-, or a divalent linker group formed by combining these, substituted with a fluorine atom or a fluorine-containing group. As a preferred embodiment, at least one of RC2 and LC2 is substituted with a fluorine atom or a group having a fluorine atom. The group having a fluorine atom is as described above.

[0312] MC+ represents an organic cation. MC+ is preferably a cation represented by the general formula (ZcI) or the general formula (ZcII).

[0313] (Compounds represented by the general formula (C3))

[0314] [Chemistry 61]

[0315] In general formula (C3), AC31 and AC32 independently represent -SO2-RPC1 or -CO-RPC2, respectively. RPC1 and RPC2 represent organic groups. MC+ represents an organic cation.

[0316] In general formula (C3), AC31 and AC32 independently represent -SO2-RPC1 or -CO-RPC2, respectively. RPC1 and RPC2 represent organic groups. RPC1 and RPC2 are preferred, respectively, represented by -L C31-R C31 and -L C32-R C32.

[0317] RC31 and RC32 represent alkyl or cycloalkyl groups, respectively. When alkyl is represented as RC31 or RC32, it is preferably a chain or branched alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. As an alkyl group, examples include methyl, ethyl, n-propyl, isopropyl, etc., with methyl or ethyl being preferred, and methyl being even more preferred.

[0318] When RC31 or RC32 represents a cycloalkyl group, it is preferably a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 5 to 10 carbon atoms. The cycloalkyl group can be monocyclic or polycyclic. Examples of cycloalkyl groups include cyclohexyl, norbornel, decahydronaphthyl, and adamantyl, with cyclohexyl or adamantyl being preferred. One or more of the carbon atoms that are members of the cycloalkyl group may be substituted by a carbonyl carbon atom.

[0319] R C31 or R C32 may also have substituents. As a preferred embodiment, when RC31 or RC32 has a substituent, examples of substituents in general formula (C1) of the preferred embodiment when RC1 has a substituent can be listed.

[0320] RC31 and RC32 are each preferably alkyl, alkyl substituted with a fluorine atom or a fluorine-containing group, or cycloalkyl, and more preferably methyl, trifluoromethyl, cyclohexyl or adamantyl.

[0321] LC31 and LC32 independently represent single-bond or divalent linkage groups, respectively. L C31 and L C32 are each preferably, independently, a single bond, an extended alkyl group, an extended cycloalkyl group, -O-, -C(=O)-, or a divalent linker group formed by combining these.

[0322] When alkyl groups are represented as L C31 or L C32, examples of alkyl groups with 1 to 20 carbon atoms can be listed, either in a chain or branched form. Examples of chain-like or branched alkyl groups having 1 to 20 carbon atoms include: methylene, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, etc., with methylene, ethyl, n-propyl, or n-butyl being preferred.

[0323] When L C31 or L C32 represents an extended cycloalkyl group, examples of monocyclic or polycyclic extended cycloalkyl groups with 3 to 20 carbon atoms can be listed. Examples of cycloalkyl groups that are monocyclic or polycyclic with 3 to 20 carbon atoms include adamantyl, cyclohexyl, cyclopentyl, cycloheptyl, and norbornyl, with adamantyl, cyclohexyl, and norbornyl being preferred.

[0324] L C31 or L C32 may have substituents. As a preferred embodiment, when LC31 or LC32 has a substituent, examples of substituents when RC31 or RC32 has a substituent can be listed.

[0325] L C31 and L C32 are each preferably, independently and preferably, single-bonded, alkyl, or fluorinated alkyl groups. As a preferred method, at least one of AC31 and AC32 is substituted with a fluorine atom or a group having a fluorine atom.

[0326] In the general formula (C3), MC+ represents an organic cation. MC+ is preferably a cation represented by the general formula (ZcI) or general formula (ZcII).

[0327] As preferred specific examples of the compound (C), the following compounds are listed. In the following compounds, the anion and cation can be interchanged arbitrarily.

[0328] [Chemistry 62]

[0329] [Chemistry 63]

[0330] [Chemistry 64]

[0331] [Chemistry 65]

[0332] [Chemistry 66]

[0333] [Chemistry 67]

[0334] The content of compound (C) in the composition of the present invention is not particularly limited, but for the purpose of further enhancing the effects of the present invention, it is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 5.0% by mass or more, relative to the total solid content of the composition. Furthermore, the content is preferably 40.0% by mass or less, more preferably 35.0% by mass or less, and even more preferably 30% by mass or less. Compound (C) may be used alone or in combination with two or more compounds.

[0335] <Compounds that produce acids upon exposure to photochemical rays or radiation, and whose acid-scavenging ability decreases upon decomposition upon exposure to photochemical rays or radiation (D)> The composition of the present invention may contain a compound that is both a photoacid generator (B) and a compound (C), that is, a compound (D) that generates acid by irradiation with photochemical rays or radiation and decomposes by irradiation with photochemical rays or radiation, thereby reducing its acid-scavenging ability (also referred to as compound (D), photoacid generator-linked quencher, or photoacid generator-linked quencher (D)). In other words, compound (D) is a compound having a structure that has the function equivalent to that of photoacid generator (B) and a structure that has the function equivalent to that of compound (C). Compound (D) is a preferred form of photoacid generator (B) and also a preferred form of compound (C).

[0336] Furthermore, as described above, in this invention, compound (C) is a compound that produces an acid that is relatively weak compared to the acid produced by the photoacid generator (B). That is, compound (C) is a compound that produces an acid with a pKa greater than that produced by the photoacid generator (B). In the case where the photoacid generator (B) and compound (C) are the same compound (D), it is assumed that the pKa of the acid produced by the structure in compound (D) having a function equivalent to that of compound (C) is greater than the pKa of the acid produced by the structure having a function equivalent to that of the photoacid generator (B).

[0337] Compound (D) can be either a nonionic compound or an ionic compound.

[0338] (Compounds represented by the general formula (PD)) There are no particular limitations on the ionic compound (D), but it is preferred to be a compound represented by the following general formula (PD).

[0339] [Chemistry 68]

[0340] In the general formula (PD), MD1+ and MD2+ represent organic cations independently. LD represents a divalent organic group. A D1- and B D1- represent anionic groups of acid radicals independently. Among them, in the compound represented by HAD1-LDBD1H, which is formed by substituting MD1+ and MD2+ of the compound represented by general formula (PD) with hydrogen atoms, the pKa of the group represented by HAD1 is lower than that of the group represented by BD1H.

[0341] The compound represented by the general formula (PD) contains, in one molecule, a structure having the function of a photoacid generator (B) (corresponding to the part of "MD1 +AD1--") and a structure having the function of a compound (C) (corresponding to the part of "-BD1 -MD2+"). Therefore, in the resist film, the respective ratio of the presence of the structures can be fixed. Therefore, the inventors speculate that even when the resist film is exposed, the amount and diffusion of acid generated in the resist film can easily become uniform, and the width of the pattern obtained after development is stable.

[0342] In the general formula (PD), MD1+ and MD2+ independently represent organic cations. The organic cations of MD1+ and MD2+ are preferably, independently, cations represented by the general formula (ZcI) or general formula (ZcII).

[0343] In the general formula (PD), LD represents a divalent organic group. Examples of divalent organic groups include -COO-, -CONH-, -CO-, alkyl groups (preferably with 1 to 6 carbon atoms, which can be linear or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. One or more methylene groups of the cycloalkane ring constituting the cycloalkyl group may be substituted with carbonyl carbons and / or oxygen atoms. These divalent linkages are also better suited to be bases selected from the group consisting of -O-, -S-, -SO- and -SO2-.

[0344] Wherein, LD is preferably the basis represented by the following general formula (LD). *A DL DA-L DB-L DC-L DD-L DE-*BD(LD)

[0345] In the general formula (LD), *AD represents the bond position with AD1- in the general formula (PD). In the general formula (LD), *BD represents the bond position with BD1- in the general formula (PD).

[0346] In the general formula (LD), L DA represents -(C(RD LA1)(RD ​​LA2)) XAD-, or exynyl aryl. The XA D represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3. RD LA1 and RD LA2 represent hydrogen atoms or substituents independently, respectively. The substituents of RD LA1 and RD LA2 are preferably fluorine atoms or fluoroalkyl groups, more preferably fluorine atoms or perfluoroalkyl groups, and even more preferably fluorine atoms or perfluoromethyl groups. When XA D is 2 or more, there are XA D RD LA1 that can be the same or different. When XA D is 2 or more, there are XA D RD LA2 that can be the same or different. -(C(RD LA1)(RD ​​LA2))- is preferably -CH 2-, -CHF-, -CH(CF 3)- or -CF 2-. Among them, -(C(RD LA1)(RD ​​LA2))- which is directly bonded to AD1- in the general formula (PD) is preferably -CH 2-, -CHF-, -CH(CF 3)- or -CF 2-. The -(C(RD LA1)(RD ​​LA2))- other than the -(C(RD LA1)(RD ​​LA2))- directly bonded to AD1 in the general formula (PD) are preferably -CH 2-, -CHF- or -CF 2-, respectively. There are no particular limitations on the aryl group used in L DA, but it is preferably an aryl group with 6 to 14 carbons, more preferably an aryl group with 6 to 10 carbons, and especially preferably an aryl group with phenyl groups. The aryl group may have substituents. There are no particular limitations on the substituents, but halogen atoms are preferred, and fluorine atoms are even more preferred.

[0347] In the general formula (LD), LDB represents a single bond, an ether group (-O-), an ester group (-COO-), or a sulfonyl group (-SO 2-).

[0348] In the general formula (LD), LDC represents a single bond, alkyl, cycloalkyl, aryl, or a combination thereof ("-alkyl-cycloalkyl-"), etc. The alkyl group can be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1; the number of carbon atoms in the cycloalkyl group is preferably 3 to 15, and more preferably 5 to 10. The cycloalkyl group can be monocyclic or polycyclic. Examples of the cycloalkyl groups mentioned above include norbornenediyl and adamantanediyl. The cycloalkyl group may preferably have alkyl substituents (which may be straight-chain or branched-chain, preferably with 1 to 5 carbon atoms). One or more methylene groups of the cycloalkane ring constituting the cycloalkyl group may also be substituted by carbonyl carbons and / or heteroatoms (nitrogen atoms, oxygen atoms, etc.). When LDC is "-extrinyl-extrincycloalkyl-", the extrinyl portion is preferably present on the LDB side. The aryl group of LDC is not particularly limited, but it is preferably an aryl group with 6 to 14 carbons, more preferably an aryl group with 6 to 10 carbons, and especially preferably an aryl group with phenyl groups. Aryl groups can have substituents. When LDB is a single bond, LDC is preferably a single bond or an extended cycloalkyl group.

