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

Abstract

The present invention provides a photosensitive radioactive or radioactive linear resin composition comprising a resin (A) having a repeating unit (a) represented by a specific general formula (a), a photosensitive radioactive or radioactive linear film formed by the above-mentioned photosensitive radioactive or radioactive linear resin composition, a pattern forming method using the above-mentioned photosensitive radioactive or radioactive linear resin composition, and a method for manufacturing an electronic device.

Description

Technical Field

[0001] This invention relates to photosensitive radioactive or radioactive linear resin compositions, photosensitive radioactive or radioactive linear films, patterning methods, and manufacturing methods of electronic devices. Prior Technology

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

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is also under development. Along with this, chemically amplified photoresist compositions and resins for use with excellent sensitivity and resolution that effectively sense various types of radiation have been developed.

[0004] For example, Patent Document 1 describes a resin comprising repeating units having acid-degradable groups and repeating units derived from p-hydroxystyrene. [Previous Technical Documents] [Patent Literature]

[0005] Patent Document 1: International Publication No. 2020 / 235608 Summary of the Invention

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

[0007] In recent years, the miniaturization of patterns has continued to advance, thus requiring further improvements in the various properties of photosensitive or radiosensitive linear resin compositions used to form such patterns. Even with the prior art described in Patent Document 1, the resolution is still insufficient and needs to be improved.

[0008] Therefore, the object of the present invention is to provide a photosensitive radioactive or radioactive linear resin composition that not only has excellent resolution and excellent roughness performance in the formation of extremely fine (especially linewidth or spacing of 20 nm or less) patterns, and can obtain excellent pattern shapes; a photosensitive radioactive or radioactive linear film formed by the above-mentioned photosensitive radioactive or radioactive linear resin composition; a pattern forming method using the above-mentioned photosensitive radioactive or radioactive linear resin composition; and a method for manufacturing electronic devices. [Methods for solving problems]

[0009] The inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[0010] [1] A photosensitive radioactive or radiosensitive linear resin composition comprising a resin (A) wherein the resin (A) comprises a repeating unit (a) represented by the following general formula (a).

[0011] [Chemical Formula 1]

[0012] In general formula (a), A represents an aromatic cyclic group or an aromatic heterocyclic group. X represents a single bond, an alkyl group, an alkenyl group, an alkyne group, a carbonyl group, a sulfonyl group, or a group composed of these. X can bond with the A ring to form a benzene ring. Y1 and Y2 independently represent an oxygen atom or a sulfur atom, respectively. R11 and R12 independently represent a hydrogen atom, an organic group, or a halogen atom, respectively.

[0013] [2] The photosensitive or radiosensitive linear resin composition as described in [1], wherein the resin (A) further comprises repeating units having acid groups.

[0014] [3] As described in [2], the photosensitive or radiosensitive linear resin composition, wherein the repeating unit having an acid group is a repeating unit having a phenolic hydroxyl group.

[0015] [4] The photosensitive radioactive or radiosensitive linear resin composition as described in [2], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (B).

[0016] [Chemical Formula 2]

[0017] In general formula (B), R3 represents a hydrogen atom or a monovalent organic group. R4 and R5 independently represent a hydrogen atom, a halogen atom, or an alkyl group, respectively. L2 represents a single bond or an ester bond. L3 represents an aromatic hydrocarbon cyclic group with a (n+m+1) valence or an alicyclic hydrocarbon cyclic group with a (n+m+1) valence. R6 represents a hydroxyl group or a fluorinated alcohol group. R7 represents a halogen atom. m represents an integer greater than or equal to 1. n represents an integer greater than or equal to 0 or 1.

[0018] [5] The photosensitive radioactive or radiosensitive linear resin composition as described in [2] or [3], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (c).

[0019] [Chemical Formula 3]

[0020] In general formula (c), R 61 to R 63 independently represent hydrogen atoms, organogroups, or halogen atoms. R 62 can bond with Ar to form a ring, in which case R 62 represents a single bond or an alkyl group. L represents a single bond or a divalent linker. Ar represents an aromatic cyclic group with a (k+1) valence; when bonded with R 62 to form a ring, it represents an aromatic cyclic group with a (k+2) valence. k represents an integer from 1 to 5.

[0021] [6] The photosensitive radioactive or radiosensitive linear resin composition as described in any of [1] to [5], wherein in general formula (a), Y1 and Y2 both represent oxygen atoms. [7] The photosensitive radioactive or radiolinear resin composition as described in any one of [1] to [6], wherein in general formula (a), X represents a single bond, methylene, ethyl or carbonyl. [8] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [7], wherein in general formula (a), X represents methylene, ethyl or carbonyl.

[0022] [9] The photosensitive radioactive or radiosensitive linear resin composition as described in any of [1] to [8], wherein in general formula (a), X represents a carbonyl group.

[10] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [9], wherein in general formula (a), A represents an aromatic cyclic group.

[0023]

[11] The photosensitive radioactive or radiosensitive linear resin composition as described in any one of [1] to

[10] , wherein the repeating unit represented by the above general formula (a) is the repeating unit represented by the following general formula (a-1).

[0024] [Chemical Formula 4]

[0025] In general formula (a-1), R11 and R12 independently represent hydrogen atoms, organogroups, or halogen atoms, respectively. R21 independently represent hydrogen atoms, organogroups, or halogen atoms, respectively. R21 atoms can bond with each other to form a ring.

[0026]

[12] A photosensitive radioactive or radioactive linear film formed using a photosensitive radioactive or radioactive linear resin composition as described in any one of [1] to

[11] .

[13] A method for forming a pattern, comprising: A process for forming a photosensitive radioactive or radioactive linear film on a substrate using any one of the photosensitive radioactive or radioactive linear resin compositions described in [1] to

[11] ; The exposure process for exposing the above-mentioned photosensitive radioactive or radiosensitive linear film; and The developing process involves developing the exposed photosensitive radioactive or radiosensitive linear film using a developing solution.

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

[13] . [Invention Effects]

[0027] The present invention provides a photosensitive radioactive or radioactive linear resin composition that not only has excellent resolution and roughness performance in the formation of extremely fine patterns (especially with linewidth or spacing of 20 nm or less), but also produces excellent pattern shapes; a photosensitive radioactive or radioactive linear film formed by the above-mentioned photosensitive radioactive or radioactive linear resin composition; a pattern forming method using the above-mentioned photosensitive radioactive or radioactive linear resin composition; and a method for manufacturing electronic devices. Simple Explanation of the Diagram

[0028] none Implementation

[0029] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the use of groups (atomic clusters) in this specification, as long as it does not depart from the spirit of this invention, any expression that does not specify substitution or non-substitution includes both groups without substituents and groups containing substituents. For example, the term "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, in this specification, the term "organic group" refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred.

[0030] In this specification, there are no particular limitations on the type, position, or number of substituents when the phrase "may have substituents" is used. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, and for example, substituents T can be selected from the following substituents.

[0031] (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 methylpropenyl. Acrylyl, methylthioalkyl, and other alkylthioalkyl; methylthioalkyl and tributylthioalkyl, and other alkylthioalkyl; phenylthioalkyl and p-tolylthioalkyl, and other arylthioalkyl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; methyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonylamino; silyl; amino; monoalkylamino; dialkylamino; arylamino; nitro; and combinations thereof.

[0032] In this manual, the terms "photochemical rays" or "radiation" refer to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV), X-rays, and electron beams (EB). In this manual, the term "light" refers to photochemical rays or radiation. In this specification, the term "exposure" unless otherwise specified includes not only exposure using the bright-line spectrum of mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light, and X-rays, but also depiction using particle beams such as electron beams and ion beams. In this manual, the term "~" is used to indicate that the values ​​recorded before and after it are included as lower and upper limits.

[0033] Unless otherwise specified, the bonding orientation of the divalent linker described in this specification is not particularly limited. For example, in compounds represented by the formula "XYZ", when Y is -COO-, Y can be either -CO-O- or -O-CO-. The above compounds can be either "X-CO-OZ" or "XO-CO-Z".

[0034] In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene conversion values ​​obtained by GPC (Gel Permeation Chromatography) apparatus (Tosoh HLC-8120GPC) by GPC determination (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)).

[0035] In this specification, the so-called acid dissociation constant (pKa) refers to the pKa in aqueous solution. Specifically, it is a value obtained by calculation using the following software package 1, based on a database of Hammett substituent constants and known literature values. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0036] pKa can also be obtained using molecular orbital calculations. One specific method is to calculate it using the H+ dissociation free energy in aqueous solution based on thermodynamic cycles. Methods for calculating the H+ dissociation free energy include, for example, DFT (Density Functional Theory), but are not limited to this; various other methods have been reported in the literature. Furthermore, several software programs are available for implementing DFT, such as Gaussian16.

[0037] As described above, in this specification, pKa refers to the value obtained by using software package 1 to calculate the value based on a database of Hammett substituent constants and known literature values. However, if pKa cannot be calculated using this method, it is assumed that the value is obtained by using Gaussian 16 based on DFT (density functional theory). As shown above, in this specification, pKa refers to "pKa in aqueous solution", but when the pKa in aqueous solution cannot be calculated, it is assumed to be "pKa in dimethyl sulfoxide (DMSO) solution". The term "solid component" refers to the component that forms the photosensitive X-ray film and does not contain solvents. Furthermore, as long as it is a component that forms the photosensitive X-ray film, it is considered a solid component even if it is in liquid form.

[0038] [Photosensitive or radiosensitive linear resin composition] The photosensitive radioactive or radiosensitive linear resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains a resin (A) comprising repeating units represented by the following general formula (a).

[0039] [Chemical Formula 5]

[0040] In general formula (a), A represents an aromatic cyclic group or an aromatic heterocyclic group. X represents a single bond, an alkyl group, an alkenyl group, an alkyne group, a carbonyl group, a sulfonyl group, or a group composed of these. X can bond with the A ring to form a benzene ring. Y1 and Y2 independently represent an oxygen atom or a sulfur atom, respectively. R11 and R12 independently represent a hydrogen atom, an organic group, or a halogen atom, respectively.

[0041] With this structure, not only is the resolution excellent, but the roughness performance is also excellent, and excellent pattern shape can be obtained in the formation of extremely fine patterns (especially those with linewidth or spacing of less than 20 nm). Although the mechanism by which the present invention can achieve the above-mentioned effects may not be clear, the inventors have made the following reasoning.

[0042] The repeating unit (a) contained in the resin (A) used in the composition of the present invention has a methylene structure bonded to two atoms selected from oxygen and sulfur atoms. In other words, it contains an acid-degradable group with a cyclic protective structure, which protects two polar groups selected from groups such as thiol, hydroxyl, and carboxyl groups by means of a methylene structure. More specifically, the raw material monomer of the repeating unit (a) represented by the following general formula (am) contains an acid-degradable group with a cyclic structure, which protects two polar groups selected from groups such as thiol, hydroxyl, and carboxyl groups by a methylene-containing methylene structure represented by -C (=CR 11R 12)-, and the raw material monomer forms the repeating unit (a) by a polymerization reaction.

[0043] [Chemical Formula 6]

[0044] As shown in the following diagram, it is speculated that the repeating unit (a) with the above structure reacts with acid, causing the methylene structure to decompose and lose its protection, generating polar groups and simultaneously causing the main chain to break. Therefore, in resin (A), polar groups are generated by the acid produced due to exposure, and the molecular weight decreases due to the decomposition of the main chain. Therefore, it can be considered that the difference in solubility of the resin in the developer between the exposed and unexposed parts before and after exposure is greater than before, thereby improving the resolution. The details of the following diagram will be described later.

[0045] [Chemical Formula 7]

[0046] Furthermore, it can be argued that since the carbon atoms in the aforementioned methylene structure are quaternary carbon atoms, their inclusion in the main chain suppresses the mobility of the main chain, thereby increasing the glass transition temperature (Tg) of the resin. This suppresses the diffusion of acid in the photosensitive or radiosensitive linear film, further improving the resolution, roughness performance, and pattern shape.

[0047] The composition of this invention is typically a photoresist composition, which can be either a positive or negative photoresist composition, preferably a positive photoresist composition. Furthermore, it can be either a photoresist composition for alkaline development or a photoresist composition for organic solvent development, preferably a photoresist composition for alkaline development. The composition of this invention is typically a chemically amplified photoresist composition.

[0048] The components of the present invention will now be described in detail.

[0049] <Resin(A)> (Repeating unit (a)) The composition of the present invention contains a resin comprising repeating units (a) represented by the following general formula (a). The repeating unit (a) is a repeating unit containing a group whose polarity increases due to decomposition by the action of acid (hereinafter also referred to as "acid-decomposing group"). An acid-decomposable group is a group that decomposes to produce a polar group by the action of an acid. Preferably, an acid-decomposable group has a structure that protects the polar group by a group that can be released by the action of an acid (a release group). In repeating unit (a), there is a structure that protects two polar groups such as hydroxyl, carboxyl, and thiol groups by a methylene structure (carbon atoms bonded to Y1 and Y2). The polarity of resin (A) increases due to the action of acid, its solubility relative to alkaline developer increases, and its solubility relative to organic solvent decreases.

[0050] [Chemical Formula 8]

[0051] In general formula (a), A represents an aromatic cyclic group or an aromatic heterocyclic group. X represents a single bond, an alkyl group, an alkenyl group, an alkyne group, a carbonyl group, a sulfonyl group, or a group composed of these. X can bond with the A ring to form a benzene ring. Y1 and Y2 independently represent an oxygen atom or a sulfur atom, respectively. R11 and R12 independently represent a hydrogen atom, an organic group, or a halogen atom, respectively.

[0052] In general formula (a), A represents an aromatic cyclic group or an aromatic heterocyclic group. Examples of aromatic cyclic groups represented by A include benzene rings, naphthalene rings, anthracene rings, and other aromatic cyclic groups with 6 to 18 carbon atoms. Examples of aromatic heterocyclic groups represented by A include thiophene rings, furan rings, thiazole rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, and thiadiazole rings.

[0053] A may have substituents. Preferred substituents include, for example, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, and halogen atoms. Examples of alkyl groups include methyl, ethyl, and isopropyl alkyl groups with 1 to 12 carbon atoms. Examples of alkenyl groups include vinyl and allyl groups, which have 2 to 12 carbon atoms. Examples of alkynyl groups include acetylenol and other alkynyl groups with 2 to 12 carbon atoms. As a cycloalkyl group, it can be monocyclic or polycyclic; for example, cyclopropyl, cyclopentyl and cyclohexyl groups with 3 to 12 carbon atoms are examples. Examples of aryl groups include phenyl and other aryl groups with 6 to 12 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, and isopropoxy, which have 1 to 12 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. When A has a plurality of substituents, these substituents can bond together to form a ring.

[0054] When A has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorine atom, or an iodine atom.

[0055] A preferably represents an aromatic ring group, and more preferably a benzene ring group.

[0056] In general formula (a), X represents a single bond, an alkyl group, an alkenyl group, an alkyne group, a carbonyl group, a sulfonylutriyl group, or a combination thereof.

[0057] The alkyl group represented by X is preferably an alkyl group with 1 to 4 carbons, such as methylene, ethyl alkyl, propyl alkyl, or butyl alkyl, and more preferably methylene or ethyl alkyl. The x-represented alkenyl group is preferably an alkenyl group with 2 to 4 carbon atoms, such as an alkenylene group. The x-represented ynyl group is preferably an ynyl group with 2 to 4 carbon atoms, such as an ynylethynyl group.

[0058] X can bond with ring A to form a benzene ring. Specifically, the repeating unit represented by general formula (a) refers to the repeating unit represented by the following general formula (aa).

[0059] [Chemical Formula 9]

[0060] The A, Y1, Y2, R11 and R12 in the general formula (aa) have the same meaning as the A, Y1, Y2, R11 and R12 in the general formula (a).

