Actinic ray–sensitive or radiation-sensitive resin composition, actinic ray–sensitive or radiation-sensitive film, pattern formation method, and production method for electronic device

Abstract

Provided are: an actinic ray–sensitive or radiation-sensitive resin composition that contains a resin that increases in polarity under the action of an acid and a photoacid generator, the composition containing two or more components that each include metal atoms, the total amount of metal atoms in the two or more components being at least 4.0 mass% of the total solid content of the composition; an actinic ray–sensitive or radiation-sensitive film that is formed using the composition; a pattern formation method that uses the composition; and a production method for an electronic device.

Description

Photosensitive or radiation-sensitive resin composition, photosensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic devices.

[0001] The present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device that can be suitably used in ultramicrolithography processes applicable to the manufacturing processes of ultra-LSI (Large Scale Integration) and high-capacity microchips, nanoimprint mold creation processes, and high-density information recording media, as well as other photofabrication processes.

[0002] Traditionally, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations), microfabrication has been performed using lithography with resist compositions. In recent years, with the increasing integration of integrated circuits, there has been a growing demand for the formation of ultrafine patterns in the submicron or quarter-micron region. Accordingly, there has been a trend toward shorter exposure wavelengths, from the g-line to the i-line, and further to KrF excimer laser light. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as the light source have been developed. Furthermore, as a technique to further improve resolution, development of the so-called immersion method has been progressing, in which a high refractive index liquid (hereinafter also called "immersion liquid") 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 being developed. Accordingly, resist compositions that are effectively sensitive to various types of active light or radiation are being developed.

[0004] Patent Document 1 describes a resist material comprising a base resin containing repeating units containing metal atoms and acid-unstable groups.

[0005] Japanese Patent Application Publication No. 2017-83505

[0006] In recent years, the performance requirements for resist compositions and pattern formation methods have become increasingly stringent. In particular, further improvements are needed in sensitivity and LCDU (Local Critical Dimension Uniformity). Furthermore, as resist films become thinner, excellent etching resistance is also required. In other words, a large residual film thickness is also required after the resist film formed on the substrate is subjected to etching.

[0007] The present invention aims to provide a photosensitive or radiation-sensitive resin composition capable of forming patterns with excellent sensitivity and LCDU, and also capable of forming resist films with excellent etching resistance. Furthermore, the present invention aims to provide a photosensitive or radiation-sensitive film formed using the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0008] The inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A photosensitive or radiation-sensitive resin composition comprising a resin whose polarity increases by the action of an acid, and a photoacid generator, wherein the composition comprises two or more components, each having a metal atom, and the total amount of metal atoms in the two or more components is 4.0% by mass or more with respect to the total solid content of the composition. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the two or more components comprise a first component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony, and a second component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony.

[0010] [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the total amount of metal atoms is 6.0% by mass or more with respect to the total solid content of the composition. [4] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the total amount of metal atoms is 8.0% by mass or more with respect to the total solid content of the composition. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein at least one of the metal atoms is an atom selected from Group 13 to Group 16.

[0011] [6] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein at least one of the metal atoms is an organometallic atom. [7] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin has metal atoms in its side chains. [8] A photosensitive or radiation-sensitive film formed using a photosensitive or radiation-sensitive resin composition according to any one of [1] to [7].

[0012] [9] A pattern forming method comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition according to any one of [1] to [7]; exposing the resist film; and developing the exposed resist film using a developer.

[10] The pattern forming method according to [9], wherein the developer is an alkaline developer or a developer containing an organic solvent.

[11] A method for manufacturing an electronic device, comprising the pattern forming method according to [9] or

[10] .

[0013] The present invention provides a photosensitive or radiation-sensitive resin composition that can form patterns with excellent sensitivity and LCDU, and can also form resist films with excellent etching resistance. Furthermore, the present invention provides a photosensitive or radiation-sensitive film formed using the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0014] The present invention will now be described in detail. The following descriptions of the constituent elements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0015] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure with emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, and EUV, but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. In this specification, "~" is used to mean that the values ​​written before and after it are included as the lower and upper limits.

[0016] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Also, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0017] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene equivalent values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0018] In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both groups with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from, for example, the following substituent T.