[0349] In the general formula (LD), L DD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

[0350] In the general formula (LD), LDE represents a single bond or -(C(RD LE1)(RD ​​LE2)) XE D-. In the -(C(RD LE1)(RD ​​LE2))XED-, XED represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3. RD LE1 and RD LE2 represent hydrogen atoms or substituents independently, respectively. When XED is 2 or more, there are XED RD LE1s that can be the same or different. When XE D is 2 or more, there are XE D RD LE2 that can be the same or different. In this case, -(C(RD LE1)(RD ​​LE2))- is preferably -CH 2-. In the general formula (LD), when LDB, LDC, and LDD are single bonds, it is preferable that LDE is also a single bond.

[0351] In the general formula (PD), A D1 - represents the anion group of the acid radical. An anionic radical is a radical that has anionic atoms. Specifically, AD1 is preferably the basis represented by the general formula (AD-1) or (AD-2).

[0352] [Chemistry 69]

[0353] In the general formulas (AD-1) to (AD-2), * indicates the bond position. In the general formula (AD-2), R AD represents an organic group. R AD is not particularly limited, but alkyl is preferred. The alkyl group can be either straight-chain or branched-chain. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The alkyl group may preferably have a fluorine atom as a substituent. The alkyl group having a fluorine atom as a substituent may be a perfluoroalkyl group or may not be a perfluoroalkyl group.

[0354] In the general formula (PD), BD1- represents the anion group of the acid radical. Specifically, B D1 is preferably a basis represented by any one of the general formulas (B-1) to (B-6). B D1 - preferably a basis represented by any one of general formulas (BD-1) to (BD-3), more preferably a basis represented by any one of general formulas (BD-1) to (BD-2).

[0355] [Chemistry 70]

[0356] In general formulas (BD-1) to (BD-6), R and BD represent organic groups independently. L BD independently represent single bonds, alkyl groups, cycloalkyl groups, aryl groups, -O-, -C(=O)-, -SO 2-, or divalent linkages formed by combining these. * indicates the location of the bond.

[0357] R BD is preferably alkyl, cycloalkyl, or aryl. When R BD represents an alkyl group, the alkyl group is preferably a chain or branched alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. As an alkyl group, examples include methyl, ethyl, n-propyl, isopropyl, etc., with methyl or ethyl being preferred, and methyl being even more preferred.

[0358] When R BD represents a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 5 to 10 carbon atoms. The cycloalkyl group can be monocyclic or polycyclic. Examples of cycloalkyl groups include cyclopentyl, norbornyl, decahydronaphthyl, and adamantyl.

[0359] When R BD represents an aryl group, the aryl group is preferably an aryl group with 6 to 15 carbon atoms. Examples of aryl groups include phenyl and naphthyl, with phenyl being the preferred choice.

[0360] R BD can have substituents. As a preferred embodiment, as a substituent when R BD has a substituent, examples of substituents when R C1 has a substituent in the general formula (C1) of the preferred embodiment can be listed. As a preferred embodiment, when R BD has substituents, examples include alkoxycarbonyl and SO 3-. The alkyl group in the alkoxycarbonyl group is not particularly limited, but is preferably a chain-like or branched alkyl group with 1 to 10 carbon atoms, and more preferably an alkyl group with 1 to 5 carbon atoms.

[0361] L BD independently represent single bonds, alkyl groups, cycloalkyl groups, aryl groups, -O-, -C(=O)-, -SO 2-, or divalent linkages formed by combining these.

[0362] When L BD represents an alkyl group, alkyl groups with 1 to 20 carbon atoms can be listed as chain-like or branched alkyl groups. Examples of chain-like or branched alkyl groups having 1 to 20 carbon atoms include: methylene, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, etc., with methylene, ethyl, n-propyl, or n-butyl being preferred.

[0363] When L BD represents an extended cycloalkyl group, examples of monocyclic or polycyclic extended cycloalkyl groups with 3 to 20 carbon atoms can be listed. Examples of cycloalkyl groups that are monocyclic or polycyclic with 3 to 20 carbon atoms include adamantyl, cyclohexyl, cyclopentyl, cycloheptyl, and norbornyl, with adamantyl, cyclohexyl, and norbornyl being preferred. When L BD represents an aryl group, there is no particular limitation, but it is preferably an aryl group with 6 to 14 carbons, more preferably an aryl group with 6 to 10 carbons, and especially preferably an aryl phenyl group.

[0364] LBD can have substituents. As a preferred embodiment, examples of substituents in the RBD when substituents are present in the LBD can be listed.

[0365] L BD is preferably a single bond, methylene, -O-, -C(=O)-, or a divalent linker composed of these, more preferably a single bond or methylene.

[0366] In the compound represented by HAD1-LDBD1H, which is formed by substituting MD1+ and MD2+ of the compound represented by the general formula (PD) with hydrogen atoms, the pKa of the group represented by HAD1 is lower than that of the group represented by BD1H. More specifically, when the acid dissociation constant of the compound represented by HA D1-L DB D1H is determined, the pKa of the group represented by HA D1 when "HA D1-L DB D1H" becomes "A D1 --L DB D1H" is set as the pKa of the group represented by HA D1, and the pKa of the group represented by BD1H when "A D1 --L DB D1H" becomes "A D1 --L DB D1 -" is set as the pKa of the group represented by BD1H. The pKa of the basis represented by HA D1 and the pKa of the basis represented by B D1H are obtained using "software package 1" or "Gaussian 16" as described above. The pKa of the base represented by HAD1 is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and even more preferably -5.00 to 0.00. The pKa of the base represented by BD1H is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and even more preferably -1.00 to 5.00. The difference between the pKa of the base represented by BD1H and the pKa of the base represented by HAD1 ("pKa of the base represented by BD1H" - "pKa of the base represented by HAD1") is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, and even more preferably 2.00 to 15.00.

[0367] The following are preferred specific examples of compounds equivalent to compound (D).

[0368] [Chemistry 71]

[0369] [Chemistry 72]

[0370] [Chemistry 73]

[0371] [Chemistry 74]

[0372] [Chemistry 75]

[0373] The content of compound (D) in the composition of the present invention is not particularly limited, but for aspects that are more advantageous to the present invention, it is preferably 5% by mass or more, more preferably 9% by mass or more, and even more preferably 15% by mass or more, relative to the total solid content of the composition. Furthermore, the content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. Compound (D) may be used alone or in combination with two or more compounds.

[0374] The composition of the present invention is preferably, in addition to containing compound (D), also containing at least one of photoacid generator (B) and compound (C). Specifically, the following forms are listed as containing compounds that are equivalent to photoacid generators (B) or compounds (C) in the composition of the present invention.

[0375] (i) Photoacid generator (B) other than compound (D) + ionic compound (C) other than compound (D) (ii) Compound (D) (iii) Compound (D) + photoacid generator (B) other than compound (D) (iv) Compound (D) + Compound (C) other than compound (D) (v) Compound (D) + photoacid generator (B) other than compound (D) + compound (C) other than compound (D)

[0376] In (iii), compound (D) needs to function as compound (C), in which case the pKa of the acid produced by the structure in compound (D) having a function equivalent to compound (C) becomes greater than the pKa of the acid produced by the photoacid generator (B). In (iv), compound (D) is required to function as a photoacid generator (B), in which case the pKa of the acid generated by compound (C) becomes greater than the pKa of the acid generated by the structure in compound (D) that has the function equivalent to the photoacid generator (B). In (v), compound (D) can function as either a photoacid generator (B) or a compound (C). When functioning as a photoacid generator (B), the pKa of the acid produced by compound (C) becomes greater than the pKa of the acid produced by the structure in compound (D) that has a function equivalent to that of the photoacid generator (B). When functioning as compound (C), the pKa of the acid produced by the structure in compound (D) that has a function equivalent to that of compound (C) becomes greater than the pKa of the acid produced by the photoacid generator (B).

[0377] <Other Acid Diffusion Control Agents (E)> The components of this invention may further include acid diffusion control agents (also referred to as other acid diffusion control agents (E) or acid diffusion control agents (E)) other than compounds (C) and (D) without impairing the effects of the invention. The acid diffusion control agents function as quenchers that capture acid generated by photoacid generators and also control the diffusion of acid within the resist film. Acid diffusion control agents (E) can be, for example, basic compounds. The basic compound is preferably a compound having the structure represented by the following general formulas (A) to (E).

[0378] [Chemistry 76]

[0379] In general formulas (A) and (E), R 200, R 201, and R 202 may be the same or different, representing hydrogen atoms, alkyl groups (preferably with 1 to 20 carbon atoms), cycloalkyl groups (preferably with 3 to 20 carbon atoms), or aryl groups (preferably with 6 to 20 carbon atoms). Here, R 201 and R 202 may also be bonded to each other to form a ring.

[0380] Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R 203, R 204, R 205 and R 206 may be the same or different, representing alkyl groups with 1 to 20 carbon atoms. The alkyl groups in these general formulas (A) and (E) are preferably unsubstituted.

[0381] As basic compounds, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl portion may be linear or branched, and some may be substituted with ether and / or ester groups. The total number of all atoms other than hydrogen atoms in the alkyl portion is preferably 1 to 17), or piperidine, etc. More preferably, compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, a carboxylic acid onium salt structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having hydroxyl groups and / or ether bonds, or aniline derivatives having hydroxyl groups and / or ether bonds, etc.

[0382] Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, and benzimidazole. Examples of compounds having a diazabicyclic structure include 1,4-diazabicyclic[2,2,2]octane, 1,5-diazabicyclic[4,3,0]non-5-ene, and 1,8-diazabicyclic[5,4,0]undecyl-7-ene. Examples of compounds having a strontium hydroxide structure include triarylstromium hydroxide, benzylmethylstromium hydroxide, and strontium hydroxides having a 2-oxoalkyl group. Specifically, examples include triphenylstromium hydroxide, tris(tert-butylphenyl)stromium hydroxide, bis(tert-butylphenyl)iodine hydroxide, benzylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Compounds with a carboxylic acid onium salt structure are compounds with an onium hydroxide structure whose anionic part becomes a carboxylic acid salt, such as acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Compounds with a trialkylamine structure include, for example, tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include, for example, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives with hydroxyl and / or ether bonds include, for example, ethanolamine, diethanolamine, triethanolamine, tri(methoxyethoxyethyl)amine, and (HO-C2H4-OC2H4)2N(-C3H6-O-CH3). Aniline derivatives with hydroxyl and / or ether bonds include, for example, N,N-bis(hydroxyethyl)aniline.

[0383] As basic compounds, amine compounds having phenoxy groups and ammonium salt compounds having phenoxy groups are preferred examples.