[0061] X may have substituents. For example, the substituents that A may have can be listed above.

[0062] X preferably represents a single bond, an alkyl group, or a carbonyl group; more preferably, it represents a single bond, a methylene group, an ethyl group, or a carbonyl group; even more preferably, it represents a methylene group, an ethyl group, or a carbonyl group; and most preferably, it represents a carbonyl group.

[0063] In general formula (a), Y1 and Y2 independently represent oxygen atoms or sulfur atoms, respectively. Preferably, at least one of Y1 and Y2 is an oxygen atom, and more preferably, both are oxygen atoms.

[0064] In general formula (a), R11 and R12 independently represent hydrogen atoms, organic groups or halogen atoms, respectively.

[0065] Examples of organic groups represented by R11 and R12 include alkyl, cycloalkyl, cyano, or alkoxycarbonyl groups.

[0066] The alkyl groups represented by R11 and R12 are preferably alkyl groups with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably alkyl groups with 8 or fewer carbon atoms, and even more preferably alkyl groups with 3 or fewer carbon atoms.

[0067] The cycloalkyl groups represented by R11 and R12 can be either monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl, are preferred. The alkyl group contained in the alkoxycarbonyl group represented by R11 and R12 is preferably the same as the alkyl group in R11 and R12 mentioned above.

[0068] Examples of halogen atoms represented by R 11 and R 12 include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the preferred choice.

[0069] Preferred substituents in R11 and R12 include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acetyl, acetoxy, alkoxycarbonyl, cyano, and nitro. The substituent preferably has 8 or fewer carbon atoms.

[0070] R11 and R12 are preferably hydrogen atoms or alkyl groups having 3 or fewer carbon atoms, and more preferably hydrogen atoms.

[0071] As described above, it is deduced that the repeating unit (a) with the above structure, as shown in the following figure, reacts with acid, thereby decomposing the methylene structure and removing its protection to generate a polar group, while simultaneously causing the main chain to break.

[0072] [Chemical Formula 10]

[0073] In the above diagram, Pn and Pm represent polymer chains. R11, R12, Y1, Y2, X and A are the same as R11, R12, Y1, Y2, X and A in the above general formula (a). When an acid is applied to the above structure, the electron-rich Y atom bonds with the protons (H+) of the acid, the Y-carbon bond breaks, the methylene structure decomposes, and the carbon atom becomes cationized. Water molecules attack the cation on the carbon atom, deprotonating it and forming an alcohol compound. If a proton is applied to this structure, the adjacent Y atom bonds with the proton to the adjacent methylene structure, becoming a cation. Due to the instability of this structure, it returns to a neutral state, thus the alcohol hydrogen deprotonates, changing into a carbonyl bond. At the same time, the main chain breaks, followed by the breakage of the methylene structure, resulting in four covalent bonds on each carbon atom. As a result, it is deduced that, through the catalytic action of the acid, the polymer main chain breaks down into alkene and carbonyl compounds.

[0074] The repeating unit represented by general formula (a) is preferably the repeating unit represented by the following general formula (a-1).

[0075] [Chemical Formula 11]

[0076] In general formula (a-1), R11 and R12 independently represent hydrogen atoms, organogroups, or halogen atoms, respectively. R21 independently represent hydrogen atoms, organogroups, or halogen atoms, respectively. R21 atoms can bond with each other to form a ring.

[0077] R11 and R12 in general formula (a-1) have the same meaning as R11 and R12 in general formula (a) above, and the preferred example is also the same.

[0078] In general formula (a-1), R 21 independently represents a hydrogen atom, an organic group, or a halogen atom. As an organic group in R 21, examples include alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and alkoxy groups. Specifically, examples of alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and alkoxy groups as substituents when A has a substituent can be given. Examples of halogen atoms that are substituents in R 21 can be given when A has substituents. Examples of ring structures formed by multiple R 21 bonds to each other include cyclopentyl or cyclohexyl.

[0079] R 21 is preferably independently represented by a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom, or an iodine atom.

[0080] Specific examples of repeating units represented by general formula (a) are shown below, but the present invention is not limited thereto. Furthermore, in the following specific examples, the structure of the raw material monomer (the monomer represented by the above general formula (am)) as the repeating unit represented by general formula (a) is shown.

[0081] [Chemical Formula 12]

[0082] The content of repeating unit (a) relative to all repeating units in resin (A) is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0083] (Repeating unit with acid-decomposing groups) In addition to the repeating unit (a) mentioned above, the resin (A) may also have repeating units containing acid-decomposable groups. As a repeating unit having an acid-decomposable group, in addition to the repeating units having an acid-decomposable group described later, it is preferred to have a repeating unit having an acid-decomposable group containing an unsaturated bond.

[0084] The acid-decomposable group is preferably a structure that has a group (dissociative group) that can be released by the action of acid to protect the polar group. As a polar group, it is preferably a base-soluble group, such as carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonimino, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imino, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups, as well as alcoholic hydroxyl. 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 by the action of an acid, for example, groups represented by formulas (Y1) to (Y4) can be cited. Equation (Y1): -C(Rx 1)(Rx 2)(Rx 3) Formula (Y2):-C(=O)OC(Rx 1)(Rx 2)(Rx 3) Equation (Y3): -C(R 36)(R 37)(OR 38) Equation (Y4): -C(Rn)(H)(Ar)

[0086] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent a hydrocarbon group, preferably an alkyl (straight-chain or branched), a cycloalkyl (monocyclic or polycyclic), an alkenyl (straight-chain or branched), or an aryl (monocyclic or polycyclic). Furthermore, when all Rx1 to Rx3 are alkyl (straight-chain or branched), at least two of Rx1 to Rx3 are preferably methyl. Wherein, Rx 1 to Rx 3 are each independently, preferably representing a straight-chain or branched alkyl group, and Rx 1 to Rx 3 are each independently, more preferably representing a straight-chain alkyl group. Two of Rx 1 to Rx 3 can be bonded together to form a single ring or multiple rings. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 5 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred. In the aforementioned cycloalkyl groups, for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a sulfur atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethyl groups constituting the cycloalkane ring may be substituted with vinylidenes. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The ring formed by the two bonds in Rx 1 to Rx 3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms. A cycloalkyl group formed by two bonds in Rx1 to Rx3, wherein one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylene. In these cycloalkyl groups, one or more ethyl groups constituting the cycloalkane ring can be replaced by vinylenes. The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl state. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the ring formed by the alkyl, cycloalkyl, alkenyl, aryl groups represented by Rx1 to Rx3 and two bonds of Rx1 to Rx3 is preferably further provided with fluorine or iodine atoms as substituents.

[0087] In formula (Y3), R36 to R38 each independently represent a hydrogen atom or a monovalent organogroup. R37 and R38 can bond together to form a ring. Examples of monovalent organogroups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R36 is also preferably a hydrogen atom. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may contain heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more methylene groups may be substituted by heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. R 38 can bond with another substituent in the main chain of the repeating unit to form a ring. The group formed by R 38 bonding with another substituent in the main chain of the repeating unit is preferably a methylene isoalkyl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the monovalent organic groups represented by R 36 to R 38 and the ring formed by the mutual bonding of R 37 and R 38 are preferably further substituents of fluorine or iodine atoms.

[0088] As for formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0089] [Chemical Formula 13]

[0090] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining these (e.g., groups formed by combining alkyl and aryl). M represents a single-bonded or divalent linker. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group composed of these (e.g., a group composed of alkyl and cycloalkyl groups). Alkyl and cycloalkyl groups, for example, in which one methylene group may be replaced by a heteroatom such as an oxygen atom, or a group containing 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 composed of alkyl and aryl groups. At least two of Q, M, and L1 can be bonded to form a loop (preferably a 5- or 6-membered loop). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tributyl and adamantyl. In this isostate sample, the glass transition temperature (Tg) and activation energy are increased, thus ensuring film strength and suppressing fogging.

[0091] When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the alkyl, cycloalkyl, aryl, and groups formed by combining these, represented by L1 and L2, preferably further have fluorine or iodine atoms as substituents. Preferably, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups contain heteroatoms such as oxygen atoms in addition to fluorine and iodine atoms. Specifically, for example, a methylene group in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups can be replaced by a heteroatom such as an oxygen atom, or a group containing heteroatoms such as a carbonyl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the heteroatom is preferably selected from the group consisting of alkyl, cycloalkyl, aryl, amino, ammonium, mercapto, cyano, aldehyde, and groups composed of these heteroatoms, which may contain heteroatoms and are represented by Q.

[0092] In formula (Y4), Ar represents an aromatic cycloalkyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond together to form a non-aromatic ring. Ar is preferably an aryl group. When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the aromatic cycloalkanes represented by Ar and the alkyl, cycloalkyl and aryl groups represented by Rn are preferably substituents having fluorine or iodine atoms.

[0093] From the viewpoint of excellent acid decomposition properties of repeating units, in the release group protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring is preferably not a halogen atom such as a fluorine atom as a substituent.

[0094] In addition, the group that is removed by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0095] As a repeating unit with an acid-decomposable group, it is also preferred to be a repeating unit represented by formula (A).

[0096] [Chemical Formula 14]

[0097] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, or an aryl group that may have a fluorine or iodine atom; and R2 represents a detached group that can have a fluorine or iodine atom after being desorbed by an acid. At least one of L1, R1, and R2 has a fluorine or iodine atom. Examples of divalent linking groups represented by L1 that may have fluorine or iodine atoms include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have fluorine or iodine atoms (e.g., alkylene, cycloalkylene, alkenylene, and arylene), and linking groups formed by multiple such groups. Preferably, L1 is -CO-, arylene, or -arylene-alkylene-with fluorine or iodine atoms, and more preferably -CO-, or -arylene-alkylene-with fluorine or iodine atoms. As an enfrylene, enfrylene is preferred. The alkyl group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferred to be 1 to 10, and more preferably 1 to 3. There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0098] The alkyl group represented by R1 can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferred to be 1 to 10, and more preferably 1 to 3. There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group represented by R1 that has fluorine or iodine atoms, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. Alkyl groups represented by R1 may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0099] As a detaching radical represented by R 2, which may have fluorine or iodine atoms, examples can be given of detaching radicals represented by the above formulas (Y1) to (Y4) that have fluorine or iodine atoms.

[0100] As a repeating unit with an acid-decomposable group, it is preferably a repeating unit represented by formula (AI).

[0101] [Chemical Formula 15]

[0102] In formula (AI), Xa 1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linker. Rx 1 to Rx 3 independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic or polycyclic). Wherein, when all Rx 1 to Rx 3 are alkyl (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl. Two of Rx 1 to Rx 3 can bond together to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0103] As represented by Xa 1, an alkyl group that may have substituents, examples include methyl or a group represented by -CH 2-R 11. R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organogroup. As a monovalent organogroup represented by R 11, examples include alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acetyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably alkyl groups with 3 or fewer carbon atoms, and more preferably methyl groups. As Xa 1, a hydrogen atom, methyl, trifluoromethyl, or hydroxymethyl group is preferred.

[0104] Examples of divalent linking groups for T include alkyl groups, aromatic cycloyl groups, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkyl or cycloalkyl group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0105] The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The cycloalkyl group formed by two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. Also preferably, it is a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Cycloalkyl groups formed by two bonds in Rx1 to Rx3, for example, in which one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylene. Furthermore, in such cycloalkyl groups, one or more of the ethyl groups constituting the cycloalkane ring can be replaced by vinylene. The repeating unit represented by formula (AI), for example, preferably Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl state.

[0106] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0107] As the repeating unit represented by formula (AI), it is preferably an acid-degradable (meth)acrylate trialkyl ester repeating unit (Xa 1 represents a hydrogen atom or methyl group, and T represents a single bond repeating unit).

[0108] Specific examples of repeating units with acid-decomposing groups are shown below, but are not limited to these. Furthermore, in the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb independently represent straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

[0109] [Chemical Formula 16]

[0110] [Chemical Formula 17]

[0111] [Chemical Formula 18]

[0112] [Chemical Formula 19]

[0113] [Chemical Formula 20]

[0114] Resin (A), as a repeating unit with an acid-degradable group, may have repeating units containing an acid-degradable group with an unsaturated bond. As a repeating unit having an acid-decomposable group containing unsaturated bonds, it is preferably a repeating unit represented by formula (B).

[0115] [Chemical Formula 21]

[0116] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group that may have substituents. L represents a single bond or a divalent linker that may have substituents. Ry 1 to Ry 3 independently represent a straight-chain or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. At least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 can bond together to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0117] As represented by Xb, an alkyl group that can have substituents, examples include groups represented by methyl or -CH2-R11. R11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, and an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably an alkyl group with 3 or fewer carbon atoms, and more preferably a methyl group. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group are preferred.

[0118] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In these formulas, Rt represents an alkyl group, an cycloalkyl group, or an aromatic cycloalkyl group, preferably an aromatic cycloalkyl group. The L group is preferably -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO-. Rt may have halogen atoms, hydroxyl groups, alkoxy groups, or other substituents.

[0119] The alkyl group of Ry 1 to Ry 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups of Ry 1 to Ry 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Ry 1 to Ry 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Ry 1 to Ry 3 is preferably vinyl. The acetylenic group of Ry1 to Ry3 is preferably acetylenic. As the cycloalkenyl group of Ry 1 to Ry 3, it is preferably a structure containing a double bond in part of a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. The cycloalkyl group formed by two bonds in Ry 1 to Ry 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups formed by two bonds in Ry 1 to Ry 3, for example, wherein one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as -SO 2- or -SO 3-, vinylene, or a combination thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethyl groups constituting the cycloalkane or cycloalkene ring can be replaced by vinylene. The repeating unit represented by formula (B), for example, preferably Ry 1 is methyl, ethyl, vinyl, allyl, or aryl, and Ry 2 and Ry 3 are bonded to form the above-mentioned cycloalkyl or cycloalkenyl state.

[0120] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0121] As the repeating unit represented by formula (B), it is preferably an acid-degradable (meth)acrylic acid trialkyl ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -CO- group repeating unit), an acid-degradable hydroxystyrene trialkyl ether repeating unit (Xb represents a hydrogen atom or methyl, and L represents a phenyl repeating unit), or an acid-degradable styrene carboxylic acid trialkyl ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -Rt-CO- group (Rt is an aromatic group) repeating unit).

[0122] The content of repeating units containing acid-degradable groups with unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (A).

[0123] Specific examples of repeating units having acid-decomposing groups containing unsaturated bonds are shown below, but are not limited thereto. Furthermore, in the formula, Xb and L1 represent any of the substituents and linkers as described above, Ar represents an aromatic group, R represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acetoxy, cyano, nitro, amino, halogen atom, ester (-OCOR''' or -COOR''', R'''' is an alkyl or fluorinated alkyl with 1 to 20 carbon atoms), or a carboxyl group, etc., R' represents a straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl, alkenyl, alkynyl, or monocyclic or polycyclic aryl, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as -SO2- or -SO3-, vinylidene, or a combination thereof, and n, m, and l represent integers greater than or equal to 0.

[0124] [Chemical Formula 22]

[0125] [Chemical Formula 23]

[0126] [Chemical Formula 24]

[0127] [Chemical Formula 25]

[0128] The content of repeating units with acid-degradable groups, excluding repeating unit (a), as the content of repeating units with acid-degradable groups including repeating unit (a), is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to all repeating units in resin (A).