[0019] (Substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl groups, etc. Examples of substituents include acyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; and non-aromatic heterocyclic groups such as tetrahydrofuranyl and morpholino groups. Furthermore, if these substituents can have one or more substituents, groups having one or more substituents selected from the substituents listed above (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) are also included as examples of substituent T.

[0020] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -COO-, Y may also be -CO-O- or -O-CO-. The above compound may also be "X-CO-O-Z" or "X-O-CO-Z".

[0021] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the following software package 1 based on a database of Hammett substituent constants and known literature values. All pKa values ​​described herein are calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0022] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated using, for example, the Density Functional Theory (DFT), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT, such as Gaussian 16.

[0023] In this specification, pKa refers to the value calculated using software package 1 based on a database of Hammett substituent constants and known literature values, as described above. However, if pKa cannot be calculated by this method, the value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above. However, if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0024] In this specification, "solids" means components contained in a photosensitive or radiation-sensitive resin composition that form a photosensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component contained in a photosensitive or radiation-sensitive resin composition that forms a photosensitive or radiation-sensitive film shall be considered a solid, even if its state is liquid.

[0025] [Photosensitive or Radiation-Sensitive Resin Composition] The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is a photosensitive or radiation-sensitive resin composition containing a resin whose polarity increases by the action of an acid, and a photoacid generator, wherein the composition contains two or more components, each having a metal atom, and the total amount of metal atoms in the two or more components is 4.0% by mass or more with respect to the total solid content of the composition.

[0026] The reason why the composition of the present invention makes it possible to form patterns with excellent sensitivity and LCDU, and also to form a resist film with excellent etching resistance, is not entirely clear, but the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism below. The presence of metal atoms in the resist composition makes it easier to absorb light, thus improving sensitivity. If only one component of the resist composition contains metal atoms, the metal atoms are localized, so it is thought that there are areas where light is absorbed and the reaction proceeds, and areas where the reaction does not proceed easily. In contrast, the composition of the present invention contains two or more components, each having metal atoms, and the total amount of metal atoms in the two or more components in the composition is above a predetermined amount, so the metal atoms can be delocalized, allowing light to be absorbed overall, which makes it easier for the reaction to proceed overall and improves sensitivity.

[0027] Furthermore, the presence of metal atoms in the resist composition suppresses shot noise (specifically EUV), and this effect improves as the metal atom content increases. However, if only one component of the resist composition contains metal atoms, the metal atoms are localized, leading to localized high concentrations and variations in concentration. While shot noise is suppressed in areas where metal atoms are locally present, it is not suppressed in other areas, resulting in overall variations. In contrast, the composition of the present invention contains two or more components, each having metal atoms, and the total amount of metal atoms in these two or more components in the composition is above a predetermined amount. Therefore, the metal atoms can be delocalized, suppressing shot noise overall, and thus improving the LCDD (Liquid Chance Unit).

[0028] While a high metal atom content in a resist composition improves the etching resistance of the resist film, if only one component of the resist composition contains metal atoms, the metal atoms are localized, leading to localized high concentrations and variations in the concentration of metal in the resist film. As a result, etching resistance improves only in the areas where metal atoms are locally present. In other words, there are areas with good etching resistance and areas with high film wear. On average, the residual film thickness decreases. In contrast, the composition of the present invention contains two or more components, each containing metal atoms, and the total amount of metal atoms in these two or more components in the composition is above a predetermined amount. Therefore, the metal atoms can be delocalized, resulting in an overall improvement in the residual film thickness after etching of the resist film, and thus the resist film exhibits superior etching resistance.

[0029] The composition of the present invention is preferably a composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid. The composition of the present invention is preferably a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. The composition of the present invention may be a resist composition for alkaline development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0030] The composition of the present invention contains two or more components each having a metal atom. In the above-mentioned two or more components, the term "component" refers to a repeating unit constituting a resin, not the resin itself, in the case of a resin. In the case of an ionic compound having a cation and an anion, the term refers to the cation and the anion, not the ionic compound itself. Furthermore, in the case of a nonionic compound having neither a cation nor an anion, the term refers to the nonionic compound. For example, when a repeating unit of a resin has a repeating unit having a photoacid-generating group described below, each of the cation and the anion in the photoacid-generating group is referred to as a "component". For example, when the photoacid generator described below is an ionic compound having a cation and an anion, and each of the cation and the anion has a metal atom, the cation and the anion are each referred to as a "component". The above-mentioned two or more components are two or more components, and may be three or more components.