[0384] As amine compounds, primary, secondary, and tertiary amine compounds can be used, with at least one alkyl group bonded to a nitrogen atom being preferred. Tertiary amine compounds are even more preferred. As long as at least one alkyl group (preferably with 1 to 20 carbon atoms) is bonded to the nitrogen atom, cycloalkyl groups (preferably with 3 to 20 carbon atoms) or aryl groups (preferably with 6 to 12 carbon atoms) may also be bonded to the nitrogen atom. Furthermore, the amine compound preferably has an oxoalkyl group. The number of oxoalkyl groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. The oxoalkyl group is also preferably oxoethyl (-CH 2CH 2O-) or oxopropyl (-CH(CH 3)CH 2O- or CH 2CH 2CH 2O-), and more preferably oxoethyl.

[0385] Ammonium salt compounds include, for example, primary, secondary, tertiary, and quaternary ammonium salt compounds, preferably ammonium salt compounds in which at least one alkyl group is bonded to a nitrogen atom. In an ammonium salt compound, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, cycloalkyl groups (preferably having 3 to 20 carbon atoms) or aryl groups (preferably having 6 to 12 carbon atoms) may also be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxoalkyl group. The number of oxoalkyl groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. The oxoalkyl group is preferably oxoethyl (-CH 2CH 2O-) or oxopropyl (-CH(CH 3)CH 2O- or -CH 2CH 2CH 2O-), and more preferably oxoethyl. Examples of anions that can be used as anions in ammonium salt compounds include halogen atoms, sulfonates, borates, and phosphates, with halogen atoms or sulfonates being preferred. Halogen atoms are preferably chlorine, bromine, or iodine atoms. Sulfonates are preferably organic sulfonates having 1 to 20 carbon atoms. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of an alkyl sulfonate may also have substituents, such as fluorine, chlorine, bromine, alkoxy, acetyl, and aromatic cyclic groups. Examples of alkyl sulfonates include methanesulfonates, ethanesulfonates, butanesulfonates, hexanesulfonates, octylsulfonates, benzyl sulfonates, trifluoromethanesulfonates, pentafluoroethanesulfonates, and nonafluorobutanesulfonates. Examples of aryl sulfonates with an aryl group include benzyl, naphthyl, and anthracene cyclic groups. The substituents that the benzyl, naphthyl, and anthracene cycloyl groups may have are preferably straight-chain or branched alkyl groups having 1 to 6 carbon atoms, or cycloalkyl groups having 3 to 6 carbon atoms. Examples of straight-chain or branched alkyl and cycloalkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, n-hexyl, and cyclohexyl. Other substituents include: alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano, nitro, acetyl, and acetoxy groups.

[0386] The so-called amine compounds with phenoxy groups and ammonium salt compounds with phenoxy groups refer to compounds in which a phenoxy group is located at the end of the alkyl group opposite to the nitrogen atom. Examples of substituents for phenoxy groups include: alkyl, alkoxy, halogen, cyano, nitro, carboxylic acid, carboxylic acid ester, sulfonate, aryl, aralkyl, acetoxy, and aryloxy groups. The substituent position can be any from position 2 to 6. The number of substituents can be any from 1 to 5.

[0387] Preferably, at least one oxyalkyl group is present between the phenoxy group and the nitrogen atom. The number of oxyalkyl groups is preferably 1 or more within the molecule, more preferably 3 to 9, and even more preferably 4 to 6. The oxyalkyl group is also preferably oxyethyl (-CH 2CH 2O-) or oxypropyl (-CH(CH 3)CH 2O- or -CH 2CH 2CH 2O-), more preferably oxyethyl.

[0388] Amine compounds with phenoxy groups can be obtained by heating and reacting a primary or secondary amine with a phenoxy group and a haloalkyl ether, followed by adding an aqueous solution of a strong base (e.g., sodium hydroxide, potassium hydroxide, or tetraalkylammonium) to the reaction system, and then extracting the reaction product with an organic solvent (e.g., ethyl acetate or chloroform). Alternatively, they can be obtained by heating and reacting a primary or secondary amine with a haloalkyl ether terminally containing a phenoxy group, followed by adding an aqueous solution of a strong base to the reaction system, and then extracting the reaction product with an organic solvent.

[0389] Low-molecular-weight compounds having a nitrogen atom and a group that is released due to acid action can also be used as acid diffusion control agents. Preferably, the low-molecular-weight compound is an amine derivative having a group that is released from the nitrogen atom due to acid action. The group that is removed due to the action of acid is preferably an acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or sesquiamine acetal ether group, and more preferably a carbamate group or a sesquiamine acetal ether group. The molecular weight of the low molecular weight compound is preferably 100-1000, more preferably 100-700, and even more preferably 100-500. Low molecular weight compounds may also have carbamate groups containing protecting groups on nitrogen atoms.

[0390] Specific examples of acid diffusion control agents (E) are described below, but the invention is not limited thereto.

[0391] [Chemistry 77]

[0392] [Chemistry 78]

[0393] When the composition of the present invention contains an acid diffusion control agent (E), the content of the acid diffusion control agent (E) is preferably 0.001% to 20.0% by mass, more preferably 0.01% to 5.0% by mass, and even more preferably does not contain the acid diffusion control agent (E) relative to the total solid components of the composition. Acid diffusion control agent (E) can be used alone or in combination with two or more.

[0394] As an acid diffusion control agent (E), for example, the compounds described in paragraphs

[0140] to

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

[0395] <Hydrophobic Resin (F)> In addition to the resin (A), the composition of the present invention may also contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to exist on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups in their molecules, and may not contribute to the uniform mixing of polar and non-polar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angle of the resist film surface relative to water, and suppressing gas escape.

[0396] Regarding the presence of the hydrophobic resin on the film surface, it is preferable that the hydrophobic resin has one or more of "fluorine atoms", "silicon atoms", and "CH3 moiety contained in the side chain portion of the resin", more preferably two or more. Furthermore, the hydrophobic resin preferably has hydrocarbon groups with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chains.

[0397] When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0398] When the hydrophobic resin contains fluorine atoms, the fluorine-containing part of the structure is preferably an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight-chain or branched alkyl group having at least one hydrogen atom substituted with a fluorine atom, and may further have substituents other than fluorine atoms. A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may further have substituents other than a fluorine atom. As an aryl group having a fluorine atom, for example, aryl groups such as phenyl and naphthyl can have at least one hydrogen atom replaced by a fluorine atom, and can further have substituents other than fluorine atoms. As a repeating unit having fluorine or silicon atoms, for example, the repeating unit illustrated in paragraph

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

[0399] In addition, as mentioned above, hydrophobic resins are also preferably those containing a CH3 moiety in the side chain portion. Here, the CH3 moiety structure of the side chain portion in the hydrophobic resin includes the CH3 moiety structure of ethyl and propyl compounds. On the other hand, methyl groups (e.g., α-methyl groups having repeating units of methacrylic acid structure) that are directly bonded to the main chain of the hydrophobic resin contribute little to the surface bias of the hydrophobic resin due to the influence of the main chain, and are therefore not included in the CH3 part structure of the present invention.

[0400] Regarding hydrophobic resins, please refer to paragraphs

[0348] to

[0415] of Japanese Patent Application Publication No. 2014-010245, and these contents are incorporated into the description of this case.

[0401] Furthermore, in addition to the above, the hydrophobic resins can also preferably be the resins described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859, and Japanese Patent Application Publication No. 2012-032544.

[0402] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01% to 20% by mass, and more preferably 0.1% to 15% by mass, relative to the total solid components of the composition.

[0403] Solvent The components of this invention may also contain solvents. The solvent is preferably a propylene glycol monoalkyl ether carboxylate (M1) and at least one of (M2), wherein (M2) is selected from at least one of the group consisting of propylene glycol monoalkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones, and alkyl carbonates. Furthermore, the solvent may also contain components other than (M1) and (M2).

[0404] The inventors have discovered that when such a solvent is used in combination with the resin, the coatability of the composition is improved, and patterns with fewer development defects can be formed. While the reason may not be entirely clear, the inventors believe it is because these solvents, due to the good balance of the resin's solubility, boiling point, and viscosity, can suppress uneven film thickness and the formation of precipitates during spin coating.

[0405] The component (M1) is preferably selected from at least one of the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and more preferably propylene glycol monomethyl ether acetate (PGMEA).

[0406] The preferred solvent for component (M2) is the following. Preferred propylene glycol monoalkyl ethers are propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE). The preferred lactate esters are ethyl lactate, butyl lactate, or propyl lactate. Preferred acetates are methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Alternatively, butyl butyrate is also preferred. The preferred alkoxypropionate is methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). Preferred chain ketones are 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone-based acetone, ionone, diacetone alcohol, acetoacetyl alcohol, acetophenone, methyl naphthyl ketone, or methyl pentyl ketone. Cyclic ketones are preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone. The preferred lactone is γ-butyrolactone. Alkyl carbonate is preferably propyl carbonate.

[0407] The preferred ingredient (M2) is propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl pentyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ-butyrolactone, or propyl carbonate.

[0408] In addition to the aforementioned components, it is preferable to use an ester solvent with 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or fewer heteroatoms.

[0409] Examples of ester solvents having 7 or more carbon atoms and 2 or fewer heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butyrate, with isoamyl acetate being preferred.

[0410] The component (M2) is preferably a solvent with a flash point (hereinafter also referred to as fp) of 37°C or higher. The component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl pentyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propyl carbonate (fp: 132°C). More preferably, it is propylene glycol monoethyl ether, ethyl lactate, amyl acetate, or cyclohexanone, and even more preferably, it is propylene glycol monoethyl ether or ethyl lactate. Furthermore, the term "flash point" here refers to the value recorded in the reagent catalogues of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

[0411] The solvent preferably contains component (M1). More preferably, the solvent is either substantially containing only component (M1) or a mixture of component (M1) and other components. In the latter case, the solvent is further preferably containing both component (M1) and component (M2).

[0412] The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably "100 / 0" to "0 / 10 [0 / 100]", more preferably "100 / 0" to "15 / 85", further preferably "100 / 0" to "40 / 60", and even more preferably "100 / 0" to "60 / 40". That is, when the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is preferably 15 / 85 or more, more preferably 40 / 60 or more, and even more preferably 60 / 40 or more. If the above configuration is adopted, the number of development defects can be further reduced.

[0413] Furthermore, when the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is set to, for example, 99 / 1 or less.

[0414] As mentioned above, the solvent may also contain components other than component (M1) and component (M2). In this case, the content of components other than component (M1) and (M2) is preferably 5% to 30% by mass relative to the total amount of solvent.

[0415] The solvent content in the composition of the present invention is preferably set to a solid component concentration of 0.5% to 30% by mass, more preferably 1% to 20% by mass. This further improves the coatability of the composition of the present invention. Furthermore, the so-called solid components refer to all components other than the solvent. The so-called solid component concentration is the mass percentage of the mass of components other than solvents relative to the total mass of the composition of this invention. The term "total solid components" refers to the total mass of the components after removing the solvent from the entire composition of the present invention. Furthermore, the term "solid components," as described above, refers to the components after removing the solvent; for example, they may be solid or liquid at 25°C.