[0129] Resin (A) may contain at least one repeating unit selected from the group consisting of group A below and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of repeating units of the following (20) to (25). (20) The repeating unit with acid groups, described later. (21) The repeating unit described later, which does not have any of the acid-decomposing groups or acid groups, but has a fluorine atom, a bromine atom, or an iodine atom. (22) Repeating units having lactone, sulcinolone, or carbonate groups, as described later. (23) The repeating unit with photoacid-generating group described later. (24) Repeating units described later, represented by equation (V-1) or equation (V-2) below. (25) Repeating units used to reduce the motion of the main chain Furthermore, the repeating units represented by equations (A) to (E) described later are equivalent to (25) repeating units used to reduce the mobility of the main chain. Group B: A group consisting of repeating units of the following (30) to (32). (30) The repeating unit described below, having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble group. (31) The repeating unit described later, which has an alicyclic hydrocarbon structure and does not exhibit acid decomposition properties. (32) The repeating unit described later, represented by formula (III), which does not have either a hydroxyl or a cyano group.

[0130] Resin (A) preferably has acid groups, and as described below, it preferably contains repeating units with acid groups. Furthermore, the definition of acid groups will be explained later along with the preferred state of repeating units with acid groups. When resin (A) has acid groups, the interaction between resin (A) and the acid generated by the photoacid generator is more excellent. As a result, acid diffusion can be further suppressed, making the cross-sectional shape of the formed pattern closer to a rectangle.

[0131] Resin (A) may have at least one repeating unit selected from the group consisting of the above-described group A. When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for EUV exposure, resin (A) preferably has at least one repeating unit selected from the group consisting of the above-described group A. Resin (A) may contain at least one of fluorine atoms and iodine atoms. When the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (A) preferably contains at least one of fluorine atoms and iodine atoms. When resin (A) contains both fluorine atoms and iodine atoms, resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may have both repeating units containing fluorine atoms and repeating units containing iodine atoms. Resin (A) may have repeating units containing aromatic groups. When the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (A) is also preferably having repeating units containing aromatic groups. Resin (A) may have at least one repeating unit selected from the group consisting of the above-described group B. When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, resin (A) preferably has at least one repeating unit selected from the group consisting of the above-described group B. Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (A) is preferably free of either fluorine atoms or silicon atoms.

[0132] (Repeating units with acid groups) Resin (A) is preferably a repeating unit containing an acid group. As an acid group, it is preferable to have an acid group with a pKa of 13 or less. The acid dissociation constant of the above-mentioned acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) contains acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, and is mostly 0.2 to 6.0 mmol / g. Preferably, it is 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the content of acid groups is within the above range, development will proceed well, resulting in excellent pattern shape and resolution. As an acid group, for example, it is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In the above hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms can be replaced by groups other than fluorine atoms (alkoxycarbonyl groups, etc.). As an acid group, -C(CF3)(OH)-CF2- is preferred. Furthermore, one or more fluorine atoms can be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group is preferably a repeating unit that is different from repeating units having a structure in which a polar group is protected by a group that is removed by the action of the acid described above, and repeating units having lactone, sulcinolone or carbonate groups as described later. Repeating units with acid groups can have fluorine or iodine atoms.

[0133] As an acid group, it is particularly good to have a phenolic hydroxyl group. In addition to the repeating unit (a) mentioned above, resin (A) preferably further contains repeating units having phenolic hydroxyl groups.

[0134] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following general formula (B).

[0135] [Chemical Formula 26]

[0136] R 3 represents a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 can be an alkyl, cycloalkyl, aryl, or a combination thereof.

[0137] R4 and R5 represent hydrogen atoms, halogen atoms, or alkyl groups, respectively. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

[0138] L2 represents a single bond or an ester bond. L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkane groups. R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Furthermore, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with an (n+m+1) valence. R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine. m represents an integer greater than or equal to 1. m is preferably an integer between 1 and 3, and even more preferably an integer between 1 and 2. n represents an integer greater than or equal to 1 or 0. Ideally, n should be an integer between 1 and 4. In addition, (n+m+1) is preferably an integer from 1 to 5.

[0139] The repeating unit having an acid group is preferably a repeating unit represented by the following general formula (c) (repeat unit (c)). The resin (A) preferably further contains a repeating unit (c) represented by the following general formula (c).

[0140] [Chemical Formula 27]

[0141] In general formula (c), R 61 to R 63 independently represent hydrogen atoms, organogroups, or halogen atoms, respectively. R 62 can bond with Ar to form a ring, in which case R 62 represents a single bond or an alkyl group. L represents a single bond or a divalent linker. Ar represents an aromatic cyclic group with a (k+1) valence; when bonded with R 62 to form a ring, it represents an aromatic cyclic group with a (k+2) valence. k represents an integer from 1 to 5.

[0142] In general formula (c), R 61 to R 63 independently represent hydrogen atoms, organic groups, or halogen atoms, respectively. Examples of organic groups represented by R 61 to R 63 include alkyl, cycloalkyl, cyano, or alkoxycarbonyl groups.

[0143] The alkyl group represented by R 61 to R 63 is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably an alkyl group with 8 or fewer carbon atoms, and even more preferably an alkyl group with 3 or fewer carbon atoms.

[0144] The cycloalkyl groups represented by R 61 to R 63 can be either monocyclic or polycyclic. Among them, cyclopropyl, cyclopentyl, and cyclohexyl groups with 3 to 8 carbon atoms and being monocyclic are preferred. The alkyl group contained in the alkoxycarbonyl group represented by R 61 to R 63 is preferably the same as the alkyl group in R 61 to R 63 mentioned above.

[0145] When R 62 forms a ring with Ar, the alkyl group of R 62 is preferably a group from the alkyl groups of R 61 to R 63 in which any one hydrogen atom has been removed.

[0146] Examples of halogen atoms represented by R 61 to R 63 include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the most preferred.

[0147] Preferred substituents among the aforementioned groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acetyl, acetoxy, alkoxycarbonyl, cyano, and nitro. The substituent preferably has 8 or fewer carbon atoms.

[0148] In general formula (c), Ar represents an aromatic cyclic group with a (k+1) valence. The divalent aromatic cyclic group when k is 1 can have substituents, such as aryl groups with 6 to 18 carbons, such as phenyl, methylphenyl, naphthyl, and anthracene, or aromatic cyclic groups containing heterocycles such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring.

[0149] As a specific example of an aromatic cyclic group with a valence of (k+1) when k is an integer greater than or equal to 2, a group formed by removing (k-1) arbitrary hydrogen atoms from the above-mentioned divalent aromatic cyclic group can be given. (k+1) valence aromatic cyclic groups can further have substituents.

[0150] Substituents that can be present as (k+1) valence aromatic cyclic groups include, for example, halogen atoms, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonoxy, alkoxycarbonyl, or aryloxycarbonyl.

[0151] Ar is preferably an aromatic ring group with 6 to 18 carbon atoms, and more preferably a benzyl ring group, naphthyl ring group, or pentophenyl ring group. The repeating unit represented by general formula (c) preferably has a hydroxystyrene structure. That is, Ar is preferably a phenyl ring group, and more preferably an exenylphenyl group (a divalent phenyl ring group).

[0152] In general formula (c), L represents a single bond or a divalent linker. As a binary linking basis represented by L, examples include *-X 4-L 4-**. In the above formula, X 4 represents a single bond, -COO- or -CONR 64-, and R 64 represents a hydrogen atom or an alkyl group. L4 indicates a single bond or an extended alkyl group. The * series bonds with the carbon atoms of the main chain in general formula (c), and the ** series bonds with Ar.

[0153] Examples of alkyl groups with 20 or fewer carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, with a preference for alkyl groups with 8 or fewer carbon atoms. As X 4, it is preferred to be a single bond, -COO- or -CONH-, and even more preferably a single bond or -COO-.

[0154] The alkyl group in L4 is preferably an alkyl group having 1 to 8 carbons, such as methylene, ethyl, propyl, butyl, hexyl, and octyl.

[0155] L is preferably a single bond, -COO-, or -CONH-, and even more preferably a single bond.

[0156] In general formula (c), k represents an integer from 1 to 5. k is preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0157] The following examples illustrate repeating units with acid groups. In the formula, a represents an integer from 1 to 3.

[0158] [Chemical Formula 28]

[0159] [Chemical Formula 29]

[0160] [Chemical Formula 30]

[0161] [Chemical Formula 31]

[0162] [Chemical Formula 32]

[0163] [Chemical Formula 33]

[0164] Furthermore, among the aforementioned repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer from 1 to 3.

[0165] [Chemical Formula 34]

[0166] [Chemical Formula 35]

[0167] The content of repeating units with acid groups is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (A).

[0168] (A repeating unit that does not have an acid-decomposing group or any of the acid groups, but has a fluorine atom, a bromine atom or an iodine atom) In addition to the aforementioned <repeating units with acid-decomposable groups> and <repeating units with acid groups>, resin (A) may also have repeating units (hereinafter also referred to as unit X) that do not have either acid-decomposable groups or acid groups but have fluorine, bromine, or iodine atoms. The <repeating units with fluorine, bromine, or iodine atoms that do not have either acid-decomposable groups or acid groups> are preferably different from other types of repeating units belonging to group A, such as <repeating units with lactone, sulopentalide, or carbonate groups> and <repeating units with photoacid-generating groups>, as described later.

[0169] As unit X, it is preferably a repeating unit represented by equation (C).

[0170] [Chemical Formula 36]

[0171] L 5 represents a single bond or an ester group. R 9 represents a hydrogen atom, or an alkyl group that may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group composed of these combinations.

[0172] The following are examples of repeating units having fluorine or iodine atoms.

[0173] [Chemical Formula 37]

[0174] The content of unit X, relative to all repeating units in resin (A), is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

[0175] In the repeating units of resin (A), the total content of repeating units containing at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and especially preferably 40 mol% or more, relative to all repeating units of resin (A). There is no particular upper limit; for example, it may be 100 mol% or less relative to all repeating units of resin (A). Furthermore, as repeating units containing at least one of fluorine, bromine, and iodine atoms, examples include: repeating units having fluorine, bromine, or iodine atoms and having an acid-decomposing group; repeating units having fluorine, bromine, or iodine atoms and having an acid group; and repeating units having fluorine, bromine, or iodine atoms.

[0176] (Repeating units with lactone, sulcinolone, or carbonate groups) Resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") containing at least one of the group consisting of lactone groups, sulcinolone groups and carbonate groups. Unit Y is also preferably free of acid groups such as hydroxyl and hexafluoropropanol groups.

[0177] As a lactone group or sulfonolactone group, it is acceptable as long as it has a lactone structure or sulfonolactone structure. The lactone structure or sulfonolactone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sulfonolactone structure. More preferably, it is a bicyclic or spirocyclic structure in which other ring structures are fused on the 5-7 membered ring lactone structure, or a bicyclic or spirocyclic structure in which other ring structures are fused on the 5-7 membered ring sulfonolactone structure. Resin (A) preferably has repeating units containing lactone or sulfonyl groups, which are formed by removing one or more hydrogen atoms from the ring-member atoms of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or a sulfonyl structure represented by any one of the following formulas (SL1-1) to (SL1-3). The lactone or sulfonyl groups can be directly bonded to the main chain. For example, the ring-member atoms of the lactone or sulfonyl groups can also constitute the main chain of resin (A).

[0178] [Chemical Formula 38]

[0179] The aforementioned lactone or sulopentalide structures can also have substituents (Rb 2). Preferred substituents (Rb 2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n 2 represents an integer from 0 to 4. When n 2 is 2 or more, the plurality of Rb 2 groups can be different, and the plurality of Rb 2 groups can also bond together to form a ring.

[0180] As a repeating unit having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3), for example, a repeating unit represented by the following formula (AI) can be cited.

[0181] [Chemical Formula 39]

[0182] In formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that can be present in the alkyl group of Rb 0 include hydroxyl groups and halogen atoms. Examples of halogen atoms that can be represented by Rb 0 include fluorine, chlorine, bromine, and iodine. Rb 0 is preferably represented by hydrogen or methyl. Ab represents a single bond, an alkyl group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linker formed by combining these. Preferably, Ab is a single bond or a linker represented by -Ab 1-CO 2-. Ab 1 is a straight-chain or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group, preferably methylene, ethyl, cyclohexyl, adamantyl, or norbornyl. V represents a group formed by removing a hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or a group formed by removing a hydrogen atom from a ring member atom of a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3).

[0183] When an optical isomer exists in a repeating unit having a lactone group or a sulcinolone group, any one of the optical isomers can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90% or higher, and more preferably 95% or higher.

[0184] As a carbonate group, a cyclic carbonate group is preferred. As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following formula (A-1).

[0185] [Chemical Formula 40]

[0186] In formula (A-1), RA1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl). n represents an integer greater than or equal to 0. RA2 represents a substituent. When n is 2 or more, there may be multiple RA2 groups, which may be identical or different. A represents a single bond or a divalent linking group. As the aforementioned divalent linking group, it is preferably an alkyl group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these. Z represents a group that forms a monocyclic or polycyclic atom together with the group represented by -O-CO-O- in the formula.

[0187] The following example illustrates unit Y. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0188] [Chemical Formula 41]

[0189] [Chemical Formula 42] (In the formula, Rx is H, CH3, CH2OH, or CF3)

[0190] [Chemical Formula 43] (In the formula, Rx is H, CH3, CH2OH, or CF3)

[0191] The content of unit Y, relative to all repeating units in resin (A), is preferably 1 mol% or more, more preferably 10 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and especially preferably 60 mol% or less.

[0192] (Repeating unit with photoacid-generating group) As a repeating unit other than those mentioned above, resin (A) may have repeating units containing groups that generate acid by irradiation with photochemical rays or radiation (hereinafter also referred to as "photoacid-generating groups"). As a repeating unit containing a photoacid generating group, the repeating unit represented by equation (4) can be cited.

[0193] [Chemical Formula 44]

[0194] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linker. L 42 represents a divalent linker. R 40 represents a structural site where acid is produced in the side chain due to decomposition caused by photochemical irradiation or radiation. The following are examples of repeating units having photoacid-generating groups.

[0195] [Chemical Formula 45]

[0196] Furthermore, as a repeating unit represented by equation (4), examples can be found in paragraphs

[0094] to

[0105] of Japanese Patent Application Publication No. 2014-041327 and paragraph

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

[0197] The content of repeating units having photoacid-generating groups is preferably 1 mol% or more, more preferably 5 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to all repeating units in resin (A).

[0198] (Repeating units represented by equation (V-1) or equation (V-2) below) Resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit that is different from the repeating unit described above.

[0199] [Chemical Formula 46]

[0200] In the formula, R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acetoxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group with 1 to 6 carbon atoms), or carboxyl group. As an alkyl group, it is preferred to be a straight-chain, branched, or cyclic alkyl group with 1 to 10 carbon atoms. n 3 represents an integer from 0 to 6. n 4 represents an integer from 0 to 4. X 4 represents a methylene group, an oxygen atom, or a sulfur atom. The following examples illustrate repeating units represented by equations (V-1) or (V-2). As a repeating unit represented by formula (V-1) or (V-2), for example, the repeating unit described in paragraph

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

[0201] (Repetitive units used to reduce the mobility of the main chain) From the viewpoint of suppressing excessive diffusion of the generated acid or pattern collapse during development, resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and most preferably greater than 125°C. Furthermore, from the viewpoint of having a good dissolution rate in the developer, Tg is preferably below 400°C, and more preferably below 350°C. Furthermore, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) (hereinafter also referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of the homopolymer consisting only of each repeating unit contained in the polymer is calculated separately using the Bicerano method. Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Then, the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to obtain the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). When calculating Tg using the Bicerano method, the polymer physical property assessment software MDL Polymer (MDL Information Systems, Inc.) can be used.