[0031] The metal atom each contained in two or more components is not particularly limited, and examples thereof include metal atoms from Groups 1 to 16 of the periodic table. Specifically, atoms in the 2nd to 7th periods of the periodic table and belonging to Groups 1 to 2, atoms in the 4th to 7th periods of the periodic table and belonging to Groups 3 to 12, atoms in the 3rd to 7th periods of the periodic table and belonging to Group 13, atoms in the 4th to 7th periods of the periodic table and belonging to Group 14, atoms in the 5th to 7th periods of the periodic table and belonging to Group 15, an atom in the 6th to 7th periods of the periodic table and belonging to Group 16, or an atom in the 7th period of the periodic table and belonging to Group 17, can be mentioned.

[0032] The metal atoms may be one type or two or more types. In a preferred embodiment, it is preferable that at least one of the metal atoms is selected from groups 13 to 16. Specifically, the atoms selected from groups 13 to 16 are, as described above, atoms from the 3rd to 7th period of the periodic table and in group 13, atoms from the 4th to 7th period of the periodic table and in group 14, atoms from the 5th to 7th period of the periodic table and in group 15, atoms from the 6th to 7th period of the periodic table and in group 16, or atoms from the 7th period of the periodic table and in group 17. It is preferable that the metal atoms are from the 4th to 6th period of the periodic table and in groups 13 to 16. The metal atom is preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, lead, indium, and antimony; more preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, and lead; even more preferably at least one selected from the group consisting of germanium, bismuth, gallium, and tin; and particularly preferably germanium or bismuth. The metal atom is preferably chemically bonded to other atoms, and more preferably covalently bonded. The metal atom may be charged. The charge may be positive or negative. In one preferred embodiment, it is preferable that at least one of the metal atoms is an organometallic. Specifically, an organometallic refers to a metal atom that is covalently bonded to at least one carbon atom.

[0033] In one preferred embodiment, the two or more components preferably include a first component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony, and a second component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony, and more preferably include a first component having a metal atom that is germanium or bismuth, and a second component having a metal atom that is germanium or bismuth.

[0034] In the composition of the present invention, the total amount of metal atoms in two or more components is 4.0% by mass or more relative to the total solid content of the composition. Preferably, the total amount of metal atoms is 6.0% by mass or more, and more preferably 8.0% by mass or more, relative to the total solid content of the composition. Furthermore, it is preferable that the total amount of metal atoms is 50% by mass or less relative to the total solid content of the composition. The types of metal atoms and their content in the composition of the present invention can be determined, for example, from the content values ​​of each compound in the formulation of the composition of the present invention. The content of metal atoms can also be measured by energy-dispersive X-ray spectroscopy, wavelength-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Rutherford X-ray spectroscopy, glow discharge emission spectroscopy, secondary ion mass spectrometry, inductively coupled plasma mass spectrometry, etc.

[0035] <Resin whose polarity increases due to the action of acid> The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") whose polarity increases due to the action of acid. Resin (A) preferably contains a group that decomposes and increases in polarity due to the action of acid (also referred to as "acid-degradable group"), and more preferably contains repeating units having an acid-degradable group. When resin (A) has an acid-degradable group, in a pattern forming method using the composition of the present invention, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic developer is used as the developer, a negative-type pattern is suitably formed. In one preferred embodiment, resin (A) preferably has a metal atom in its side chain. The metal atom is not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, it is the same as above, and the preferred range is also the same.

[0036] (Repeating units having acid-degradable groups) The acid-degradable groups are preferably groups that decompose upon the action of an acid to produce polar groups. The acid-degradable groups are preferably in a structure in which the polar groups are protected by groups that leave upon the action of an acid (leaving groups). The resin (A) preferably has repeating units having groups that decompose upon the action of an acid to produce polar groups, thereby increasing polarity upon the action of an acid, increasing solubility in alkaline developers, and decreasing solubility in organic solvents.