[0416] <surfactants> The composition of this invention may also contain surfactants. If surfactants are included, patterns with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorinated and / or silicone surfactant. As a fluorinated and / or silicone surfactant, for example, the surfactant described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425 can be cited. Alternatively, Eftop EF301 or EF303 (manufactured by Shin-Akita Chemical); Fluorad FC430, 431, and 4430 (manufactured by Sumitomo 3M); Megafac F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by Asahi Glass); Troysol S-366 (manufactured by Troy Chemical); GF-300 or GF-150 (manufactured by Toa Synthetic Chemicals); and Surflon S-393 (manufactured by Shimizu Chemicals) can also be used. Chemical (manufactured by) (stock company); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Jemco (stock company); PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei (stock company); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (manufactured by NEOS (stock company). Furthermore, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry (stock company)) can also be used as a silicone-based surfactant.

[0417] In addition to the known surfactants described above, surfactants can also be synthesized using fluorinated aliphatic compounds produced by short-chain polymerization (telomerization, also known as telomerization) or oligomerization (also known as oligomerization). Specifically, polymers possessing fluorinated aliphatic groups derived from such fluorinated aliphatic compounds can also be used as surfactants. Such fluorinated aliphatic compounds can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2002-90991. Alternatively, surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph

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

[0418] These surfactants can be used alone or in combination with more than one type.

[0419] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001% to 2% by mass, and more preferably 0.0005% to 1% by mass, relative to the total solid components of the composition.

[0420] <Other Additives> The composition of the present invention may further include 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 carboxylic acid group).

[0421] The composition of this invention may further contain a solubility-inhibiting compound. Here, "solution-inhibiting compound" refers to a compound with a molecular weight of 3000 or less that decomposes due to the action of acid and thus has reduced solubility in organic developing solutions.

[0422] [use] The composition of this invention relates to a photosensitive radioactive or radiosensitive linear resin composition that reacts and changes in properties upon irradiation by photochemical rays or radiation. More specifically, the composition of this invention relates to a photosensitive radioactive or radiosensitive linear resin composition used in semiconductor manufacturing processes such as integrated circuits (ICs), the manufacture of circuit boards such as liquid crystal or thermal heads, the fabrication of die structures for imprinting, other photofabrication processes, or the manufacture of lithographic printing plates or acid-curable compositions. The patterns formed in this invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and microelectromechanical systems (MEMS), etc.

[0423] [Photosensitive X-ray or radiation-sensitive linear membrane] This invention also relates to a photosensitive radioactive or radioactive linear resin composition of the present invention, forming a photosensitive radioactive or radioactive linear film (typically a "resist film"). Such a film can be formed, for example, by coating the composition of the present invention onto a support such as a substrate. The thickness of the film is preferably 0.02 μm to 0.1 μm. As a method for coating onto a substrate, appropriate coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating can be used, but spin coating is preferred, with a preferred rotation speed of 1000 rpm to 3000 rpm (rotations per minute). The coated film is pre-baked at 60°C to 150°C for 1 minute to 20 minutes, preferably at 80°C to 120°C for 1 minute to 10 minutes to form a thin film. Regarding the materials constituting the substrate being processed and its outermost layer, in the case of semiconductor wafers, silicon wafers can be used. Examples of materials that can be used as the outermost layer include: Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective films, etc.

[0424] [Pattern Formation Method] The procedure for pattern formation using the aforementioned photosensitive radioactive or radiosensitive linear resin composition is not particularly limited, but it is preferred to include the following steps. Step 1: Forming a photosensitive radioactive or radioactive linear film on a substrate using a photosensitive radioactive or radioactive linear resin composition. Step 2: Exposure of the photosensitive linear or radiosensitive film (preferably with EUV light). Step 3: The step of developing the exposed photosensitive radioactive or radiosensitive linear film using a developing solution to form a pattern. The following is a detailed description of the sequence of each step.

[0425] <Step 1: Formation of a photosensitive or radiosensitive linear film> Step 1 is the step of forming a photosensitive radioactive or radioactive linear film on a substrate using a photosensitive radioactive or radioactive linear resin composition.

[0426] As a method for forming a photosensitive radioactive or radioactive linear film on a substrate using a photosensitive radioactive or radioactive linear resin composition, for example, a method of coating a photosensitive radioactive or radioactive linear resin composition onto a substrate can be cited. Furthermore, it is preferable to filter the photosensitive or radiosensitive linear resin composition 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. Additionally, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0427] Photosensitive or radiosensitive linear resin compositions can be applied to substrates (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit components using appropriate coating methods such as spin coaters or coaters. Spin coating using a spin coater is preferred. The preferred rotation speed for spin coating using a spin coater is 1000 rpm to 3000 rpm. After coating the substrate with a photosensitive or radiosensitive linear resin composition, the substrate can be dried to form a photosensitive or radiosensitive linear film. Furthermore, various substrate films (inorganic films, organic films, antireflective films) can be formed on the underside of the resist film as needed.

[0428] As a drying method, methods involving heating can be cited as an example. Heating can be carried out using mechanisms included in conventional exposure machines and / or developing machines, or using heating plates, etc. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C, and even more preferably 80°C to 130°C. The heating time is preferably 30 seconds to 1000 seconds, more preferably 60 seconds to 800 seconds, and even more preferably 60 seconds to 600 seconds.

[0429] There are no particular limitations on the thickness of the photosensitive or radiosensitive linear film, but in terms of forming finer patterns with higher precision, it is preferably 10 nm to 65 nm, and more preferably 15 nm to 50 nm.

[0430] Furthermore, a topcoat can be formed by using a topcoat composition on top of a photosensitive or radiosensitive linear film. The composition of the top coating is preferably not mixed with the photosensitive or radiosensitive linear film, so that it can be uniformly coated on the upper layer of the photosensitive or radiosensitive linear film. Furthermore, it is preferable to dry the photosensitive radioactive or radioactive linear film before forming the top coating. Next, a top coating composition is applied to the obtained photosensitive radioactive or radioactive linear film using a component that is the same as the method for forming the photosensitive radioactive or radioactive linear film, and then dried to form the top coating. The thickness of the top coating is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm, and even more preferably 40 nm to 80 nm. There are no particular limitations on the top coating. The top coating can be formed by existing known methods, for example, based on 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 as described in Japanese Patent Application Publication No. 2013-61648 on a photosensitive radioactive or radioactive linear film. Specific examples of alkaline compounds that may be contained in the top coating include alkaline compounds that may be contained in the aforementioned photosensitive or radioactive linear resin composition. In addition, 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.

[0431] <Step 2: Exposure Step> Step 2 is the step of exposing the photosensitive radioactive or radiosensitive linear film (preferably with EUV light). As an exposure method, for example, EUV light can be irradiated onto the formed photosensitive radioactive or radiosensitive linear film through a prescribed mask.

[0432] It is preferable to bake (heat) the exposed area after exposure and before development. Baking promotes the reaction of the exposed area, resulting in better 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 seconds to 1000 seconds, more preferably 10 seconds to 180 seconds, and even more preferably 30 seconds to 120 seconds. Heating can be performed using mechanisms included in conventional exposure and / or developing machines, or using heating plates, etc. This step is also known as post-exposure baking.

[0433] <Step 3: Development Step> Step 3 is a step of developing the exposed photosensitive radioactive or radiosensitive linear film with a developing solution 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).

[0434] Examples of development methods include: immersing a substrate in a tank filled with developer for a fixed time (immersion method); using surface tension to accumulate developer on the substrate surface and allowing it to stand still for a fixed time for development (puddle method); spraying developer onto the substrate surface (spray method); and continuously spraying developer onto a substrate rotating at a fixed speed while scanning the developer nozzle at a fixed speed (dynamic distribution method). Alternatively, after the development step, a step can be performed where the development is stopped while the solvent is replaced with another solvent. There is no particular limitation on the development time if it is the time for the resin in the unexposed part to fully dissolve, but 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℃.

[0435] Alkaline developers preferably use alkaline aqueous solutions containing 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, aqueous solutions containing quaternary ammonium salts, represented by tetramethylammonium hydroxide (TMAH), are preferred. Appropriate amounts of alcohols and surfactants may also be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1% to 20% by mass. Furthermore, the pH of the alkaline developer is typically 10.0 to 15.0.

[0436] 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.

[0437] Examples of ketone solvents include: 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone-based acetone, ionone, diacetone alcohol, acetoethyl alcohol, acetophenone, methyl naphthyl ketone, isophorone, and propyl carbonate, etc.

[0438] Examples of ester-based solvents include: methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[0439] As an alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, for example, the solvents disclosed in paragraphs

[0715] to

[0718] of the specification in U.S. Patent Application Publication No. 2016 / 0070167A1 may be used.

[0440] The solvent can be mixed with multiple solvents, or with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and most preferably substantially free of water. The content of organic solvent 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, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

[0441] <Other Steps> The pattern forming method preferably includes a cleaning step using a rinsing solution after step 3.

[0442] As a rinsing solution used in the rinsing step following the development step with an alkaline developer, pure water can be an example. Alternatively, an appropriate amount of surfactant can be added to the pure water.

[0443] The rinsing solution used in the rinsing step after the developing step using an organic developer is not particularly limited as long as it does not dissolve the resist pattern; a solution containing a common organic solvent 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. Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents are those identical to those described in the developing solutions containing organic solvents.

[0444] There are no particular limitations on the method of rinsing. For example, the following methods can be listed: continuously spraying rinsing liquid onto a substrate rotating at a fixed speed (spin coating method), immersing the substrate in a tank filled with rinsing liquid for a fixed time (immersion method), and spraying rinsing liquid onto the surface of the substrate (spray method). Furthermore, the pattern forming method of the present invention may also include a post-bake step after the rinsing step. This step removes residual developer and rinsing solution between and within the pattern using baking. Additionally, this step also forms a resist pattern and improves the surface roughness of the pattern. The post-rinsing step is typically performed at 40°C to 250°C (preferably 90°C to 200°C) for a typical duration of 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0445] Alternatively, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step 3 can also be used as a mask to process the substrate (or the lower film and substrate) to form a pattern on the substrate. There is no particular limitation on the processing method of the substrate (or the lower film and the substrate), but it is preferable to form a pattern on the substrate by dry etching the substrate (or the lower film and the substrate) using the pattern formed in step 3 as a mask. Dry etching can be a single-segment etching or an etching process involving multiple segments. In the case of a multi-segment etching process, each segment can be etched using the same or different methods. Etching can be performed using any known method, with various conditions determined according to the type and application of the substrate. For example, etching can be performed according to the "Proceedings of the Society of Photo-optical Instrumentation Engineers (Proc. of SPIE)" Vol. 6924, 692420 (2008) and Japanese Patent Application Publication No. 2009-267112. Alternatively, the method described in "Chapter 4 Etching" of "Semiconductor Processing Textbook 4th Edition, 2007, Publisher: SEMI Japan" can also be used. Among them, dry etching is preferred for oxygen plasma etching.