[0202] To increase the temperature gradient (Tg) of resin (A) (preferably, to exceed 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introducing large-volume substituents into the main chain (b) Introducing multiple substituents into the main chain (c) Introducing substituents near the main chain to induce interactions between resins (A). (d) Formation of the main chain in the ring structure (e) Linking ring structures to the main chain Furthermore, resin (A) is preferably a repeating unit having a Tg of 130°C or higher as a homopolymer. Furthermore, there are no particular restrictions on the types of repeating units whose Tg of the homopolymer is above 130°C, as long as the repeating unit whose Tg of the homopolymer is above 130°C as calculated using the Bicerano method is acceptable. In addition, the repeating units represented by equations (A) to (E) described later, depending on the type of functional groups therein, are equivalent to repeating units whose Tg of the homopolymer is above 130°C.

[0203] As one example of a specific implementation of (a) above, a method of introducing a repeating unit represented by formula (A) into resin (A) can be cited.

[0204] [Chemical Formula 47]

[0205] In formula (A), RA represents a group containing a polycyclic structure. Rx represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and these multiple ring structures may or may not be fused. As a specific example of a repeating unit represented by formula (A), the repeating unit described in paragraphs

[0107] to

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

[0206] As one example of a specific implementation of (b) above, a method of introducing repeating units represented by formula (B) into resin (A) can be cited.

[0207] [Chemical Formula 48]

[0208] In formula (B), Rb1 to Rb4 independently represent hydrogen atoms or organic groups, and at least two of Rb1 to Rb4 represent organic groups. There are no particular restrictions on the types of other organic groups if at least one of the organic groups is a group that is directly linked to the main chain of the repeating unit in the ring structure. Furthermore, if none of the organic groups are directly linked to the main chain of the ring structure and repeating unit, then at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms. As a specific example of a repeating unit represented by equation (B), the repeating unit described in paragraphs

[0113] to

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

[0209] As one example of a specific implementation of (c) above, a method of introducing a repeating unit represented by formula (C) into resin (A) can be cited.

[0210] [Chemical Formula 49]

[0211] In formula (C), Rc1 to Rc4 independently represent hydrogen atoms or organic groups, and at least one of Rc1 to Rc4 is a group containing hydrogen atoms with hydrogen bonding in the main chain carbon up to 3 atoms. Preferably, for inducing the interaction between the main chains of resin (A), hydrogen atoms with hydrogen bonding in the main chain up to 2 atoms (closer to the main chain side) are preferred. As a specific example of a repeating unit represented by formula (C), the repeating unit described in paragraphs

[0119] to

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

[0212] As one example of a specific implementation of (d) above, a method of introducing a repeating unit represented by formula (D) into resin (A) can be cited.

[0213] [Chemical Formula 50]

[0214] In formula (D), "Cyclic" represents a group whose main chain is formed in a cyclic structure. There is no particular restriction on the number of atoms constituting the ring. As a specific example of a repeating unit represented by formula (D), the repeating unit described in paragraphs

[0126] to

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

[0215] As one example of a specific implementation of (e) above, a method of introducing a repeating unit represented by formula (E) into resin (A) can be cited.

[0216] [Chemical Formula 51]

[0217] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups that can have substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in a cyclic group. As a specific example of a repeating unit represented by formula (E), the repeating unit described in paragraphs

[0131] to

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

[0218] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble groups) Resin (A) may have repeating units containing at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups. As for the repeating units containing lactone, sulfonyl, or carbonate groups in resin (A), examples include the repeating units described in the above-mentioned <Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups>. A preferred content is also as described in the above-mentioned <Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups>.

[0219] Resin (A) may have repeating units containing hydroxyl or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl or cyano group. The repeating unit having a hydroxyl or cyano group is preferably free of acid-degradable groups. Examples of repeating units having a hydroxyl or cyano group include those described in paragraphs

[0081] to

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

[0220] Resin (A) may have repeating units containing base-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonimide groups, disulfonimide groups, and aliphatic alcohol groups substituted with electron-withdrawing groups at the α-position (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units with alkali-soluble groups in the resin (A), resolution in contact hole applications can be increased. Examples of repeating units with alkali-soluble groups include those described in paragraphs

[0085] and

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

[0221] (A repeating unit with an alicyclic hydrocarbon structure that does not exhibit acid decomposition properties) Resin (A) can have repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties. This reduces the leaching of low-molecular-weight components from the photoresist film into the immersion bath during immersion exposure. Examples of repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties include repeating units derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0222] (A repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either hydroxyl or cyano groups.

[0223] [Chemical Formula 52]

[0224] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH₂-O-Ra₂ group. In the formula, Ra₂ represents a hydrogen atom, an alkyl group, or a acetyl group. As a repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group, the repeating unit described in paragraphs

[0087] to

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

[0225] (Other repeating units) In addition, resin (A) may have other repeating units besides the repeating units mentioned above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. The following are specific examples of repeating units other than the repeating units mentioned above.

[0226] [Chemical Formula 53]

[0227] In addition to the repeating units mentioned above, resin (A) may also have various repeating units to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist profile, resolution, heat resistance, and sensitivity.

[0228] As resin (A), particularly when the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, it is preferable that all repeating units are composed of repeating units derived from compounds having ethylene unsaturated bonds. In particular, it is also preferable that all repeating units are composed of (meth)acrylate repeating units. When all repeating units are composed of (meth)acrylate repeating units, it is permissible to use any of the following: all repeating units are methacrylate repeating units, all repeating units are acrylate repeating units, or all repeating units are composed of both methacrylate and acrylate repeating units. Preferably, the acrylate repeating units constitute 50 moles or less of all repeating units.

[0229] Resin (A) can be synthesized using conventional methods (such as free radical polymerization). Using the GPC method with polystyrene equivalents, the weight average molecular weight of resin (A) is preferably below 30,000, more preferably 1,000 to 30,000, further preferably 3,000 to 30,000, and especially preferably 5,000 to 15,000. The dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, and especially preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and photoresist shape, and the smoother the sidewalls and the better the roughness of the photoresist pattern.

[0230] In the composition of the present invention, the content of resin (A) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, relative to the total solid content of the composition. Resin (A) may be used in one or in combination with multiple types.

[0231] <Photoacid Generator (B)> The composition of the present invention preferably includes a compound that produces acid by irradiation with photochemical rays or radiation (hereinafter also referred to as photoacid generator, photoacid generator (B)). The photoacid generator (B) can be in the form of a low molecular weight compound or in the form incorporated into a polymer (e.g., the resin (A) described above). Alternatively, it can be in both the form of a low molecular weight compound and the form incorporated into a polymer (e.g., the resin (A) described above). When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular limitation on the lower limit, but it is preferably 100 or more. When the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it can be incorporated into a part of the resin (A) or into a resin different from the resin (A). In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0232] As a photoacid generator (B), for example, compounds represented by "M + X -" (onium salts) can be cited, preferably compounds that generate organic acids by exposure. Examples of the aforementioned 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 tris(alkyl sulfonyl) methylated acids.

[0233] In compounds denoted by "M +X -", M + represents an organic cation. There are no particular restrictions on whether an organic cation can be monovalent or divalent or higher. The preferred organic cations are strontium cations or iodonium cations. Among them, the organic cations mentioned above are preferably cations represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or cations represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0234] [Chemical Formula 54]

[0235] In the above formula (ZaI), R 201, R 202 and R 203 each independently represent an organic group. The number of carbon atoms in the organic groups of R 201, R 202, and R 203 is preferably 1 to 30, more preferably 1 to 20. 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, for example, alkyl groups (e.g., butyl and pentyl) and -CH 2-CH 2-O-CH 2-CH 2-.

[0236] Suitable examples of organic cations in formula (ZaI) include cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b), which will be described later.

[0237] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is an aryl strontium cation, wherein at least one of R 201 to R 203 in the above formula (ZaI) is aryl. Aryl strontium cations can be 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. The ring structure can be formed by one of R 201 to R 203 being an aryl group and the remaining two bonds of R 201 to R 203, or it can contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group within the ring. Examples of groups formed by the two bonds of R 201 to R 203 include alkyl groups (e.g., butyl, pentyl, and -CH 2-CH 2-O-CH 2-CH 2-), wherein one or more methylene groups can be substituted 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 arylbicycloalkyl strontium cations.

[0238] The aryl group contained in the aryl strontium cation is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. 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, the two or more aryl groups can be the same or different. The aryl strontium cation may contain alkyl or cycloalkyl groups as desired, preferably straight-chain alkyl groups having 1 to 15 carbon atoms, branched alkyl groups having 3 to 15 carbon atoms, or cycloalkyl groups having 3 to 15 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, dibutyl, tributyl, cyclopropyl, cyclobutyl, or cyclohexyl.

[0239] The substituents that may be present in the aryl, alkyl, and cycloalkyl groups of R 201 to R 203 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 atoms (e.g., fluorine and iodine), hydroxyl, carboxyl, ester, sulfinyl, sulfonyl, alkylthio, or phenylthio. If possible, the above-mentioned substituents may be further substituents, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent and becomes a trifluoromethyl or other haloalkyl group. The aforementioned substituents are preferably formed by any combination to create acid-degradable groups. Furthermore, the term "acid-decomposable group" refers to a group that decomposes to produce a polar group through the action of an acid, preferably a group that is released by the action of an acid to protect the structure of the polar group. The aforementioned polar group and release group are as described above.

[0240] Next, the cation (ZaI-2) will be explained. In the cation (ZaI-2) system formula (ZaI), R 201 to R 203 independently represent cations with organic groups that do not have aromatic rings. An aromatic ring also includes aromatic rings containing heteroatoms. The number of carbon atoms in the non-aromatic organic groups of R 201 to R 203 is preferably 1 to 30, more preferably 1 to 20. R 201 to R 203 are each independently, preferably alkyl, cycloalkyl, allyl or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0241] Alkyl and cycloalkyl groups of R 201 to R 203, for example, include straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl). R 201 to R 203 can be further substituted with halogen atoms, alkoxy groups (e.g., carbon 1 to 5), hydroxyl groups, cyano groups, or nitro groups. The substituents of R 201 to R 203 are respectively independent, or preferably formed by any combination of substituents to form acid-degradable groups.

[0242] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0243] [Chemical Formula 55]

[0244] In formula (ZaI-3b), R1c to R5c independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atoms, hydroxyl, nitro, alkylthio or arylthio. R6c and R7c independently represent a hydrogen atom, an alkyl group (e.g., tert-butyl), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Rx and Ry independently represent alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl, respectively. The substituents R1c~R7c, as well as Rx and Ry, are respectively, independently, and preferably formed by any combination of substituents to form acid-degradable groups.

[0245] 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 each other to form a ring, which can independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds. Examples of the aforementioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings composed of two or more such rings. Examples of rings include 3 to 10-membered rings, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0246] Examples of alkyl groups formed by the bonding of any two or more of R1c to R5c, R6c and R7c, and Rx and Ry include alkyl groups such as butylyl and pentylyl. The methylene group in the alkyl group may be replaced by heteroatoms such as oxygen atoms. The group formed by the bond between R5c and R6c, and between R5c and Rx, is preferably a single bond or an alkyl group. Examples of alkyl groups include methylene and ethyl groups.

[0247] Rings formed by the mutual bonding of R1c to R5c, R6c, R7c, Rx, Ry, and any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry may have substituents.

[0248] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0249] [Chemical Formula 56]

[0250] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. R 13 represents a hydrogen atom, a halogen atom (e.g., fluorine and iodine atoms), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be the cycloalkyl group itself or a group that partially contains a cycloalkyl group). These groups may have substituents. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, a haloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which can be the cycloalkyl group itself or a group that partially contains a cycloalkyl group). These groups may have substituents. When there are multiple R 14 groups, each of the above-mentioned groups, such as the hydroxyl group, represents an independent group. R 15 can independently represent alkyl, cycloalkyl, or naphthyl groups. Two R 15 groups can bond together to form a ring. When two R 15 groups bond together to form a ring, the ring skeleton can contain heteroatoms such as oxygen or nitrogen atoms. In one state, it is preferred that the two R 15s are alkyl groups and are bonded together to form a ring structure. Furthermore, the aforementioned alkyl group, the aforementioned cycloalkyl group, the aforementioned naphthyl group, and the ring formed by the bonded two R 15s may have substituents.

[0251] In formula (ZaI-4b), the alkyl groups of R13, R14, and R15 can be straight-chain or branched. The alkyl groups preferably have 1 to 10 carbon atoms. The alkyl groups are preferably methyl, ethyl, n-butyl, or tributyl, etc. Each substituent of R13~R15, as well as Rx and Ry, is preferably formed independently, or more preferably, by any combination of substituents to form an acid-decomposing group.

[0252] Next, we will explain equation (ZaII). In 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 can be a heterocyclic aryl group having an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic aryl groups include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As for the alkyl and cycloalkyl groups of R 204 and R 205, they 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).

[0253] The aryl, alkyl, and cycloalkyl groups in R 204 and R 205 can each independently have substituents. Examples of substituents that can be present in the aryl, alkyl, and cycloalkyl groups of R 204 and R 205 include alkyl groups (e.g., 1-15 carbon atoms), cycloalkyl groups (e.g., 3-15 carbon atoms), aryl groups (e.g., 6-15 carbon atoms), alkoxy groups (e.g., 1-15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Furthermore, the substituents in R 204 and R 205 are preferably formed by any combination of substituents to create acid-degradable groups.

[0254] The following are specific examples of organic cations, but the invention is not limited thereto.

[0255] [Chemical Formula 57]

[0256] [Chemical Formula 58]

[0257] [Chemical Formula 59]

[0258] In compounds denoted by "M +X -", X - represents an organic anion. There are no particular limitations on what constitutes an organic anion; examples of organic anions with a valence of 1 or 2 or higher can be given. As an organic anion, it is preferably an anion with very low ability to induce nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0259] Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfadiene anions, bis(alkylsulfadiene) sulfadiene anions, and tris(alkylsulfadiene) methylated anions.

[0260] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion can be a straight-chain or branched alkyl group, or a cycloalkyl group, preferably a straight-chain or branched alkyl group with 1 to 30 carbon atoms, or a cycloalkyl group with 3 to 30 carbon atoms. The aforementioned alkyl group, for example, can be a fluoroalkyl group (which may have substituents other than fluorine atoms. It can also be a perfluoroalkyl group).

[0261] The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group with 6 to 14 carbon atoms, for example, phenyl, tolyl and naphthyl.

[0262] The alkyl, cycloalkyl, and aryl groups mentioned above may have substituents. There are no particular limitations on the substituents; for example, halogen atoms such as nitro, fluorine, and chlorine, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably 1-15 carbon atoms), alkyl (preferably 1-10 carbon atoms), cycloalkyl (preferably 3-15 carbon atoms), aryl (preferably 6-14 carbon atoms), alkoxycarbonyl (preferably 2-7 carbon atoms), acetyl (preferably 2-12 carbon atoms), alkoxycarbonyloxy (preferably 2-7 carbon atoms), alkylthio (preferably 1-15 carbon atoms), alkylsulfonyl (preferably 1-15 carbon atoms), alkyliminosulfonyl (preferably 1-15 carbon atoms), and aryloxysulfonyl (preferably 6-20 carbon atoms) are also possible.

[0263] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms. Examples of aryl alkyl groups having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0264] Examples of sulfadiazine anions include, for instance, saccharin anion.

[0265] The alkyl group in the bis(alkylsulfonyl)imine anion and the trialkyl(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for such alkyl groups include 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. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imidin anion can also bond with each other to form a ring structure. This can increase the acid strength.

[0266] Other non-nucleophilic anions include, for example, phosphorus fluoride (e.g., PF6-), boron fluoride (e.g., BF4-), and antimony fluoride (e.g., SbF6-).

[0267] As a non-nucleophilic anion, it is preferably an aliphatic sulfonic acid anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imidion anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methylated anion in which the alkyl group is substituted with a fluorine atom. More preferably, it is a perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms), or a benzenesulfonic acid anion having a fluorine atom, and even more preferably, a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, or a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

[0268] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN1).