[0446] The components of this invention and the various materials used in the pattern forming method of this invention (e.g., solvents, developers, rinsing solutions, components for forming antireflective films, components for forming topcoats, etc.) are preferably free of impurities such as metals. The content of impurities contained in these materials is preferably less than 1 ppm by mass, more preferably less than 10 ppb by mass, further preferably less than 100 ppt by mass, particularly preferably less than 10 ppt by mass, and most preferably less than 1 ppt by mass. Examples of metallic impurities include, for instance, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0447] As a method for removing impurities such as metals from various materials, filtration using filters can be cited as an example. The filter pore size is preferably less than 100 nm, more preferably less than 10 nm, and even more preferably less than 5 nm. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. The filter may also include a composite material combining the filter raw material and an ion exchange medium. The filter may also be a filter that has been pre-cleaned with an organic solvent. Multiple filters can be connected in series or parallel during the filtration process. When using multiple filters, filters with different pore sizes and / or materials can be combined. Furthermore, various materials can be filtered multiple times; this multiple filtration process can be a circulating filtration process. In the manufacture of the components of this invention, it is preferred, for example, that after dissolving the resin and photoacid generator, etc., in a solvent, multiple filters made of different raw materials are used for circulating filtration. For example, it is preferred to arrange and connect a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 3 nm, and perform circulating filtration more than 10 times. The smaller the pressure difference between the filters, the better, typically 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The smaller the pressure difference between the filter and the filling nozzle, the better, typically 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less. The interior of the manufacturing apparatus for the composition of the present invention is preferably purged with an inert gas such as nitrogen. This suppresses the dissolution of reactive gases such as oxygen into the composition. The components of the present invention are filtered through a filter and then filled into a clean container. The components of the present invention filled into the container are preferably stored under refrigeration. This suppresses performance degradation caused by time. The shorter the time from the completion of filling the container with the components to the start of refrigeration, the better, typically within 24 hours, preferably within 16 hours, more preferably within 12 hours, and even more preferably within 10 hours. The storage temperature is preferably 0°C to 15°C, more preferably 0°C to 10°C, and even more preferably 0°C to 5°C.

[0448] In addition, as a method to reduce impurities such as metals contained in various materials, the following methods can be listed: selecting raw materials with low metal content as raw materials for various materials, filtering the raw materials for various materials with filters, and lining the device with Teflon (registered trademark) and distilling under conditions that suppress contamination as much as possible.

[0449] Besides filtration, impurities can also be removed using adsorbent materials, or a combination of filtration and adsorbent materials can be used. As adsorbent materials, known adsorbent materials can be used, such as inorganic adsorbent materials like silicone and zeolite, and organic adsorbent 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. The content of metal components in the cleaning solution used to clean the manufacturing apparatus can be measured to confirm whether metal impurities have been sufficiently removed from the manufacturing apparatus. The content of metal components 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.

[0450] To prevent malfunctions in chemical piping and various components (filters, O-rings, tubes, etc.) caused by static electricity and subsequent electrostatic discharge, conductive compounds can be added to organic processing solutions such as rinsing solutions. There are no particular limitations on the conductive compounds; methanol is an example. There are no particular limitations on the amount added, but for maintaining better developing or rinsing properties, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For pharmaceutical piping, various pipes coated with SUS (stainless steel) or antistatic-treated polyethylene, polypropylene, or fluoropolymer (PTFE or perfluoroalkoxy resin, etc.) membranes can be used. Similarly, filters and O-rings can also be made of antistatic-treated polyethylene, polypropylene, or fluoropolymer (PTFE or perfluoroalkoxy resin, etc.).

[0451] For patterns formed by the method of the present invention, methods for improving the surface roughness of the pattern can be applied. Examples of methods for improving the surface roughness of the pattern include, for instance, the method disclosed in International Patent Publication No. 2014 / 002808, which uses a plasma containing hydrogen gas to process the pattern. In addition, known methods described in Japanese Patent Application Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, Japanese Patent Application Publication No. 2008-83384, and the Proceedings of the International Society for Optical Engineering (SPIE) Vol. 8328 83280N-1, entitled "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement".

[0452] When the resulting pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and even more preferably 1.7 or less. When the formed pattern is a groove pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0453] The patterning method of the present invention can also be used for guided patterning in Directed Self-Assembly (DSA) (e.g., see "ACS Nano" Vol.4 No.8 4815-4823).

[0454] Furthermore, the pattern formed by the method can be used, for example, as the core material in the spacer manufacturing process disclosed in Japanese Patent Application Publication No. 3-270227 and Japanese Patent Application Publication No. 2013-164509.

[0455] In addition, the present invention also relates to a method for manufacturing an electronic component incorporating the pattern forming method, and an electronic component manufactured using the method. The electronic components of this invention can be preferably mounted in electrical and electronic machines (home appliances, office automation (OA), media-related machines, optical machines, and communication machines, etc.). [Example]

[0456] The present invention will be further described in detail below based on embodiments. The materials, amounts, proportions, processing contents, and processing order 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 limitedly by the embodiments shown below.

[0457] [Various components of photosensitive or radiosensitive linear resin compositions] [Resin (A)] The following shows the resins A (resin A-1 to resin A-69, resin A'-1 to resin A'-2) shown in Table 3. Resins A-1 to A-68 and A'-1 to A'-2 are resins synthesized according to the synthesis method of resin A-1 described later (synthesis example 2). Table 1 shows the composition ratio (moles %; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown later. Furthermore, the weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of resins A-1 to A-69 and resins A'-1 to A'-2 were determined by GPC (solvent: tetrahydrofuran, THF). Additionally, the composition ratio (moles%) of the resins was determined by 13C nuclear magnetic resonance (NMR). Furthermore, resins A'-1 to A'-2 are not resins (A), but for ease of explanation, they are listed as resins (A) in Table 1.

[0458] [Table 1-1] Table 1 Mole ratio of repeating unit 1 Mole ratio of repeating unit 2 Mole ratio of repeating unit 3 Mole ratio of repeating unit 4 Mole ratio of repeating unit 5 Mw Mw / Mn Resin A-1 - - - - M-70 50 M-31 50 - - 6500 1.60 Resin A-2 - - - - M-71 35 M-32 40 M-33 25 8000 1.54 Resin A-3 - - - - M-72 30 M-33 70 - - 9000 1.67 Resin A-4 - - - - M-73 40 M-34 60 - - 7500 1.55 Resin A-5 - - - - M-74 20 M-35 80 - - 8500 1.59 Resin A-6 - - - - M-75 50 M-36 30 M-37 20 5500 1.68 Resin A-7 - - - - M-76 45 M-37 30 M-38 25 4500 1.77 Resin A-8 M-69 10 - - M-77 40 M-38 50 - - 12000 1.84 Resin A-9 - - M-68 15 M-78 25 M-39 60 - - 14000 1.65 Resin A-10 M-67 5 - - M-79 35 M-40 60 - - 8800 1.55 Resin A-11 M-66 10 - - M-80 30 M-41 45 M-32 15 22000 1.56 Resin A-12 - - M-1 35 M-81 25 M-42 40 - - 14000 1.65 Resin A-13 - - M-2 15 M-82 25 M-43 60 - - 6500 1.40 Resin A-14 - - M-3 15 M-83 35 M-44 50 - - 6700 1.50 Resin A-15 - - M-4 10 M-84 55 M-45 15 M-41 20 7200 1.54 Resin A-16 - - M-5 5 M-85 40 M-46 55 8000 1.29 Resin A-17 - - M-6 30 M-70 10 M-47 60 - - 4500 1.35 Resin A-18 M-7 10 - - M-71 35 M-48 55 - - 5000 1.25 Resin A-19 M-8 25 - - M-72 25 M-49 40 M-40 10 5500 1.50 Resin A-20 M-9 10 - - M-73 40 M-50 50 - - 5600 1.60 Resin A-21 M-10 10 - - M-74 25 M-51 35 M-58 30 7800 1.56 Resin A-22 M-11 15 - - M-75 40 M-52 45 - - 9000 1.54 Resin A-23 M-12 15 - - M-76 35 M-53 50 - - 8000 1.74 Resin A-24 M-13 10 - - M-77 25 M-54 65 - - 7500 1.55 Resin A-25 M-14 5 - - M-78 35 M-55 60 - - 8600 1.72 Resin A-26 M-15 30 - M-79 10 M-56 60 - - 12500 1.80 Resin A-27 - - M-16 5 M-80 25 M-57 70 - - 5500 1.33 Resin A-28 M-17 15 - - M-81 40 M-58 45 - - 4500 1.40 Resin A-29 M-18 20 - - M-82 25 M-59 55 - - 6500 1.55 Resin A-30 M-19 25 - - M-83 15 M-60 60 - - 6000 1.65 Resin A-31 M-20 20 - - M-84 10 M-61 70 - - 5900 1.56 Resin A-32 M-21 10 - - M-85 40 M-62 50 - - 8900 1.55 Resin A-33 M-22 15 - - M-70 25 M-63 60 - - 12000 1.65 Resin A-34 M-23 10 - - M-71 20 M-64 70 - - 8000 1.55 Resin A-35 M-24 5 - M-72 20 M-65 75 - 14000 1.56

[0459] [Table 1-2] Table 1 (Continued) Mole ratio of repeating unit 1 Mole ratio of repeating unit 2 Mole ratio of repeating unit 3 Mole ratio of repeating unit 4 Mole ratio of repeating unit 5 Mw Mw / Mn Resin A-36 M-25 5 - - M-73 30 M-31 65 - - 12000 1.65 Resin A-37 M-26 10 - - M-74 30 M-32 60 - - 8000 1.40 Resin A-38 - - M-27 15 M-75 30 M-33 55 - - 6500 1.54 Resin A-39 M-23 15 - - M-76 35 M-34 50 - - 5500 1.29 Resin A-40 M-29 10 - - M-77 30 M-35 60 - - 4000 1.35 Resin A-41 - - M-30 10 M-78 35 M-36 55 - - 8800 1.25 Resin A-42 - - M-1 20 M-79 10 M-37 70 - - 10000 1.50 Resin A-43 - - M-2 15 M-80 20 M-38 65 - - 7100 1.67 Resin A-44 - - M-3 15 M-81 15 M-39 70 - - 6600 1.65 Resin A-45 - - M-4 10 M-82 45 M-40 45 - - 12200 1.55 Resin A-46 - - M-5 5 M-83 45 M-41 50 - - 7700 1.56 Resin A-47 - - M-6 5 M-84 40 M-42 55 - - 6700 1.65 Resin A-48 M-13 10 - - M-85 25 M-43 65 - - 5400 1.40 Resin A-49 - - M-4 30 M-70 15 M-31 55 - - 4300 1.54 Resin A-50 M-15 15 - - M-71 45 M-32 40 - - 5400 1.29 Resin A-51 M-19 15 M-1 5 M-72 45 M-33 35 - - 6800 1.35 Resin A-52 M-22 15 M-2 10 M-73 20 M-34 55 - - 7100 1.25 Resin A-53 - - M-3 20 M-74 30 M-35 50 - - 7400 1.50 Resin A-54 - - M-4 15 M-75 25 M-36 60 - - 6900 1.60 Resin A-55 - - M-5 25 M-76 10 M-31 65 - - 8500 1.55 Resin A-56 - - M-6 30 M-77 20 M-32 50 - - 6500 1.55 Resin A-57 M-9 10 - - M-78 45 M-33 45 - - 5500 1.55 Resin A-58 M-13 15 - - M-79 35 M-43 50 - - 4000 1.55 Resin A-59 - - M-1 20 M-80 15 M-32 65 - - 8800 1.55 Resin A-60 - - M-2 15 M-81 25 M-43 60 - - 10000 1.55 Resin A-61 - - M-3 15 M-82 15 M-33 70 - - 7100 1.55 Resin A-62 - - M-4 30 M-83 15 M-31 55 - - 6600 1.55 Resin A-63 - - M-5 35 M-84 30 M-32 35 - - 12200 1.55 Resin A-64 - - M-6 25 M-85 35 M-33 40 - - 7700 1.55 Resin A-65 - - - - M-70 50 M-33 50 - - 6700 1.55 Resin A-66 - - - - M-86 50 M-33 50 - - 6700 1.55 Resin A-67 - - - - M-87 50 M-33 50 - - 6700 1.55 Resin A-68 - - - - M-88 50 M-33 50 - - 6700 1.55 Resin A-69 - - - - M-91 50 M-33 50 - - 6700 1.55 Resin A'- 1 M-89 50 - - - - M-31 50 - - 6500 1.60 Resin A'-2 M-90 50 - - - - M-31 50 - - 6500 1.60

[0460] The following shows the structure of monomers M-1 to M-91, which are the repeating units that constitute resins A-1 to A-69 and A'-1 to A'-2 as shown in Table 1.

[0461] [Chemistry 79]

[0462] [Chemistry 80]

[0463] [Chemistry 81]

[0464] [Chemistry 82]

[0465] [Chemistry 83]

[0466] <Synthesis Example 1: Synthesis of M-70>

[0467] [Chemistry 84]

[0468] 100 g of the compound represented by formula (M-70-a) and 96 g of the compound represented by formula (M-70-b) were dissolved in 1000 ml of tetrahydrofuran and stirred at -10°C. 28 ml of a tetrahydrofuran solution (concentration: 1M) of the compound represented by formula (M-70-c) was added dropwise to the obtained liquid. After stirring at -10°C for 1 hour, another 600 ml of a tetrahydrofuran solution (concentration: 1M) of the compound represented by formula (M-70-c) was added dropwise. After stirring the obtained solution at 25°C for 1 hour, it was cooled to 5°C, and 346 g of the compound represented by formula (M-70-d) was added dropwise. After stirring the obtained liquid at 50°C for 6 hours, 800 ml of saturated sodium bicarbonate solution was added, and the mixture was stirred for another 2 hours. The obtained liquid was concentrated, and 1000 ml of ethyl acetate and 600 ml of 1M hydrochloric acid solution were added to the concentrated mixture. After stirring at 25°C for 30 minutes, the mixture was separated, and the organic layer was extracted. 600 ml of deionized water was added to the obtained organic layer, and the mixture was stirred at 25°C for 30 minutes. The layers were then separated, and the organic layer was extracted. This washing operation was repeated 6 times. The obtained organic layer was concentrated to obtain 170 g of the compound represented by formula (M-70-e).

[0469] [Chemistry 85]

[0470] 170 g of the compound represented by formula (M-70-e) was mixed with 680 g of acetone and 93.5 g of 4M hydrochloric acid, and stirred at 50 °C for 24 hours. 2040 g of ethyl acetate was added to the obtained liquid, and the mixture was stirred at 25 °C for 30 minutes. The liquid was then separated, and the organic layer was extracted. 600 ml of deionized water was added to the obtained organic layer, and the mixture was stirred at 25 °C for 30 minutes. The liquid was then separated, and the organic layer was extracted. This washing operation was repeated three times. Na₂SO₄ was added to the obtained organic layer, and the mixture was stirred at 25 °C for 30 minutes. The mixture was then filtered, and the obtained liquid was concentrated. 700 g of hexane was added to the obtained liquid for crystallization. The solid was filtered off and dried to obtain 110 g of the compound represented by formula (M-70). The 1H-NMR determination results of the compound represented by formula (M-70) are shown below. 1H-NMR(CDCl 3): δ=7.36(m,2H), 6.85(m,2H), 6.28(s,1H), 6.12(q, 1H), 5.71(m, 1H), 5.00(s, 1H), 1.99(s, 3H)

[0471] <Synthesis Example 2: Synthesis of Resin A-1> Cyclohexanone (226 g) was heated to 80°C under a nitrogen atmosphere. While stirring the solution, a mixed solution of monomer (60 g) represented by formula M-70, monomer (40 g) represented by formula M-31, cyclohexanone (420 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (12.42 g) was added dropwise over 6 hours to obtain a reaction solution. After the addition was complete, the reaction solution was stirred at 80°C for another 2 hours. After cooling the resulting reaction solution, it was reprecipitated using a large amount of methanol / water (mass ratio 6:4), filtered, and the resulting solid was vacuum dried to obtain 83 g of resin A-1.

[0472] [Chemistry 86]

[0473] The obtained resin A-1 had a weight-average molecular weight (Mw: polystyrene conversion) of 6500, calculated from GPC (carrier: tetrahydrofuran (THF)), and a dispersion (Mw / Mn) of 1.60. The composition ratio, determined by 13C-NMR (nuclear magnetic resonance), was 40 / 50 / 50 in moles.

[0474] Other resins are synthesized in the same way.

[0475] [Photoacid generator] <Photoacid Generator (B)> The structures of the photoacid generators (B) (compounds B-1 to B-39) shown in Table 3 are shown below.

[0476] [Chemistry 87]

[0477] [Chemistry 88]

[0478] [Chemistry 89]

[0479] [Chemistry 90]

[0480] [Chemistry 91]

[0481] [Photodegradable quenchers] <Photodegradable Quencher (C)> The structures of the photodegradable quenchers (C) (compounds C-1 to C-17) shown in Table 3 are shown below.

[0482] [Chemistry 92]

[0483] [Chemistry 93]

[0484] [Photoacid generator-linked photodegradable quencher] <Photoacid generator linked to photodegradable quencher (D)> The specific compounds of the photoacid generator-linked photodegradable quencher (D) are listed in the photoacid generator (B) column.

[0485] [Acid diffusion control agent] The structures of the acid diffusion control agents (E) (compounds G-1 to G-5) shown in Table 3 are shown below.

[0486] [Chemistry 94]

[0487] [Resin F] The following shows the resins (F) shown in Table 3 (resin I-1 to resin I-7). Resins I-1 to I-7 were synthesized using the method described for resin A-1 (Synthesis Example 2). Table 2 shows the composition ratio (mass %; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit disclosed below. Furthermore, the weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of resins I-1 to I-7 were determined by GPC (solvent carrier: tetrahydrofuran (THF)) (converted to polystyrene). Additionally, the composition ratio (mass %) of the resins was determined by 13C nuclear magnetic resonance (NMR).

[0488] [Table 2] Table 2 mass ratio of repeating units Mw Mw / Mn Resin I-1 50 45 5 - - 6500 1.52 Resin I-2 50 50 - - - 25000 1.65 Resin I-3 30 65 5 - - 22000 1.55 Resin I-4 40 40 20 - - 12000 1.68 Resin I-5 40 50 5 5 - 5500 1.49 Resin I-6 90 8 2 - - 12000 1.63 Resin I-7 20 30 40 10 - 13000 1.55

[0489] The following shows the structural formulas of resins I-1 to I-7 as shown in Table 2.

[0490] [Chem. 95]

[0491] [Surfactants] The following table shows the surfactants listed in Table 3. H-1: Megafac F176 (manufactured by DIC, a fluorinated surfactant) H-2: Megafac R08 (manufactured by DIC (stock), fluorine and silicone surfactants) H-3: PF656 (manufactured by OMNOVA, a fluorinated surfactant)

[0492] [Solvent] The solvents shown in Table 3 are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-Heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene carbonate

[0493] [Preparation of the resist composition] The components shown in Table 3 were mixed to a solid content of 2.0% by mass. The resulting mixture was then passed through and filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, to prepare the resist composition (Re-1~Re-69, Re'-1~Re'-2). Furthermore, the term "solid components" refers to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples. In addition, the "Quantity" column in the table indicates the content (mass%) of each component relative to the total solid components in the resist composition.

[0494] [Table 3-1] Table 3 solid components solvent Resin A Photoacid generator B Photodegradable base C Acid diffusion control agent E Resin F surfactants type quantity type quantity type quantity type quantity type quantity type quantity type Mixing ratio (mass ratio) Re-1 A-1 65.0 B-28 25.0 C-10 10 - - - - - - F-1 / F-2 80 / 20 Re-2 A-2 60.0 B-1 40.0 - - - - - - - - F-1 / F-5 85 / 15 Re-3 A-3 56.0 B-2 44.0 - - - - - - - - F-1 / F-2 80 / 20 Re-4 A-4 55.0 B-3 45.0 - - - - - - - - F-1 / F-2 / F-8 40 / 20 / 40 Re-5 A-5 60.0 B-4 40.0 - - - - - - - - F-1 / F-2 80 / 20 Re-6 A-6 65.0 B-5 35.0 - - - - - - - - F-1 / F-9 85 / 15 Re-7 A-7 54.0 B-6 45.9 - - - - - - H-1 0.1 F-1 / F-7 90 / 10 Re-8 A-8 45.0 B-7 55.0 - - - - - - - - F-1 / F-2 80 / 20 Re-9 A-9 50.0 B-8 35.0 C-1 15.0 - - - - - - F-1 / F-2 80 / 20 Re-10 A-10 50.0 B-9 40.0 C-2 10.0 - - - - - - F-1 / F-2 / F-6 70 / 20 / 10 Re-11 A-11 55.0 B-10 30.0 C-3 15.0 - - - - - - F-1 / F-2 80 / 20 Re-12 A-12 60.0 B-11 30.0 C-4 10.0 - - - - - - F-1 / F-4 80 / 20 Re-13 A-13 90.0 B-12 6.0 C-5 2.0 - - I-1 2.0 - - F-1 / F-2 80 / 20 Re-14 A-14 70.0 B-13 20.0 C-6 7.0 - - I-2 2.9 H-2 0.1 F-4 100 Re-15 A-15 65.0 B-14 32.0 - - G-1 3.0 - - - - F-1 / F-2 85 / 15 Re-16 A-16 80.0 B-15 15.0 - - G-2 5.0 - - - - F-1 / F-5 80 / 20 Re-17 A-17 63.5 B-16 26.0 C-7 6.5 - - I-3 4.0 - - F-1 / F-2 75 / 25 Re-18 A-18 90.0 B-17 8.0 - - G-3 2.0 - - - - F-1 / F-2 / F-8 34 / 33 / 33 Re-19 A-19 65.5 B-18 20.0 C-8 12.5 - - I-4 2.0 - - F-1 / F-2 80 / 20 Re-20 A-20 88.5 B-19 6.5 - - G-4 5.0 - - - - F-1 / F-9 80 / 20 Re-21 A-21 74.0 B-20 22.0 - - G-5 4.0 - - - - F-1 / F-7 80 / 20 Re-22 A-22 80.0 B-21 7.0 C-9 4.0 - - I-5 8.9 H-3 0.1 F-1 / F-2 85 / 15 Re-23 A-23 80.0 B-22 12.0 C-10 5.0 - - I-6 3.0 - - F-1 / F-2 80 / 20 Re-24 A-24 85.0 B-23 8.0 C-11 2.0 - - I-7 5.0 - - F-1 / F-2 / F-6 80 / 15 / 5 Re-25 A-25 70.0 B-24 20.0 C-12 10.0 - - - - - - F-1 / F-2 90 / 10