[0269] [Chemical Formula 60]

[0270] In formula (AN1), R1 and R2 independently represent hydrogen atoms or substituents, respectively. There are no particular restrictions on the substituents, but they are preferably non-electron-withdrawing groups. Examples of non-electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbonyl groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. The non-electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', each independently and preferably. R' is a monovalent hydrocarbon group.

[0271] Examples of monovalent hydrocarbon groups represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propynyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornyl; aryl groups such as phenyl, tolyl, xylyl, trimethylmethyl, naphthyl, methylnaphthyl, anthracene, and methylanthrayl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenemethyl. R1 and R2 are each, independently, preferably, a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0272] L represents a divalent linker. When there are multiple Ls, each L can be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these. Among these, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2-, -O-CO-O-alkylene-, -COO-alkylene-, or -CONH-alkylene- are preferred, and more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO 2-, or -COO-alkylene-.

[0273] L, for example, is preferably a group represented by the following formula (AN1-1). * a-(CR 2a 2) XQ-(CR 2b 2) Y-* b(AN1-1)

[0274] In equation (AN1-1), *a represents the bond position with R3 in equation (AN1). * b indicates the bond position with -C(R 1)(R 2)- in equation (AN1). X and Y represent integers from 0 to 10, preferably integers from 0 to 3. R 2a and R 2b represent hydrogen atoms or substituents independently, respectively. When there are multiple R2a and R2b respectively, the multiple R2a and R2b can be the same or different. When Y is 1 or more, the R2b atom in CR2b2 that is directly bonded to -C(R1)(R2)- in formula (AN1) is a non-fluorine atom. Q represents *AO-CO-O-*B, *A-CO-*B, *A-CO-O-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO 2-*B. Where X+Y in formula (AN1-1) is 1 or more, and R2a and R2b in formula (AN1-1) are both hydrogen atoms, Q represents *AO-CO-O-*B, *A-CO-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO2-*B. * A represents the bond position on the R 3 side in equation (AN1), * B represents the bond position on the -SO 3 - side in equation (AN1).

[0275] In formula (AN1), R3 represents an organic group. There are no particular restrictions on the presence of one or more carbon atoms in the aforementioned organic groups. They can be straight-chain groups (e.g., straight-chain alkyl groups), branched-chain groups (e.g., branched-chain alkyl groups such as tert-butyl), or cyclic groups. The aforementioned organic groups may or may not have substituents. The aforementioned organic groups may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.).

[0276] R3 is preferably an organic group with a cyclic structure. The cyclic structure can be monocyclic or polycyclic, and can also have substituents. The ring in the organic group containing the cyclic structure is preferably directly bonded to L in formula (AN1). Organic groups having the above-mentioned cyclic structure may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.). Heteroatoms may replace one or more carbon atoms forming the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group, a lactone cyclic group, or a sulfonyl lactone cyclic group. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group with a cyclic structure. The hydrocarbon group in the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The aforementioned cycloalkyl group can be monocyclic (such as cyclohexyl) or polycyclic (such as adamantyl), with a preferred number of carbon atoms being 5 to 12. The lactone group and sulfonolactone group described above are preferably, for example, groups formed by removing a hydrogen atom from the ring member atom constituting the lactone structure or sulfonolactone structure in any of the structures represented by formulas (LC1-1) to (LC1-21) and formulas (SL1-1) to (SL1-3).

[0277] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0278] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN2).

[0279] [Chemical Formula 61]

[0280] In equation (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0281] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organogroup without a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0282] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are multiple R4s and R5s, R4s and R5s may be the same or different. The alkyl group represented by R4 and R5 is preferably composed of 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred as R4 and R5.

[0283] L represents a binary linking basis. The definition of L is synonymous with L in equation (AN1).

[0284] W represents an organic group, preferably an organic group containing a cyclic structure. Preferably, it is a cyclic organic group. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Preferably, these are alicyclic groups with a large volumetric structure, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0285] The aryl group can be monocyclic or polycyclic. Examples of the aforementioned aryl groups include phenyl, naphthyl, phenanthryl, and anthracene. The heterocyclic group can be monocyclic or polycyclic. When it is a polycyclic heterocyclic group, it can further inhibit acid diffusion. The heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. The preferred heterocycles in the heterocyclic group are furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings.

[0286] The aforementioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be either linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atom constituting the cyclic organic group (the carbon atom that contributes to ring formation) may also be a carbonyl carbon.

[0287] The preferred anions represented by formula (AN2) are SO₃-CF₂-CH₂-OCO₃-(L) q'-W, SO₃-CF₂-CHF-CH₂-OCO₃-(L) q'-W, SO₃-CF₂-COO₃-(L) q'-W, SO₃-CF₂-CF₂-CH₂-CH₂-(L) qW, or SO₃-CF₂-CH(CF₃)-OCO₃-(L) q'-W. Here, L, q, and W are the same as in formula (AN2). q' represents an integer from 0 to 10.

[0288] As a non-nucleophilic anion, it is also preferred to be an aromatic sulfonic acid anion represented by the following formula (AN3).

[0289] [Chemical Formula 62]

[0290] In formula (AN3), Ar represents an aryl group (phenyl, etc.), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of substituents that may be further included include, for example, fluorine atoms and hydroxyl groups. n represents an integer greater than or equal to 0. Preferably, n is 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0291] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, urethane groups, urethane groups, sulfonate groups, ester groups, and groups consisting of two or more of these.

[0292] B represents a hydrocarbon group. As B, it is preferably an aliphatic hydrocarbon group, more preferably isopropyl, cyclohexyl, or an aryl group (such as tricyclohexylphenyl) that may further have substituents.

[0293] As a non-nucleophilic anion, disulfonamide anion is also preferred. For example, the disulfonamide anion is an anion represented by N-(SO₂-Rq)₂. Here, R q represents an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. Two R q groups may bond together to form a ring. The group formed by the bonding of two R q groups is preferably an enylalkyl group that may have substituents, more preferably a fluoroenylalkyl group, and even more preferably a perfluoroenylalkyl group. The enylalkyl group preferably has 2 to 4 carbon atoms.

[0294] Furthermore, as non-nucleophilic anions, anions represented by the following formulas (d1-1) to (d1-4) can also be cited.

[0295] [Chemical Formula 63]

[0296] [Chemical Formula 64]

[0297] In formula (d1-1), R 51 represents a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0298] In formula (d1-2), Z 2c represents a hydrocarbon group with 1 to 30 carbon atoms that can have substituents (where the carbon atom adjacent to S is not replaced by a fluorine atom). The hydrocarbon group in Z 2c can be linear, branched, or cyclic. Furthermore, the carbon atom in the hydrocarbon group (preferably a carbon atom that is a ring member when the hydrocarbon group has a cyclic structure) can be a carbonyl carbon (-CO-). Examples of hydrocarbon groups include norbornyl groups, which can have substituents. The carbon atom forming the norbornyl group can be a carbonyl carbon. In formula (d1-2), "Z 2c-SO 3 -" is preferably different from the anion represented by formulas (AN1) to (AN3) above. For example, Z 2c is preferably other than an aryl group. For example, in Z 2c, the atoms at the α and β positions relative to -SO 3 - are preferably atoms other than carbon atoms having fluorine atoms as substituents. For example, in Z 2c, the atoms at the α position and / or β position relative to -SO 3 - are preferably ring-member atoms in a cyclic group.

[0299] In formula (d1-3), R52 represents an organic group (preferably a hydrocarbon group with fluorine atoms), Y3 is a linear, branched, or cyclic alkyl, aryl, or carbonyl group, and Rf represents a hydrocarbon group.

[0300] In formula (d1-4), R53 and R54 independently represent organic groups (preferably hydrocarbon groups with fluorine atoms). R53 and R54 can bond together to form a ring.

[0301] Organic anions can be used alone or in combination with two or more.

[0302] (Compounds represented by general formula (1)) The photoacid generator (B) is preferably a compound represented by the following general formula (1) (hereinafter also referred to as "compound (B)").

[0303] [Chemical Formula 65]

[0304] In general formula (1), R1 and R5 independently represent aryl or heteroaryl groups, respectively. R2 to R4 independently represent hydrogen atoms or substituents, respectively. Mn+ represents a cation. n represents an integer greater than or equal to 1.

[0305] Regarding aryl groups as R1 and R5, examples include aryl groups with 6 to 15 carbon atoms, and more specifically, phenyl, naphthyl, anthracene, etc. are preferred examples. Regarding heteroaryl groups that are R1 and R5, examples include heteroaryl groups with 2 to 15 carbon atoms, and those with 5 to 10 member rings. Specifically, examples include furanyl, thiophene, pyrrole, oxazolyl, pyridinyl, quinolinyl, carbazolyl, etc. As for the substituents of R2 to R4, any monovalent substituent is acceptable and there are no particular limitations. Examples include alkyl, alkenyl, cycloalkyl, aryl, halogen atoms, groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms, and combinations of two or more of these.

[0306] Examples of alkyl groups with R2 to R4 include alkyl groups with 1 to 30 carbon atoms. The preferred alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl, dodecyl, or other alkyl groups having 1 to 20 carbon atoms, and more preferably alkyl groups having 1 to 8 carbon atoms.

[0307] As an alkenyl group of R2 to R4, examples include alkenyl groups with 2 to 30 carbon atoms, with alkenyl groups having 2 to 8 carbon atoms being more preferred. As R2 to R4, the cycloalkyl group can be either monocyclic or polycyclic. The carbon number system of the cycloalkyl group is not particularly limited, but is preferably 3 to 8.

[0308] Aryl groups with R2 to R4, for example, aryl groups with 6 to 15 carbon atoms, specifically phenyl, naphthyl, anthracene, etc., are preferred examples. Examples of halogen atoms that are R2 to R4 include fluorine, chlorine, bromine, and iodine atoms.

[0309] Examples of heteroatom-containing groups include, for example, hydroxyl, carboxyl, alkoxy, thiol, thioether, nitro, nitroso, cyano, amino, acetoxy, acetylamino, heteroaryl, ether bond, carbonyl bond, and combinations of two or more of these.

[0310] The carbon number of the alkoxy, acetoxy, and acetylamidine groups is preferably 20 or less, and more preferably 8 or less. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tributoxy, and octoxy. Particularly preferred are methoxy, ethoxy, propoxy, isopropoxy, and tributoxy. Furthermore, regarding the thioether group, except that the oxygen atom is replaced by a sulfur atom, the same as the alkoxy group can be mentioned. Examples of acetylamidine groups include acetylamidine. Examples of acetylamidine groups include acetylamidine. As heteroaryl groups, examples can be found that are the same as those that are R1 and R5.

[0311] As aryl and heteroaryl groups of R1 and R5, they may further have substituents. Examples of further substituents include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and combinations of two or more of these. Alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof, respectively identical to the alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof in the specific examples of substituents as R2 to R4. When the aryl and heteroaryl systems that are R1 and R5 have a plurality of substituents, at least two of the plurality of substituents can bond together to form a ring.

[0312] Alkyl, alkenyl, cycloalkyl, aryl, or heteroatoms containing oxygen, sulfur, nitrogen, and silicon atoms, which are substituents of R2 to R4, may further have substituents. Examples of further substituents include alkyl, alkenyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acetyl, aceoxy, alkoxycarbonyl, cyano, and nitro, as well as combinations of two or more of these.

[0313] The above R1 and R5 can constitute the following groups: groups containing polar groups as described below; groups containing groups whose polarity increases due to decomposition by the action of acid; or groups containing groups whose solubility in alkaline developing solutions increases due to decomposition by the action of alkaline developing solutions. The above R2 to R4 can constitute the following groups: groups containing polar groups as described below; groups containing groups whose polarity increases due to decomposition by the action of acid; or groups containing groups whose solubility in alkaline developing solutions increases due to decomposition by the action of alkaline developing solutions.

[0314] In the above general formula (1), R3 preferably represents aryl. As an aryl group of R3, examples can be found that are identical to those of aryl groups of R1 and R5. As an aryl group of R3, it may further have substituents. Specific examples of substituents that may be further present in R1 and R5 are the groups described above. When the aryl group of R3 has a complex number of substituents, at least two of the complex substituents can bond together to form a ring.

[0315] In the above general formula (1), at least one of R1 to R5 is preferably: a group containing a polar group; a group containing a group whose polarity increases due to decomposition by the action of an acid; or a group containing a group whose solubility in an alkaline developer increases due to decomposition by the action of an alkaline developer.

[0316] Examples of polar groups among at least one of R1 to R5 that contain a polar group include, for example, carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonamide, sulfonimino, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imino, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, as well as acidic groups such as alcoholic hydroxyl.

[0317] Furthermore, the term "alcoholic hydroxyl group" refers to a hydroxyl group bonded to a hydrocarbon group, excluding hydroxyl groups directly bonded to an aromatic ring (phenolic hydroxyl groups), and excludes aliphatic alcohols (e.g., hexafluoroisopropanol group) whose α-position is replaced by an electron-withdrawing group such as a fluorine atom. Preferably, an alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 or more and less than 20. Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).

[0318] Groups containing polar groups can also include those with carbonyl bonds. Examples of groups containing carbonyl bonds include alkyl carbonyl groups and aryl carbonyl groups. As an alkyl group, examples include those that are the same as those that are R2 to R4 alkyl groups. As an aryl group, for example, those identical to those as R1 and R5 can be cited. A group containing a carbonyl bond is a group in which the carbonyl bond and the ether bond are not adjacent.

[0319] Alkyl carbonyl and aryl carbonyl groups, which are groups containing carbonyl bonds, can further have substituents. Examples of further substituents include alkyl, alkenyl, cycloalkyl, aryl, halogen atoms, groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms, and combinations of two or more of these. Alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof, respectively identical to the alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof in the specific examples of substituents as R2 to R4.

[0320] There are no particular limitations on the groups containing polar groups, but examples of organic groups containing polar groups can be given. Examples of organic groups containing polar groups include: alkyl; alkenyl; cycloalkyl; aryl; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; and combinations of two or more of these, which give these groups a polar group. Alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof, respectively identical to the alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof in the specific examples of substituents as R2 to R4.

[0321] Examples of groups containing polar groups include alkyl groups and aryl groups. As an alkyl group containing a polar group, examples include those that are the same as those that are R2 to R4 alkyl groups. For example, aryl groups containing polar groups can be identified as those that are the same as aryl groups as R1 and R5. Furthermore, groups containing polar groups can be polar in nature.

[0322] Among the groups comprising at least one of R1 to R5 that have a group whose polarity increases due to decomposition by acid action (hereinafter also referred to as "acid-decomposable group"), the group whose polarity increases due to decomposition by acid action (hereinafter also referred to as "acid-decomposable group") preferably has a structure that has a group (detached group) that is decomposed and detached by acid action to protect the polar group. As a polar group, examples include those that are the same as the polar group in a group containing a polar group that is at least one of R1 to R5.

[0323] As a group that is released by decomposition through the action of acid (release group), for example, groups represented by formulas (Y1) to (Y4) can be cited. Equation (Y1): -C(Rx 1)(Rx 2)(Rx 3) Formula (Y2):-C(=O)OC(Rx 1)(Rx 2)(Rx 3) Equation (Y3): -C(R 36)(R 37)(OR 38) Equation (Y4): -C(Rn)(H)(Ar)

[0324] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic). Furthermore, when all Rx1 to Rx3 are alkyl (straight-chain or branched), at least two of Rx1 to Rx3 are preferably methyl. Wherein, Rx 1 to Rx 3 are each independently, preferably representing a straight-chain or branched alkyl group, and Rx 1 to Rx 3 are each independently, more preferably representing a straight-chain alkyl group. Two of Rx 1 to Rx 3 can be bonded together to form a single ring or multiple rings. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The cycloalkyl group formed by two bonds in 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. Cycloalkyl groups formed by two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by heteroatoms such as oxygen atoms or groups with heteroatoms such as carbonyl groups. The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl state.

[0325] In formula (Y3), R36 to R38 independently represent a hydrogen atom or a monovalent organogroup. R37 and R38 can bond together to form a ring. Examples of monovalent organogroups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R36 is preferably a hydrogen atom.

[0326] As for formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0327] [Chemical Formula 66]

[0328] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining these (e.g., groups formed by combining alkyl and aryl). M represents a single-bonded or divalent linker. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group composed of these (e.g., a group composed of alkyl and cycloalkyl groups). Alkyl and cycloalkyl groups, for example, in which one methylene group may be substituted with a heteroatom such as an oxygen atom or a group having 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 a group composed of alkyl, cycloalkyl, aryl, or alkylene and aryl groups. At least two of Q, M, and L1 can be bonded to form a loop (preferably a 5- or 6-membered loop). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tributyl or adamantyl. In this isostate sample, the glass transition temperature (Tg) and activation energy are increased, thus ensuring film strength and suppressing fogging.

[0329] In formula (Y4), Ar represents an aromatic cycloalkyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond together to form a non-aromatic ring. Ar groups are preferably aryl groups.

[0330] The acid-degradable group is preferably an acetal structure. An acetal structure is, for example, a structure in which polar groups such as carboxyl, phenolic hydroxyl, and fluorinated alcohol are protected by a group represented by the above formula (Y3).

[0331] The group containing an acid-degradable group is not particularly limited as long as it contains an acid-degradable group, and examples of organic groups containing acid-degradable groups can be given. Examples of organic groups containing acid-degradable groups include: alkyl; alkenyl; cycloalkyl; aryl; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; and combinations of two or more of these, which constitute groups having acid-degradable groups. Alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof, respectively identical to the alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof in the specific examples of substituents as R2 to R4.

[0332] Examples of groups containing acid-degradable groups include alkyl groups and aryl groups. As an alkyl group containing an acid-decomposable group, examples include those that are the same as those that are R2 to R4 alkyl groups. For example, aryl groups containing acid-degradable groups can be identified as those that are the same as aryl groups as R1 and R5. Furthermore, groups containing acid-decomposing groups can be acid-decomposing basic elements themselves.

[0333] Among the groups that are at least one of R1 to R5 and contain a group whose solubility in alkaline developer increases due to decomposition by alkaline developer, the group whose solubility in alkaline developer increases due to decomposition by alkaline developer is also called a "polarity conversion group". Specific examples include lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC(O)-), aceimine group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate ester group (-OSO 2O-), sulfonate group (-SO 2O-), etc.

[0334] Examples of groups containing a polar conversion group include aceoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, aminomethylacetylated, and aceimino.

[0335] The number of carbon atoms in the acetylated group is preferably 1 to 30, and more preferably 1 to 8. The number of carbon atoms in the alkoxycarbonyl group is preferably 1 to 30, and more preferably 1 to 8.

[0336] The number of carbon atoms in the aryl group of the aryl group is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms in the aryl group of the aryloxycarbonyl group is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms in the alkoxycarbonyl group is preferably 1 to 30, and more preferably 1 to 8. The nimodiamine group is a group that has had one hydrogen atom removed from nimodiamine.

[0337] The acetooxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, aminomethylacetoyl, and aceimino groups may further have substituents. As further substituents, specific examples of substituents that can be further present in R1 and R5 can be found in the groups described above.

[0338] As a preferred embodiment of the present invention, the polarity conversion group is the group represented by X in a portion of the structure represented by the general formula (KA-1) or (KB-1).

[0339] [Chemical Formula 67]

[0340] In general formula (KA-1) or (KB-1), X represents carboxylic acid ester group: -COO-, acid anhydride group: -C(O)OC(O)-, aceimine group: -NHCONH-, carboxylic acid thioester group: -COS-, carbonate group: -OC(O)O-, sulfate ester group: -OSO 2O-, and sulfonate group: -SO 2O-. Y1 and Y2 can be the same or different, representing electron-withdrawing groups. Furthermore, as a preferred embodiment of the present invention, the above-mentioned compound (B) is a group containing a polar conversion group, containing a group having a partial structure represented by general formula (KA-1) or (KB-1). However, in cases such as the partial structure represented by general formula (KA-1), or the partial structure represented by (KB-1) when Y1 and Y2 are monovalent, if the above-mentioned partial structure does not have a bond, the group having the above-mentioned partial structure is a group having a group in which at least one arbitrary hydrogen atom of monovalent or higher has been removed from the above-mentioned partial structure.

[0341] The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure together with the group that is X. In the general formula (KA-1), X is preferably a carboxylic acid ester group (i.e., in the case where KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group. More preferably, it is a carboxylic acid ester group. The ring structure represented by the general formula (KA-1) can have substituents, for example, it can have nka substituents Z ka1. When there are multiple Z ka1, Z ka1 independently represents alkyl, cycloalkyl, ether, hydroxy, acetamyl, aryl, lactone cycloyl or electron-withdrawing group. Z ka1 can bond together to form a ring. Examples of rings formed by Z ka1 bonding together include cycloalkyl rings and heterocycles (cyclic ether rings, lactone rings, etc.). nka represents an integer from 0 to 10. Preferably, it is an integer from 0 to 8, more preferably an integer from 0 to 5, even more preferably an integer from 1 to 4, and best of all, an integer from 1 to 3.

[0342] As the electron-withdrawing group of Z ka1, it is the same as the electron-withdrawing group of Y 1 and Y 2, which are represented by halogen atoms later. Furthermore, the aforementioned electron-withdrawing groups can be replaced by other electron-withdrawing groups.

[0343] Z ka1 is preferably an alkyl, cycloalkyl, ether, hydroxyl, or electron-withdrawing group, more preferably an alkyl, cycloalkyl, or electron-withdrawing group. Furthermore, as an ether group, it is preferably substituted with an alkyl or cycloalkyl group, i.e., an alkyl ether group. Preferred examples of electron-withdrawing groups are the same as those described later as electron-withdrawing groups for Y 1 and Y 2. Examples of halogen atoms that can be used as Z ka1 include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the most preferred. The alkyl group of Z ka1 may have substituents, which may be straight-chain or branched. As a straight-chain alkyl group, it is preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples include methyl, ethyl, n-propyl, n-butyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. As a branched alkyl group, it is preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and examples include isopropyl, isobutyl, tributyl, isopentyl, tripentyl, isohexyl, trihexyl, isoheptyl, triheptyl, isooctyl, trioctyl, isononyl, tridecyl, etc. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, etc., having 1 to 4 carbon atoms are preferred. The cycloalkyl group of Z ka1 can have substituents and can be monocyclic, polycyclic, or cross-linked. For example, the cycloalkyl group can have a cross-linked structure. As a monocyclic group, it is preferred to be a cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, cyclooctyl, etc. As a polycyclic group, it can be a group with 5 or more carbon atoms having bicyclic, tricyclic, or tetracyclic structures, etc., and is preferably a cycloalkyl group with 6 to 20 carbon atoms, such as adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, and androstenyl, etc. As a cycloalkyl group, the following structure is also preferred. In addition, a portion of the carbon atoms in the cycloalkyl group can be replaced by heteroatoms such as oxygen atoms.

[0344] [Chemical Formula 68]

[0345] Preferred alicyclic moieties include adamantyl, noradamantyl, decahydronaphthyl, tricyclodecyl, tetracyclododecyl, norbornel, cedrolyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. More preferably, adamantyl, decahydronaphthyl, norbornel, cedrolyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and tricyclododecyl are also preferred. Examples of substituents for these alicyclic structures include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. Alkyl groups are preferably lower alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, and more preferably methyl, ethyl, propyl, and isopropyl. Alkoxy groups are preferably methoxy, ethoxy, propoxy, and butoxy groups with 1 to 4 carbon atoms. Substituents that can be present on alkyl and alkoxy groups include hydroxyl groups, halogen atoms, and alkoxy groups (preferably with 1 to 4 carbon atoms).

[0346] As the lactone ring group of Z ka1, examples can be given of groups that remove hydrogen atoms from the structures represented by any of (KA-1-1) to (KA-1-17) described below.

[0347] Aryl groups, such as phenyl and naphthyl groups, can be used as examples of Z ka1.

[0348] Examples of substituents that can be further present in the alkyl, cycloalkyl, and aryl groups of Z ka1 include: hydroxyl; halogen atoms (fluorine, chlorine, bromine, iodine); nitro; cyano; the above-mentioned alkyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, dibutoxy, and terbutoxy; alkoxy groups such as methoxycarbonyl and ethoxycarbonyl; aralkyl groups such as benzyl, phenethyl, and isopropylphenyl; aralkyl groups; acetoalkoxy groups such as methyl, aceto, butyl, benzoyl, cinnamyl, and pentayl; acetooxy groups such as butoxy; the above-mentioned alkenyl groups; alkenyloxy groups such as vinyloxy, propoxy, allyloxy, and butenoxy; the above-mentioned aryl groups; aroxy groups such as phenoxy; and aroxycarbonyl groups such as benzoyloxy.

[0349] In the general formula (KA-1), X is a carboxylic acid ester group. The partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5-7 membered lactone ring. Furthermore, as shown in (KA-1-1) to (KA-1-17) below, it is preferable to form a bicyclic or spirocyclic structure, with other ring structures fused on the 5 to 7-membered lactone ring, which is a partial structure represented by general formula (KA-1). Regarding the ring structure represented by the general formula (KA-1), the surrounding ring structures that can be bonded include, for example, those listed below (KA-1-1) to (KA-1-17) or those based thereon.

[0350] The structure containing the lactone ring structure represented by the general formula (KA-1) is preferably the structure represented by any one of (KA-1-1) to (KA-1-17) below. Furthermore, the lactone structure can be directly bonded to the main chain. Preferred structures are (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), and (KA-1-17).

[0351] [Chemical Formula 69]

[0352] Structures containing the above-described lactone ring structure may or may not have substituents. As preferred substituents, examples can be found that are the same as those that may be present in the ring structure represented by the above general formula (KA-1).

[0353] Although some lactone structures contain optically active substances, any optically active substance can be used. Furthermore, a single optically active substance can be used alone, or multiple optically active substances can be used in combination. When primarily using one optically active substance, its optical purity (ee) is preferably 90% or higher, more preferably 95% or higher, and most preferably 98% or higher.

[0354] As for X in general formula (KB-1), a carboxylic acid ester group (-COO-) is preferably cited.

[0355] In the general formula (KB-1), Y1 and Y2 independently represent electron-withdrawing groups.

[0356] The electron-withdrawing group is preferably a partial structure represented by the following formula (EW). In formula (EW), * indicates a bond directly bonded to (KA-1) or a bond directly bonded to X in (KB-1).

[0357] [Chemical Formula 70]

[0358] In formula (EW), `new` is the repetition number of the linker base represented by `-C(Rew1)(Rew2)-`, and is an integer representing 0 or 1. When `new` is 0, it represents a single bond, indicating a direct bond `Yew1`. Regarding Yew1, examples include halogen atoms, cyano groups, nitrile groups, nitro groups, haloalkyl (cycloalkyl), haloaryl, oxygen, carbonyl, sulfonyl, sulfinyl, and combinations thereof represented by -C(Rf1)(Rf2)-Rf3 as described later. Electron-withdrawing groups can be, for example, the structures described below. Furthermore, "haloalkyl (cycloalkyl)" refers to at least a partially halogenated alkyl or cycloalkyl group. Yew3 and Yew4 each independently represent arbitrary structures. Regardless of the structure of Yew3 and Yew4, the portion of the structure represented by formula (EW) also has electron-withdrawing groups, preferably alkyl, cycloalkyl, or fluorinated alkyl groups.

[0359] [Chemical Formula 71]

[0360] When Yew1 is a divalent or higher group, the remaining bonds are those that form bonds with any atom or substituent. Yew1 is preferably a halogen atom, or a haloalkyl or haloaryl group represented by -C(Rf1)(Rf2)-Rf3. Rew1 and Rew2 each independently represent any substituent, for example, a hydrogen atom, alkyl, cycloalkyl, or aryl group. At least two of R ew1, R ew2 and Y ew1 can be connected to each other to form a loop.

[0361] Here, R f1 represents a halogen atom, a perhaloalkyl, a perhalocycloalkyl, or a perhaloaryl, more preferably a fluorine atom, a perfluoroalkyl, or a perfluorocycloalkyl, and even more preferably a fluorine atom or a trifluoromethyl. Rf2 and Rf3 independently represent a hydrogen atom, a halogen atom, or an organic group, and Rf2 and Rf3 can be linked to form a ring. As an organic group, it may represent, for example, an alkyl group, a cycloalkyl group, an alkoxy group, etc., which can be substituted with a halogen atom (preferably a fluorine atom), and more preferably, Rf2 and Rf3 are (halogenated) alkyl groups. Rf2 is more preferably a group identical to Rf1, or linked with Rf3 to form a ring. Rf1 and Rf3 can be linked to form a ring. Examples of the rings formed include (halogenated) cycloalkyl rings and (halogenated) aryl rings. As for the (halogenated) alkyl groups in Rf1 to Rf3, for example, the alkyl groups in Zka1 mentioned above and their halogenated structures can be cited. In the ring formed by the linkage of Rf1 to Rf3, or Rf2 and Rf3, as (full) halocycloalkyl and (full) haloaryl groups, for example, the cycloalkyl halogenated structure in Z ka1 above can be cited, and more preferably, fluorocycloalkyl groups represented by -C(n)F(2n-2)H and perfluoroaryl groups represented by -C(n)F(n-1) can be cited. Here, the number of carbons n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0362] As a ring formed by linking at least two of Rew1, Rew2 and Yew1 together, cycloalkyl or heterocyclic groups are preferred, with lactone cyclic groups being more preferred as heterocyclic groups. As a lactone ring, for example, structures represented by the above formulas (KA-1-1) to (KA-1-17) can be cited.

[0363] Furthermore, the above compound (B) may have a plurality of partial structures represented by general formula (KA-1), a plurality of partial structures represented by general formula (KB-1), or both partial structures represented by general formula (KA-1) and partial structures represented by general formula (KB-1). Furthermore, some or all of the structures represented by general formula (KA-1) can also function as electron-withdrawing groups as Y1 or Y2 in general formula (KB-1). For example, when X in general formula (KA-1) is a carboxylic acid ester group, that carboxylic acid ester group may also function as an electron-withdrawing group as Y1 or Y2 in general formula (KB-1).

[0364] There are no particular limitations on the group containing the polar conversion group, and examples of organic groups containing polar conversion groups can be given. Examples of organic groups containing polar conversion groups include: alkyl; alkenyl; cycloalkyl; aryl; halogen atom; groups containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and combinations of two or more of these, and groups that give these groups the polar conversion group. Alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof, respectively identical to the alkyl; alkenyl; cycloalkyl; aryl; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; and two or more combinations thereof in the specific examples of substituents as R2 to R4.

[0365] Examples of groups containing a polar conversion group include alkyl groups and aryl groups. As an alkyl group containing a polar conversion group, examples include those that are the same as alkyl groups that are R2 to R4. For example, aryl groups containing polar conversion groups can be identified as those that are the same as aryl groups as R1 and R5.

[0366] In the above general formula (1), R1, R3 and R5 are preferably groups represented by the following general formula (Ar).

[0367] [Chemical Formula 72]

[0368] In the general formula (Ar), R6 to R10 independently represent hydrogen atoms or substituents. At least one of R6 to R10 is: a group containing a polar group; a group containing a group whose polarity increases due to decomposition by the action of an acid; or a group containing a group whose solubility increases in an alkaline developer due to decomposition by the action of an alkaline developer. * indicates a bond formed with the benzene ring in general formula (1).