[0495] [Table 3-2] Table 3 (Continued) solid components solvent Resin A Photonic acid generator B Photodegradable alkali C Acid diffusion control agent E Resin F surfactants Kind quantity Kind quantity Kind quantity Kind quantity Kind quantity Kind quantity type Mixing ratio (mass ratio) Re-26 A-26 65.0 B-25 25.0 C-13 10.0 - - - - - - F-1 / F-4 80 / 20 Re-27 A-27 55.0 B-26 30.0 C-14 15.0 - - - - - - F-1 / F-2 80 / 20 Re-28 A-28 45.0 B-27 35.0 C-15 19.9 - - - - H-3 0.1 F-4 100 Re-29 A-29 40.0 B-28 45.0 C-16 15.0 - - - - - - F-1 / F-3 85 / 15 Re-30 A-30 75.0 B-29 20.0 C-1 5.0 - - - - - - F-1 / F-5 80 / 20 Re-31 A-31 75.0 B-30 15.0 C-2 9.9 - - - - H-1 0.1 F-1 / F-2 75 / 25 Re-32 A-32 75.0 B-31 15.0 C-3 10.0 - - - - - - F-1 / F-2 / F-8 40 / 20 / 40 Re-33 A-33 70.0 B-32 15.0 C-4 15.0 - - - - - - F-1 / F-2 80 / 20 Re-34 A-34 70.0 B-33 20.0 C-5 10.0 - - - - - - F-1 / F-9 80 / 20 Re-35 A-35 60.0 B-34 30.0 C-6 10.0 - - - - - - F-1 / F-7 80 / 20 Re-36 A-36 65.0 B-35 35.0 - - - - - - - - F-1 / F-2 85 / 15 Re-37 A-37 70.0 B-36 30.0 - - - - - - - - F-1 / F-2 90 / 10 Re-38 A-38 55.0 B-37 45.0 - - - - - - - - F-1 / F-2 / F-6 80 / 10 / 10 Re-39 A-39 55.0 B-38 45.0 - - - - - - - - F-1 / F-2 90 / 10 Re-40 A-40 55.0 B-1 / B-12 30.0 / 15.0 - - - - - - - - F-1 / F-4 80 / 20 Re-41 A-41 60.0 B-39 30.0 C-17 10.0 - - - - - - F-1 / F-2 80 / 20 Re-42 A-42 65.0 B-3 35.0 - - - - - - - - F-4 100 Re-43 A-43 60.0 B-4 40.0 - - - - - - - - F-1 / F-2 80 / 20 Re-44 A-44 70.0 B-5 30.0 - - - - - - - - F-1 / F-5 80 / 20 Re-45 A-45 65.0 B-6 35.0 - - - - - - - - F-1 / F-2 85 / 15 Re-46 A-46 65.0 B-7 35.0 - - - - - - - - F-1 / F-2 / F-8 80 / 10 / 10 Re-47 A-47 60.0 B-8 40.0 - - - - - - - - F-1 / F-2 80 / 20 Re-48 A-48 55.0 B-9 45.0 - - - - - - - - F-1 / F-9 80 / 20 Re-49 A-49 45.0 B-10 55.0 - - - - - - - - F-1 / F-7 70 / 30 Re-50 A-50 50.0 B-11 50.0 - - - - - - - - F-1 / F-2 90 / 10

[0496] [Table 3-3] Table 3 (Continued) solid components solvent Resin A Photonic acid generator B Photodegradable alkali C Acid diffusion control agent E Resin F surfactants type quantity type quantity type quantity type quantity type quantity type quantity type Mixing ratio (mass ratio) Re-51 A-51 55.0 B-12 35.0 C-9 10.0 - - - - - - F-1 / F-2 80 / 20 Re-52 A-52 70.0 B-13 25.0 C-10 5.0 - - - - - - F-1 / F-2 / F-6 80 / 10 / 10 Re-53 A-53 80.0 B-14 10.0 C-11 10.0 - - - - - - F-1 / F-2 80 / 20 Re-54 A-54 55.0 B-15 35.0 C-12 10.0 - - - - - - F-1 / F-4 80 / 20 Re-55 A-55 60.0 B-16 30.0 C-13 10.0 - - - - - - F-1 / F-2 80 / 20 Re-56 A-56 75.0 B-17 20.0 C-14 5.0 - - - - - - F-4 100 Re-57 A-57 75.0 B-18 15.0 C-15 10.0 - - - - - - F-1 / F-2 80 / 20 Re-58 A-58 65.0 B-19 30.0 C-16 5.0 - - - - - - F-1 / F-5 80 / 20 Re-59 A-59 80.0 B-20 15.0 C-7 5.0 - - - - - - F-1 / F-2 80 / 20 Re-60 A-60 65.0 B-21 25.0 C-8 10.0 - - - - - - F-1 / F-2 / F-8 34 / 33 / 33 Re-61 A-61 45.0 B-22 45.0 C-1 10.0 - - - - - - F-1 / F-2 80 / 20 Re-62 A-62 65.0 B-23 30.0 C-2 5.0 - - - - - - F-1 / F-2 85 / 15 Re-63 A-63 25.0 B-24 70.0 C-3 5.0 - - - - - - F-1 / F-7 90 / 10 Re-64 A-64 55.0 B-25 40.0 C-4 5.0 - - - - - - F-1 / F-2 80 / 20 Re-65 A-65 65.0 B-26 30.0 C-5 5.0 - - - - - - F-1 / F-2 80 / 20 Re-66 A-66 55.0 B-27 30.0 C-6 15.0 F-1 / F-7 90 / 10 Re-67 A-67 70.0 B-28 20.0 C-7 10.0 F-1 / F-2 80 / 20 Re-68 A-68 55.0 B-29 30.0 C-8 15.0 F-1 / F-2 80 / 20 Re-69 A-69 55.0 B-29 30.0 C-8 15.0 F-1 / F-2 80 / 20 Re'-1 A'-1 65.0 B-28 25.0 C-10 10.0 - - - - - - F-1 / F-2 80 / 20 Re'-2 A'-2 65.0 B-28 25.0 C-10 10.0 - - - - - - F-1 / F-2 80 / 20

[0497] [Pattern Formation] [EUV exposure, organic solvent development] A substrate film with a thickness of 20 nm was formed by coating a base film with the underlying film formation composition AL412 (manufactured by Brewer Science) onto a 12-inch diameter silicon wafer and baking it at 205°C for 60 seconds. The resist composition shown in Table 3 was then coated onto the substrate and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36), a silicon wafer with the obtained resist film was patterned to achieve an average linewidth of 20 nm. Furthermore, a mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as a reticle. After baking the exposed resist film at 90°C for 60 seconds, it is developed with n-butyl acetate for 30 seconds and then rotated to dry to obtain a negative pattern.

[0498] 〔evaluate〕 <Defect Evaluation (Defect Suppression)> For the patterns obtained using the described method, the number of defects per silicon wafer was calculated using UVision5 (manufactured by AMAT) and SEMVisionG4 (manufactured by AMAT), and evaluated according to the following evaluation criteria. The fewer the number of defects, the better the defect suppression. "A": Number of defects is less than 50 "B": Number of defects exceeds 50 but is less than 100 "C": Number of defects exceeds 100 but is less than 200 "D": Number of defects exceeds 200 but is less than 300 "E": Number of defects exceeds 300 but is less than 400 "F": Number of defects exceeds 400 but is less than 500 "G": Number of defects exceeds 500 but is less than 600

[0499] <Roughness performance (LWR performance, nm)> The pattern obtained using the described method was observed from the top using a length-measuring scanning electron microscope (SEM) (S-9380II, Hitachi, Ltd.). The linewidth of the pattern was observed at 250 nm, and its measurement deviation was evaluated using 3σ, which was set as the line width roughness (LWR) (nm). The smaller the LWR value, the better the roughness performance. In addition, the best LWR performance (nm) is in the order of below 4.1 nm, below 3.8 nm, below 3.5 nm, and below 3.2 nm.

[0500] The evaluation results are shown in Table 4 below.

[0501] [Table 4-1] Table 4 Anti-corrosion composition Evaluation Item 1 Defect suppression Evaluation Item 2 Roughness performance (nm) Example 1-1 Re-1 A 3.2 Examples 1-2 Re-2 A 3.1 Examples 1-3 Re-3 A 3.1 Examples 1-4 Re-4 A 3.0 Examples 1-5 Re-5 A 2.9 Examples 1-6 Re-6 A 3.0 Examples 1-7 Re-7 A 2.8 Examples 1-8 Re-8 A 2.8 Examples 1-9 Re-9 A 2.9 Examples 1-10 Re-10 A 3.0 Examples 1-11 Re-11 A 3.1 Examples 1-12 Re-12 A 2.9 Examples 1-13 Re-13 A 2.8 Examples 1-14 Re-14 A 2.8 Examples 1-15 Re-15 A 2.8 Examples 1-16 Re-16 C 3.6 Examples 1-17 Re-17 B 3.4 Examples 1-18 Re-18 B 3.3 Examples 1-19 Re-19 B 3.4 Examples 1-20 Re-20 B 3.3 Examples 1-21 Re-21 B 3.3 Examples 1-22 Re-22 B 3.3 Examples 1-23 Re-23 B 3.4 Examples 1-24 Re-24 B 3.4 Examples 1-25 Re-25 A 2.9 Examples 1-26 Re-26 A 3.2 Examples 1-27 Re-27 A 3.2 Examples 1-28 Re-28 B 3.5 Examples 1-29 Re-29 B 3.4 Examples 1-30 Re-30 B 3.5 Examples 1-31 Re-31 B 3.3 Examples 1-32 Re-32 C 3.6 Examples 1-33 Re-33 B 3.3 Examples 1-34 Re-34 B 3.5 Examples 1-35 Re-35 B 3.3

[0502] [Table 4-2] Table 4 (continued) Anti-corrosion composition Evaluation Item 1 Defect suppression Evaluation Item 2 Roughness performance (nm) Examples 1-36 Re-36 A 3.2 Examples 1-37 Re-37 A 3.2 Examples 1-38 Re-38 A 3.2 Examples 1-39 Re-39 A 3.2 Examples 1-40 Re-40 A 3.0 Examples 1-41 Re-41 B 3.5 Examples 1-42 Re-42 A 3.0 Examples 1-43 Re-43 A 2.9 Examples 1-44 Re-44 A 3.0 Examples 1-45 Re-45 A 3.0 Examples 1-46 Re-46 A 2.9 Examples 1-47 Re-47 A 2.8 Examples 1-48 Re-48 B 3.3 Examples 1-49 Re-49 A 2.8 Examples 1-50 Re-50 A 3.0 Examples 1-51 Re-51 A 2.9 Examples 1-52 Re-52 A 2.8 Examples 1-53 Re-53 A 2.9 Examples 1-54 Re-54 A 3.0 Examples 1-55 Re-55 A 3.0 Examples 1-56 Re-56 A 3.0 Examples 1-57 Re-57 A 2.9 Examples 1-58 Re-58 A 2.9 Examples 1-59 Re-59 A 3.0 Examples 1-60 Re-60 A 2.9 Examples 1-61 Re-61 A 3.0 Examples 1-62 Re-62 A 3.0 Examples 1-63 Re-63 A 3.0 Examples 1-64 Re-64 B 3.3 Examples 1-65 Re-65 A 3.2 Examples 1-66 Re-66 A 3.0 Examples 1-67 Re-67 A 3.1 Examples 1-68 Re-68 A 3.2 Examples 1-69 Re-69 A 3.2 Comparative Example 1-1 Re'-1 G 4.9 Comparative Examples 1-2 Re'-2 G 5.1

[0503] As shown in Table 4, the resist composition of the present invention demonstrates excellent roughness performance and suppresses the formation of pattern defects when forming extremely fine patterns using organic solvents. On the other hand, these properties are not sufficient in the resist compositions of the comparative examples.

[0504] For Example 1-1, except that the resin A-1 used in the resist composition Re-1 was changed to an equivalent mass of resin A-1 and resin A-2 (specifically, the mass ratio of resin A-1 to resin A-2 was 1:1, and the total "amount" was 65 parts), the same procedure was followed to prepare the resist composition Re-70. The same evaluation as in Example 1-1 was performed, and the same results as in Example 1-1 were obtained.

[0505] For Example 1-1, except that the resin A-1 used in the resist composition Re-1 was changed to a mixture of resin A-1 and resin A'-1 (by mass ratio, (resin A-1):(resin A'-1) = 9:1, total "amount" of 65 parts), the same procedure was followed to prepare resist composition Re-71. The same evaluation as in Example 1-1 was performed, and the same results as in Example 1-1 were obtained.

[0506] [EUV exposure, alkaline aqueous solution development] A substrate film with a thickness of 20 nm was formed by coating a base film with the underlying film formation composition AL412 (manufactured by Brewer Science) onto a 12-inch diameter silicon wafer and baking it at 205°C for 60 seconds. The resist composition shown in Table 4 was then coated onto the substrate and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36), a silicon wafer with the obtained resist film was patterned to achieve an average linewidth of 20 nm. Furthermore, a mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as a reticle. After baking the exposed resist film at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. Then, it was rotated and dried to obtain a positive pattern. Using the obtained positive pattern, the occurrence of defects and roughness performance of the pattern were evaluated in the same manner as described above.

[0507] The evaluation results are shown in Table 5 below.

[0508] [Table 5-1] Table 5 Anti-corrosion composition Evaluation Item 1 Defect suppression Evaluation Item 2 Roughness performance (nm) Example 2-1 Re-1 A 3.2 Example 2-2 Re-2 A 3.1 Example 2-3 Re-3 A 3.0 Examples 2-4 Re-4 A 3.0 Examples 2-5 Re-5 A 3.0 Examples 2-6 Re-6 A 2.9 Examples 2-7 Re-7 A 2.8 Examples 2-8 Re-8 A 2.9 Examples 2-9 Re-9 A 3.0 Example 2-10 Re-10 A 3.0 Example 2-11 Re-11 A 3.1 Example 2-12 Re-12 A 2.9 Example 2-13 Re-13 A 2.8 Example 2-14 Re-14 A 2.8 Example 2-15 Re-15 A 2.8 Example 2-16 Re-16 C 3.6 Example 2-17 Re-17 B 3.4 Example 2-18 Re-18 B 3.3 Example 2-19 Re-19 B 3.4 Example 2-20 Re-20 B 3.3 Example 2-21 Re-21 B 3.4 Example 2-22 Re-22 B 3.3 Example 2-23 Re-23 B 3.4 Example 2-24 Re-24 B 3.4 Example 2-25 Re-25 A 2.9 Example 2-26 Re-26 A 3.2 Example 2-27 Re-27 A 3.2 Example 2-28 Re-28 B 3.5 Example 2-29 Re-29 B 3.4 Examples 2-30 Re-30 B 3.5 Example 2-31 Re-31 B 3.3 Example 2-32 Re-32 C 3.6 Example 2-33 Re-33 B 3.3 Examples 2-34 Re-34 B 3.5 Example 2-35 Re-35 B 3.3

[0509] [Table 5-2] Table 5 (continued) Anti-corrosion composition Evaluation Item 1 Defect suppression Evaluation Item 2 Roughness performance (nm) Examples 2-36 Re-36 A 3.2 Example 2-37 Re-37 A 3.2 Example 2-38 Re-38 A 3.2 Example 2-39 Re-39 A 3.2 Example 2-40 Re-40 A 3.0 Example 2-41 Re-41 B 3.5 Example 2-42 Re-42 A 3.0 Examples 2-43 Re-43 A 2.9 Example 2-44 Re-44 A 3.0 Example 2-45 Re-45 A 3.0 Example 2-46 Re-46 A 2.8 Example 2-47 Re-47 A 3.0 Example 2-48 Re-48 B 3.3 Example 2-49 Re-49 A 2.8 Example 2-50 Re-50 A 3.0 Example 2-51 Re-51 A 2.9 Example 2-52 Re-52 A 2.8 Examples 2-53 Re-53 A 2.9 Example 2-54 Re-54 A 2.9 Example 2-55 Re-55 A 3.0 Examples 2-56 Re-56 A 3.0 Example 2-57 Re-57 A 2.9 Example 2-58 Re-58 A 2.9 Example 2-59 Re-59 A 3.0 Example 2-60 Re-60 A 3.0 Example 2-61 Re-61 A 3.0 Example 2-62 Re-62 A 3.0 Example 2-63 Re-63 A 3.0 Example 2-64 Re-64 B 3.3 Example 2-65 Re-65 A 3.2 Example 2-66 Re-66 A 3.0 Example 2-67 Re-67 A 3.0 Example 2-68 Re-68 A 3.2 Example 2-69 Re-69 A 3.2 Comparative Example 2-1 Re'-1 G 5.0 Comparative Example 2-2 Re'-2 G 4.9

[0510] As shown in Table 5, the resist composition of the present invention demonstrates excellent roughness performance even when patterns are formed using alkaline development, and can suppress the occurrence of pattern defects. On the other hand, these properties are not sufficient in the resist compositions of the comparative examples.

[0511] The resist composition Re-1 was changed to the resist composition Re-70, and the same evaluation as in Example 2-1 was performed, yielding the same results as in Example 2-1. The resist composition Re-1 was changed to the resist composition Re-71, and the same evaluation as in Example 2-1 was performed, yielding the same results as in Example 2-1.

[0512] none

Claims

1. A photosensitive or radiosensitive linear resin composition comprising: (A) a resin having repeating units derived from a compound represented by formula (3) below; and (B) a compound that produces an acid upon irradiation by photosensitive rays or radiation, wherein in formula (3), X represents a hydrogen atom, methyl, ethyl, alkenyl, cycloalkyl, aryl, or alkoxy; L2 represents a single bond or a linking group consisting of -COO-, -CO-, -O-, alkyl, cycloalkyl, aryl, and a plurality of such linked groups; R1 represents a halogen atom or an organic group having a halogen atom; R2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group; R3 represents a halogen atom, an amino group, a thiol group, or an organic group; R4 represents a hydrogen atom or an organic group; n represents an integer greater than or equal to 1; m represents an integer greater than or equal to 0; p represents an integer greater than or equal to 0; wherein, n, m, and p satisfy the relationship n+m≦5+2p. When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

2. The photosensitive radioactive or radiosensitive linear resin composition as claimed in claim 1, wherein the compound (B) is an onium salt.

3. The photosensitive radioactive or radiosensitive linear resin composition as claimed in claim 1 or claim 2, wherein the resin (A) further has repeating units represented by the following formula (4), in which X11 represents a hydrogen atom, a halogen atom, a hydroxyl group, or an organic group, and R11 represents an alkyl group independently, and the two R11s can be bonded to form a ring.

4. A photosensitive radioactive or radioactive linear film formed from a photosensitive radioactive or radioactive linear resin composition as described in any one of claims 1 to 3.

5. A method for forming a pattern, comprising: The steps of forming a photosensitive radioactive or radioactive linear film on a substrate using any one of claims 1 to 3; exposing the photosensitive radioactive or radioactive linear film; and developing the exposed photosensitive radioactive or radioactive linear film with a developer to form a pattern.

6. A method for manufacturing an electronic component, comprising the pattern forming method as described in claim 5.

7. A compound represented by the following formula (3), in which X represents a hydrogen atom, methyl, ethyl, alkenyl, cycloalkyl, aryl, or alkoxy; L2 represents a single bond or a linking group consisting of -COO-, -CO-, -O-, alkyl, cycloalkyl, aryl, and a plurality of such linked groups; R1 represents a halogen atom or an organic group having a halogen atom; R2 represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or an organic group; R3 represents a halogen atom, an amino group, a thiol group, or an organic group; R4 represents a hydrogen atom or an organic group; n represents an integer greater than or equal to 1; m represents an integer greater than or equal to 0; p represents an integer greater than or equal to 0; wherein, n, m, and p satisfy the relationship n+m≦5+2p. When m represents an integer greater than 2, multiple R3s can be the same or different. When n represents an integer greater than 2, multiple R4s can be the same or different.

8. A resin having repeating units derived from the compound as claimed in claim 7.

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