[0369] Specific examples of substituents for R6 to R10 are the same as those of substituents for R2 to R4 described above. At least one of R6 to R10 is: a group containing a polar group; a group containing a group whose polarity increases due to decomposition by the action of an acid; or a group containing a group whose solubility in an alkaline developer increases due to decomposition by the action of an alkaline developer. A group containing a polar group is the same as a group containing a polar group that is at least one of R1 to R5. A group containing a group whose polarity increases due to decomposition by the action of an acid is the same as a group containing a group whose polarity increases due to decomposition by the action of an acid, which is at least one of R1 to R5. A group containing a group that decomposes under the action of an alkaline developer and thus increases its solubility in an alkaline developer is the same as a group containing a group that decomposes under the action of an alkaline developer and thus increases its solubility in an alkaline developer, which is at least one of R1 to R5.

[0370] Furthermore, in the above general formula (1), R1, R3 and R5 are preferably groups represented by the following general formula (Ar1).

[0371] [Chemical Formula 73]

[0372] In the general formula (Ar1), R11 to R15 each independently represent a hydrogen atom or a substituent, and at least one of R11 to R15 represents the substituent Y described below. * indicates a bond with the benzene ring in general formula (1). Substituent Y: hydroxyl, carboxyl, group with carbonyl bond, acetoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, aminomethyl, or aceimino.

[0373] Specific examples of substituents R11 to R15 are the same as those of substituents R2 to R4 described above. At least one of R 11 to R 15 represents the aforementioned substituent Y.

[0374] Specific examples of groups having carbonyl bonds as substituent Y are the same as the specific examples of groups having carbonyl bonds as polar groups described above. The number of carbon atoms in the acetooxy group of the substituent Y is preferably 1 to 30, and more preferably 1 to 8. The number of carbon atoms in the alkoxycarbonyl group of the substituent Y is preferably 1 to 30, and more preferably 1 to 8. The number of carbon atoms in the aryl group of the aryloxycarbonyl group Y is preferably 6 to 14, and more preferably 6 to 10. The number of carbons in the aryl group of the aryloxycarbonyl group of the substituent Y is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms in the alkoxycarbonyl group of the substituent Y is preferably 1 to 30, and more preferably 1 to 8. The amide group, as a substituent Y, is a group that removes a hydrogen atom from an amide.

[0375] Substituent Y may have carbonyl groups, aceoxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, and aceimin groups, and may further have substituents. As further substituents, specific examples of substituents that can be further present in R1 and R5 can be found in the groups described above.

[0376] In the anion part of general formula (1), n ​​represents the number of anions. n represents an integer greater than or equal to 1. There is no particular upper limit to the value of n, for example, 4. The optimal value for n is 1.

[0377] In general formula (1), Mn+ represents a cation. In the cation part of general formula (1), n ​​represents the valence of the cation. n represents an integer greater than or equal to 1. There is no particular upper limit to the value of n, for example, 4. The optimal value for n is 1. As for the cation of Mn+, there is no particular limitation if it is a cation with a valence of 1 or higher, but it is preferred to be an onium cation, and even more preferably a cation represented by the above formula (ZaI) or formula (ZaII).

[0378] As preferred examples of cations in formula (ZaI), the above-mentioned cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) can be cited. When n is 2 or more, a divalent or higher cation can be a cation having a plurality of structures represented by formula (ZaI). Examples of such cations include divalent cations having a structure in which at least one of R 201 to R 203 of a cation represented by formula (ZaI) is bonded to at least one of R 201 to R 203 of another cation represented by formula (ZaI) by a single bond or a linking group.

[0379] As a preferred example of Mn+ (cation) in general formula (1), specific examples of organic cations of M+ in compounds represented by "M+X-" above can be given.

[0380] The following shows a preferred example of the anionic portion in general formula (1), but the invention is not limited thereto. Me represents methyl.

[0381] [Chemical Formula 74]

[0382] [Chemical Formula 75]

[0383] [Chemical Formula 76]

[0384] [Chemical Formula 77]

[0385] [Chemical Formula 78]

[0386] [Chemical Formula 79]

[0387] The acid produced by the above compound (B) preferably has a pKa of -10 or higher and 5 or lower.

[0388] The following shows a preferred example of a photoacid generator (B), but the invention is not limited thereto. Me represents methyl. Furthermore, as a preferred example of a photoacid generator (B), compounds formed by combining the above-described anion and the above-described cation can also be cited.

[0389] [Chemical Formula 80]

[0390] [Chemical Formula 81]

[0391] [Chemical Formula 82]

[0392] [Chemical Formula 83]

[0393] [Chemical Formula 84]

[0394] Regarding compound (B), for example, it can be synthesized by using a coupling reaction method.

[0395] The so-called coupling reaction, for example, can be applied by Suzuki coupling, etc. For example, by using the known anion exchange method described in Japanese Patent Application Publication No. 6-184170 or other known methods, or by using a conversion method using an ion exchange resin, the counter cation can be converted into the desired cation M+. As a coupling reaction, for example, the following can be cited.

[0396] [Chemical Formula 85]

[0397] X represents a halogen atom, A represents an alkyl group, and R represents a substituent. Y represents the group that forms compound XY through a coupling reaction.

[0398] When the composition of the present invention contains a photoacid generator (B), its content is not particularly limited. However, from the viewpoint that the cross-sectional shape of the formed pattern is closer to a rectangle, its content relative to the total solid content of the composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The above-mentioned content relative to the total solid content of the composition is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less. Photoacid generator (B) can be used alone or in combination with two or more.

[0399] <Acid Diffusion Control Agent (C)> The composition of this invention may contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher, which captures the acid generated from photoacid generators and the like during exposure and inhibits the reaction of acid-decomposing resin in the unexposed area caused by excess generated acid. There are no particular limitations on the types of acid diffusion control agents. For example, basic compounds (CA), low molecular weight compounds (CB) with nitrogen atoms and groups that can be removed by the action of acid, and compounds (CC) whose acid diffusion control ability is reduced or disappears by irradiation with photochemical rays or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids relative to photoacid generators, and basic compounds (CE) whose basicity decreases or disappears upon exposure to photochemical rays or radiation. As a specific example of a basic compound (CA), for example, those described in paragraphs

[0132] to

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

[0137] to

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

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

[0156] to

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

[0305] to

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

[0400] In addition to the above, for example, well-known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[0401] When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (if there are multiple types, the sum of them) relative to the total solid content of the composition is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass. In the composition of this invention, the acid diffusion control agent can be used alone or in combination with two or more.

[0402] <Hydrophobic Resin (D)> The composition of the present invention may further contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to exist on the surface of photoresist films. However, unlike surfactants, their molecules do not necessarily have hydrophilic groups and can also help to uniformly mix polar and non-polar substances. As an effect of adding hydrophobic resin, it can be cited that it controls the static and dynamic contact angle of the photoresist film surface with respect to water, and suppresses gas escape.

[0403] From the viewpoint of surface-biased membrane formation, the hydrophobic resin preferably has one or more of the following structures: fluorine atoms, silicon atoms, and CH3 moieties contained in the side chain portion of the resin; more preferably, it has two or more of these. The aforementioned hydrophobic resin preferably has a hydrocarbon group having five or more carbon atoms. These groups can exist in the main chain of the resin or can be substituted in the side chain. As a hydrophobic resin, the compounds described in paragraphs

[0275] to

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

[0404] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin relative to the total solid content of the composition is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass.

[0405] <Surfactant (E)> The composition of this invention may contain surfactants. When surfactants are present, patterns with better adhesion and fewer development defects can be formed. Fluorine-based and / or silicone-based surfactants are preferred. As fluorine-based and / or silicon-based surfactants, examples include the surfactants disclosed in paragraphs

[0218] and

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

[0406] These surfactants can be used alone or in combination with more than one type.

[0407] When the composition of the present invention contains a surfactant, the content of the surfactant, relative to the total solid content of the composition, is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0408] <Solvent(F)> The composition of the present invention preferably contains a solvent. The solvent preferably comprises at least one of (M1) and (M2), wherein (M1) is a propylene glycol monoalkyl ether carboxylic acid ester, and (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones, and alkyl carbonates. Furthermore, the solvent may further comprise components other than (M1) and (M2).

[0409] From the viewpoint of improving the coatability of the photoresist composition and reducing the number of development defects in the pattern, it is preferable to combine the above-mentioned solvent and the above-mentioned resin. Since the above-mentioned resin has a good balance of solubility, boiling point and viscosity, the above-mentioned solvent can suppress uneven film thickness of the photoresist film and the generation of precipitates during spin coating. Details of the ingredients (M1) and (M2) are described in paragraphs

[0218] to

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

[0410] When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of solvent.

[0411] The solvent content in the composition of the present invention is preferably set such that the solid component concentration is 0.5-30% by mass, more preferably 1-20% by mass. This can further improve the coatability of the composition.

[0412] Furthermore, the term "solid component" refers to all components other than the solvent, as mentioned above, meaning the components that form photosensitive or radiosensitive linear films. The term "solid component concentration" refers to the percentage of the mass of components other than the solvent relative to the total mass of the composition of this invention. The term "total solids content" refers to the total mass of the components after removing the solvent from the entire composition of the present invention. Furthermore, the term "solids content," as described above, refers to the components after removing the solvent; for example, it may be a solid or a liquid at 25°C.

[0413] <Other Additives> The composition of the present invention may further contain a solubility-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility relative to the developer (e.g., a phenolic compound with a molecular weight of less than 1000, or an alicyclic or aliphatic compound containing a carboxyl group).

[0414] The aforementioned "dissolution-inhibiting compounds" refer to compounds with a molecular weight of less than 3000 that have reduced solubility in organic developing solutions due to acid decomposition.

[0415] The composition described in this specification is suitable for use as a photosensitive composition for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm). Therefore, the number of incident photons is lower when exposed at the same sensitivity. Consequently, "photon shot noise," which has a probabilistic bias in the number of photons, has a greater impact, leading to LER degradation and bridging defects. To reduce photon shot noise, one method is to increase the exposure to increase the number of incident photons, but this must be balanced with the requirement for high sensitivity.

[0416] [Photosensitive or radiosensitive linear films, pattern formation methods] The steps of the pattern forming method using the composition of the present invention described above are not particularly limited, but a pattern forming method having the following process is preferred. Process 1: A process for forming a photosensitive radiosensitive or radiosensitive linear film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition. Process 2: The process of exposing the above-mentioned photosensitive radioactive or radiosensitive linear film. Process 3: The process of developing the exposed photosensitive or radiosensitive linear film with a developing solution. The steps of each of the above processes will be described in detail below.

[0417] (Process 1: Formation process of photosensitive radioactive or radiosensitive linear film) Process 1 is a process of forming a photosensitive radioactive or radiosensitive linear film on a substrate using the components of the present invention.

[0418] As a method for forming a photosensitive radioactive or radioactive linear film on a substrate by means of 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. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0419] Photosensitive or radiosensitive linear resin compositions can be applied to substrates (e.g., silicon, silicon dioxide coatings) used for manufacturing integrated circuit elements by appropriate coating methods such as spin coaters or coaters. Spin coater application is preferred. The rotation speed when using a spin coater is preferably 1000–3000 rpm. After coating with a photosensitive or radiosensitive linear resin composition, the substrate can be dried to form a photosensitive or radiosensitive linear film. Furthermore, depending on the requirements, various substrate films (inorganic films, organic films, antireflective films) can be formed under the photosensitive or radiosensitive linear film.

[0420] As a drying method, for example, drying by heating can be cited. Heating can be carried out using the equipment provided in a conventional exposure machine and / or developing machine, or it can be carried out using a hot plate. The heating temperature is preferably 80~150°C, more preferably 80~140°C, and even more preferably 80~130°C. The heating time is preferably 30~1000 seconds, more preferably 60~800 seconds, and even more preferably 60~600 seconds.

[0421] There is no particular limitation on the thickness of the photosensitive or linearly photosensitive film (typically a photoresist film), but from the viewpoint of forming finer patterns with higher precision, a thickness of 10 to 120 nm is preferred. Specifically, when using EUV exposure, the thickness of the photoresist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the thickness of the photoresist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0422] In addition, a topcoat composition can be used to form a topcoat on the top layer of the photoresist film. The composition of the top coating is preferably not mixed with the photoresist film and can be uniformly coated on the upper layer of the photoresist film. The top coating is not particularly limited and can be formed by previously known methods, for example, the top coating can be formed according to paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the photoresist film. Specific examples of alkaline compounds that can be contained in the top coating include alkaline compounds that can be contained in photosensitive or radiosensitive linear resin compositions. 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.

[0423] (Process 2: Exposure Process) Process 2 is a process for exposing photosensitive radioactive or radiosensitive linear films. As a method of exposure, one example is irradiating the formed photosensitive or radiosensitive linear film with photosensitive rays or radiation through a prescribed mask. Examples of photochemical rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Far ultraviolet light with wavelengths below 250 nm, more preferably below 220 nm, and especially preferably 1-200 nm can be cited. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0424] It is preferable to bake (heat) after exposure and before development. Baking promotes the reaction of the exposed part, thereby improving sensitivity and pattern shape. The preferred heating temperature is 80~150℃, more preferably 80~140℃, and even more preferably 80~130℃. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using the equipment found in conventional exposure machines and / or developing machines, or it can be done using hot plates, etc. This process is also known as post-exposure baking.

[0425] (Process 3: Development Process) Process 3 uses a developer to develop the exposed photosensitive or radiosensitive linear film to form a pattern. The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as an organic developer).

[0426] Examples of development methods include, for instance, immersing the substrate in a tank filled with developer for a certain time (immersion method), using surface tension to cause developer to accumulate on the substrate surface and leave it to stand for a certain time to perform development (puddle method), spraying developer onto the substrate surface (spraying method), and continuously spraying developer from a nozzle on a substrate rotating at a certain speed while scanning at a certain speed (dynamic distribution method). Furthermore, after the developing process, a process can also be implemented where the developing process is stopped while the solvent is being replaced with another solvent. The development time is only the time required for the resin in the unexposed areas to fully dissolve, and there are no particular restrictions. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The optimal temperature for the developer is 0~50℃, and more preferably 15~35℃.

[0427] Alkaline developer is preferably an alkaline aqueous solution containing an alkali. There are no particular limitations on the type of alkaline aqueous solution; examples include alkaline aqueous solutions containing quaternary ammonium salts (represented by tetramethylammonium hydroxide), inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, or cyclic amines. Among these, an aqueous solution of a quaternary ammonium salt (represented by tetramethylammonium hydroxide, TMAH) is preferred. Appropriate amounts of alcohols, surfactants, etc., can be added to the alkaline developer. The alkali concentration of the alkaline developer is typically preferred to be 0.1% to 20% by mass. The pH of the alkaline developer is typically preferred to be 10.0 to 15.0.

[0428] 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.

[0429] The solvents described above can be mixed in multiple ways, or mixed with solvents other than those described above, or with water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and most preferably substantially water-free. The content of organic solvent relative to the organic developer, relative to the total amount of developer, is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and especially preferably 95% by mass or more and 100% by mass or less.

[0430] (Other processes) The above-mentioned pattern formation method preferably includes a cleaning process with rinsing solution after process 3.

[0431] As a rinsing solution used in the rinsing process following development with an alkaline developer, pure water can be cited as an example. Furthermore, an appropriate amount of surfactant can be added to the pure water. An appropriate amount of surfactant can also be added to the rinsing solution.

[0432] The rinsing solution used in the rinsing process after the developing process using an organic developer is not particularly restricted, as long as it does not dissolve the pattern. Solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0433] There are no particular limitations on the rinsing process. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion), and spraying rinsing liquid onto the surface of the substrate (spraying). Furthermore, the pattern forming method can include a post-bake process after the washing process. This process removes residual developer and washing solution between and inside the pattern through baking. Additionally, this process also anneals the photoresist pattern and improves its surface roughness. The post-wash heating process is typically performed at 40–250°C (preferably 90–200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0434] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the lower film and substrate) and form a pattern on the substrate. There are no particular limitations on the processing method of the substrate (or the lower film and the substrate), but it is preferable to use the pattern formed in process 3 as a mask and form the pattern on the substrate (or the lower film and the substrate) by dry etching. Dry etching is preferably oxygen plasma etching.

[0435] The components of this invention and the various materials used in the pattern forming method described herein (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. There is no particular limitation on the lower limit, but it is preferably 0 ppt by mass or more. Examples of metallic impurities include, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0436] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. Details of filtration using a filter are described in paragraph

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

[0437] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials for various materials, filtering the raw materials for various materials with filters, and using TEFLON (registered trademark) to form a lining in the apparatus to carry out distillation under conditions that suppress contamination as much as possible.

[0438] In addition to filtration, impurities can also be removed using adsorption materials, or a combination of filtration and adsorption materials can be used. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the metal content in the cleaning solution used to clean the manufacturing apparatus. The metal content in the used cleaning solution is preferably less than 100 parts per trillion (ppt), more preferably less than 10 ppt, and even more preferably less than 1 ppt. There is no particular lower limit, but it is preferably 0 ppt or more.

[0439] Conductive compounds can be added to organic processing solutions such as rinsing solutions to prevent malfunctions in the solution piping and various components (filters, O-rings, and tubing) caused by static electricity and subsequent electrostatic discharge. There are no particular limitations on the conductive compounds; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining better developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There are no particular limitations on the lower limit, but it is preferably 0.01% by mass or more. For example, SUS (stainless steel) or various pipes coated with anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used for chemical fluid piping. Similarly, for filters and O-rings, anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can also be used.

[0440] Manufacturing methods for electronic devices This specification also includes the above-mentioned pattern forming method, which relates to a method for manufacturing electronic devices and electronic devices manufactured by the method. As a preferred embodiment of the electronic device described in this specification, it may be embodied in electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.). [Example]

[0441] The present invention will be described in more detail below based on embodiments. The materials, amounts, ratios, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0442] <Synthesis Example 1: Synthesis of Resin A-11> (Synthesis of monomer (a-1)) Synthesized according to the method described in Polym. Chem. 2019, 10, 2764.

[0443] (Synthesis of Resin A-11)

[0444] [Chemical Formula 86]

[0445] Using (M-1), (M-2), and (a-1) as monomers, the monomers were mixed in a molar ratio of (M-1):(M-2):(a-1) = 65 / 10 / 25. Cyclohexanone was added to prepare a monomer solution with a concentration of 30% by mass. 8 mol% of dimethyl 2,2'-azobis(2-methylpropionate) was added as an initiator to prepare the monomer solution. Under a nitrogen atmosphere, 0.1 times the mass of cyclohexanone in the above monomer solution was heated to 85°C. After 2 hours, the monomer solution was added dropwise, and the reaction was carried out at 85°C for another 2 hours. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), allowing the resin to precipitate. After precipitation, filtration, recovery, and vacuum drying, resin A-11 was obtained in a yield of 66%.

[0446] [Various components of photosensitive or radiosensitive linear resin compositions] <Resin(A)> The structure of the resin (A) used (resin A-1 to A-46) is shown below. The raw material monomers, excluding monomer (a-1), in the repeating unit represented by general formula (a) are synthesized according to the description in Polym. Chem. 2016, 7, 4427 2 and International Publication No. 2021 / 071432, etc. Resins A-1 to A-10 and A-12 to A-46 are synthesized using the same method as resin A-11 described above. Table 1 shows the type and content (content ratio (mol%), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit. In Table 1, the repeating units (a-1) to (a-20) corresponding to the repeating unit (a) shown in repeating unit 2 are repeating units derived from the raw material monomers (a-1) to (a-20) described later. The weight-average molecular weight (Mw) and dispersity (Mw / Mn) of resins A-1 to A-46 were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the ratio of each repeating unit was determined by 13C-NMR (nuclear magnetic resonance).

[0447] [Table 1]

[0448] The structural formulas of each repeating unit shown in Table 1 are as follows. For repeating units corresponding to repeating unit (a) shown in repeating unit 2, the structural formulas of the corresponding raw material monomers are shown.

[0449] [Chemical Formula 87]

[0450] [Chemical Formula 88]

[0451] [Chemical Formula 89]

[0452] [Chemical Formula 90]

[0453] In the comparative examples, resins (AX-1) to (AX-3) were used. The content (content ratio (mol%)), weight-average molecular weight (Mw), and dispersibility (Mw / Mn) of each repeating unit are shown. The weight-average molecular weight (Mw) and dispersibility (Mw / Mn) were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the ratio of each repeating unit was determined by 13C-NMR (nuclear magnetic resonance).

[0454] [Chemical Formula 91]

[0455] [Photoacid generator (B)] The structure of the photoacid generator (B) used is shown below. Compounds (B-1) to (B-80) are formed by combining the cations and anions listed in Table 2. In the preparation of the composition, compounds (B-3), (B-4), (B-7), (B-8), (B-11), (B-12), (B-15), (B-17)~(B-19), (B-29)~(B-32), (B-35)~(B-37), (B-43)~(B-49), (B-53), (B-56), (B-58), (B-62), (B-63), (B-66), (B-67), (B-70), (B-72), (B-73), (B-76), (B-77), and (B-80) from the above-mentioned compounds were used.

[0456] [Table 2]

[0457] The structures of the cations listed in Table 2 are shown below. Me represents methyl, and Bu represents n-butyl.

[0458] [Chemical Formula 92]

[0459] [Chemical Formula 93]

[0460] The structures of the anions listed in Table 2 are shown below. Me represents methyl, and Bu represents n-butyl.

[0461] [Chemical Formula 94]

[0462] [Chemical Formula 95]

[0463] [Chemical Formula 96]

[0464] [Chemical Formula 97]

[0465] [Chemical Formula 98]

[0466] [Acid diffusion control agent] The structure of the acid diffusion control agent used is shown below.

[0467] [Chemical Formula 99]

[0468] [Surfactants] The following W-1 to W-4 were used as surfactants. W-1:MEGAFAC R08 (Made by Dai Nippon Ink & Chemical Co., Ltd.; Fluorine and Silicon Based) W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.; silicon-based) W-3: Troysol S-366 (manufactured by Troy Chemical Industries; fluorine-based) W-4: PF6320 (manufactured by Omnova; fluorine-based)

[0469] [Solvent] The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Diacetone alcohol (DAA) S-3: Propylene glycol monomethyl ether (PGME) S-4: Ethyl lactate (EL) S-5: Ethyl 3-ethoxypropionate (EEP) S-6:2-Heptanone (MAK) S-7: Methyl 3-methoxypropionate (MMP) S-8: 3-Methoxybutyl Acetate S-9: γ-Butyrolactone

[0470] [Preparation and application of coating solution for photoresist composition] (1) Preparation of the support An 8-inch wafer (which has been subjected to a masking film treatment used for a normal blank photomask) with Cr oxynitride vapor-deposited thereon was prepared. (2) Preparation of the photoresist composition The components shown in Table 3 were dissolved in the solvent shown in the same table, and a solution was prepared according to the solid component concentration shown in the same table. The solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a photoresist composition. In addition, in Table 3 below, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid components. Also, the content ratio (mass %) of the solvent used relative to the total solvent is described in Table 3 below. (3) Fabrication of the photoresist film Using a spin coater Mark8 manufactured by Tokyo Electron Limited, the photoresist composition was coated on the above-mentioned 8-inch wafer and dried on a hot plate at 120 °C for 600 seconds to obtain a photoresist film with a film thickness of 100 nm. That is, a wafer coated with the photoresist was obtained.

[0471] [Table 3]

[0472] [Table 4]

[0473] [EB exposure and development] (4) Fabrication of the photoresist pattern Using an electron beam lithography apparatus (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV), the photoresist film obtained in (3) above was irradiated with a pattern. After the irradiation, it was heated on a hot plate at 100 °C for 600 seconds, immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, then rinsed with water for 30 seconds and dried.

[0474] [Evaluation] (5) Evaluation of the photoresist pattern The resolution, roughness performance, and pattern shape of the obtained pattern were evaluated by the following method. The results are shown in Table 4 below.

[0475] The irradiation energy when analyzing a 1:1 line and space pattern with a line width of 50 nm was used as the sensitivity (Eop).

[0476] <L / S resolution> The resolution (nm) will be the minimum linewidth at which the line and space (line:space = 1:1) are separated and resolved at the exposure of the above sensitivity (Eop).

[0477] <Roughness performance> As described below, the roughness performance was evaluated using linewidth roughness (LWR). The linewidth roughness is determined under the aforementioned Eop condition. For any 50 points with a linewidth of 50 nm and a spatial pattern (line:space = 1:1) with a long side of 0.5 μm, the linewidth is measured, and the standard deviation is calculated to obtain 3σ (nm). The smaller this value, the better the performance.

[0478] <Pattern Shape> The cross-sectional shape of a 1:1 line with a linewidth of 50 nm and a spatial pattern under the above-mentioned irradiation dose was observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). Among the observed cross-sectional shapes of the line patterns, those with a ratio of [linewidth at the top (surface part) of the line pattern / linewidth at the middle part of the line pattern (position of half the height of the line pattern)] of 1.1 or more were defined as "inverted cone", those with a ratio of 1.03 or more but less than 1.1 were defined as "slightly inverted cone", and those with a ratio less than 1.03 were defined as "rectangular".

[0479] [Table 5]

[0480] As can be seen from the results in Table 4, the composition of the present invention has excellent resolution and excellent roughness performance in the formation of extremely fine patterns (especially when the line width or spacing is less than 20 nm), and can obtain excellent pattern shapes.

[0481] Extreme ultraviolet (EUV) exposure and development (4) Fabrication of photoresist patterns Using an EUV exposure apparatus (manufactured by Exitech Company, Micro Exposure Tool, numerical aperture (NA) 0.3, Quadrupole, outer sigma (σ) 0.68, inner sigma (σ) 0.36), with an exposure mask (line / space = 1 / 1), pattern exposure was performed on the wafer coated with a photoresist film obtained in (3) above. After exposure, on a hot plate, after heating at 100 °C for 90 seconds, it was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Then, the wafer was rotated at a speed of 4,000 rpm for 30 seconds, and then baked at 95 °C for 60 seconds for drying.

[0482] [Evaluation] (5) Evaluation of photoresist pattern The resolution, roughness performance, and pattern shape of the obtained pattern were evaluated by the following method. The results are shown in Table 5 below.

[0483] The irradiation energy when analyzing a 1:1 line and space pattern with a line width of 50 nm was taken as the sensitivity (Eop).

[0484] <L / S Resolution> The limit resolution (the minimum line width for separating a line and space (line:space = 1:1) analysis) at the exposure amount showing the above sensitivity (Eop) was taken as the resolution (nm).

[0485] <Roughness Performance> As described below, the roughness performance was evaluated using line width roughness (LWR). The line width roughness was measured at 50 arbitrary points in the long side direction of 0.5 μm of a line and space pattern (line:space = 1:1) with a line width of 50 nm at the above Eop, the line widths of these were measured, the standard deviation of these was calculated, and 3σ (nm) was thus calculated. The smaller this value, the better the performance.

[0486] <Pattern Shape> The cross-sectional shape of a 1:1 line with a linewidth of 50 nm and a spatial pattern under the above-mentioned irradiation dose was observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). Among the observed cross-sectional shapes of the line patterns, those with a ratio of [linewidth at the top (surface portion) of the line pattern / linewidth at the middle (half the height of the line pattern)] of 1.1 or more were defined as "inverted cone", those with a ratio of 1.03 or more but less than 1.1 were defined as "slightly inverted cone", and those with a ratio less than 1.03 were defined as "rectangular".

[0487] [Table 6]

[0488] As can be seen from the results in Table 5, the composition of the present invention has excellent resolution and excellent roughness performance in the formation of extremely fine patterns (especially when the line width or spacing is less than 20 nm), and can obtain excellent pattern shapes. [Industrial Applicability]

[0489] The present invention provides a photosensitive radioactive or radioactive linear resin composition that not only has excellent resolution and roughness performance in the formation of extremely fine patterns (especially with linewidth or spacing of 20 nm or less), but also produces excellent pattern shapes; a photosensitive radioactive or radioactive linear film formed from the photosensitive radioactive or radioactive linear resin composition; a pattern forming method using the photosensitive radioactive or radioactive linear resin composition; and a method for manufacturing electronic devices.

[0490] Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2022-027347, filed on February 24, 2022, the contents of which are incorporated herein by reference.

[0491] none

Claims

1. A photosensitive radioactive or radiosensitive linear resin composition comprising a resin (A) comprising a repeating unit (a) represented by the following general formula (a) and repeating units having acid groups, wherein the content of acid groups in the resin (A) is 0.2 to 6.0 mmol / g, wherein in the general formula (a), A represents an aromatic cyclic group or an aromatic heterocyclic group, X represents a single bond, an alkyl group, an alkenyl group, an alkyne group, a carbonyl group, a sulfonyl group, or a group composed of such combinations, X can be bonded to the A ring to form a benzene ring, Y1 and Y2 independently represent an oxygen atom or a sulfur atom, respectively, and R11 and R12 independently represent a hydrogen atom, an organic group, or a halogen atom, respectively.

2. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The repeating unit with an acid group is a repeating unit with a phenolic hydroxyl group.

3. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The repeating unit with an acid group is a repeating unit represented by the following general formula (B), in which R3 represents a hydrogen atom or a monovalent organic group, R4 and R5 independently represent a hydrogen atom, a halogen atom or an alkyl group, L2 represents a single bond or an ester bond, L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1), R6 represents a hydroxyl group or a fluorinated alcohol group, R7 represents a halogen atom, m represents an integer greater than or equal to 1, and n represents an integer greater than or equal to 0 or 1.

4. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The repeating unit with an acid group is represented by the following general formula (c), in which R61 to R63 independently represent a hydrogen atom, an organogroup or a halogen atom, wherein R62 can bond with Ar to form a ring, in which case R62 represents a single bond or an alkyl group, L represents a single bond or a divalent linker, Ar represents an aromatic cyclic group with a (k+1) valence, and when it bonds with R62 to form a ring, it represents an aromatic cyclic group with a (k+2) valence, where k represents an integer from 1 to 5.

5. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 4, wherein, In general formula (a), Y1 and Y2 both represent oxygen atoms.

6. The photosensitive radioactive or radiolinear resin composition as described in any one of claims 1 to 4, wherein, In general formula (a), X represents a single bond, methylene, ethyl or carbonyl.

7. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 4, wherein, In general formula (a), X represents methylene, ethyl, or carbonyl.

8. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 4, wherein, In general formula (a), X represents carbonyl group.

9. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 4, wherein, In general formula (a), A represents an aromatic ring group.

10. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 4, wherein, The repeating unit represented by the general formula (a) is the repeating unit represented by the following general formula (a-1). In general formula (a-1), R11 and R12 independently represent hydrogen atoms, organic groups or halogen atoms, respectively, and R21 independently represent hydrogen atoms, organic groups or halogen atoms, respectively. R21 can bond with each other to form a ring.

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

12. A method for forming a pattern, comprising: A process for forming a photosensitive radioactive or radioactive linear film on a substrate using any one of claims 1 to 10; an exposure process for exposing the photosensitive radioactive or radioactive linear film; and a development process for developing the exposed photosensitive radioactive or radioactive linear film using a developing solution.

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