[0037] Examples of the polar group include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group. Preferably, the polar group is a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

[0038] Examples of the group that is eliminated by the action of an acid include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx １ )(Rx ２ )(Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ )(Rx ２ )(Rx ３ ) Formula (Y3): -C(R ３６ )(R ３７ )(OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0039] In formulas (Y1) and (Y2), Rx １ to Rx ３ each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx １ to Rx ３ are alkyl groups (linear or branched), it is preferable that at least two of Rx １ to Rx ３ are methyl groups. Among these, it is preferable that Rx １ to Rx ３ each independently represent a linear or branched alkyl group, and Rx１ ~Rx ３ It is more preferable that each of these independently represents a linear alkyl group. １ ~Rx ３ These two may combine to form a monocycle or polycycle. Rx １ ~Rx ３ The alkyl group is preferably a C1-C10 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group, and more preferably a C1-C5 alkyl group. １ ~Rx ３ The cycloalkyl group preferably has 3 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms. Rx １ ~Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group, or an anthyl group. １ ~Rx ３ Examples of alkenyl groups include alkenyl groups having 2 to 20 carbon atoms, with alkenyl groups having 2 to 10 carbon atoms being preferred, such as vinyl groups and allyl groups. １ ~Rx ３ A cycloalkane ring is preferred as the ring formed by the bonding of these two. １ ~Rx ３ The cycloalkane ring formed by the bonding of these two elements may be a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, tetracyclodecane ring, tetracyclododecane ring, or adamantane ring. A monocyclic cycloalkane ring with 5 to 6 carbon atoms is preferred. １ ~Rx ３The cycloalkane ring formed by the bonding of these two groups may have one or more methylene groups replaced by heteroatoms such as oxygen, sulfur, or nitrogen atoms, heteroatom-containing groups such as carbonyl groups, or vinylidene groups. Furthermore, one or more ethylene groups may be replaced by vinylene groups. Rx １ ~Rx ３ The ring formed by the bonding of these two may have substituents. The group represented by formula (Y1) or formula (Y2) may be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded to form a cycloalkane ring. When the composition of the present invention is, for example, an EUV lithography resist composition, Rx １ ~Rx ３ Alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and Rx are represented by １ ~Rx ３ The ring formed by the bonding of these two elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0040] In formula (Y3), R ３６ ~R ３８ Each of these independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. ３６ It is also preferable that the atom is a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. ３８ R may bond with other substituents on the main chain of resin (A) to form a ring. ３８The group formed by the bonding of the original component and another substituent on the main chain of resin (A) is preferably an alkylene group such as a methylene group. When the composition of the present invention is, for example, an EUV lithography resist composition, R ３６ ~R ３８ A monovalent organic group represented by, and R ３７ and R ３８ The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0041] The base represented by formula (Y3-1) below is preferred for formula (Y3).

[0042]

[0043] Here, L Ｙ１ and L Ｙ２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). Ｙ１ represents a single bond or a divalent linking group. Q Ｙ１ This represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which may contain a heteroatom such as a carbonyl group which may contain a heteroatom. Ｙ１ and L Ｙ２ Preferably, one of the groups is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group. Ｙ１ M Ｙ１ , and L Ｙ１ At least two of these may be joined to form a ring (preferably a five-membered or six-membered ring). In terms of pattern refinement, L Ｙ２It is preferable that the group is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging. In formula (Y3-1), * represents the bond position.

[0044] L in equation (Y3-1) Ｙ１ , L Ｙ２ Q Ｙ１ and M Ｙ１ Preferably, at least one of them contains a metal atom.

[0045] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar.

[0046] From the standpoint of excellent acid decomposition properties, in the case of a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0047] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0048] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0049]

[0050] In equation (AI), Xa １ Rx represents a hydrogen atom, a halogen atom (such as a fluorine atom), or an alkyl group which may have substituents. T represents a single bond or a divalent linking group.１ to Rx ３ each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic), provided that Rx １ to Rx ３ are all alkyl groups (linear or branched), at least two of Rx １ to Rx ３ are preferably methyl groups. Two of Rx １ to Rx ３ may be bonded to each other to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0051] Xa １ , examples of the optionally substituted alkyl group represented by include a methyl group and a group represented by -CH ２ -R １１ . R １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples of the monovalent organic group represented by R １１ include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom; an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xa １ , a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.

[0052] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is more preferably -CH ２ - group, -(CH ２ ) ２ - group, or -(CH ２ ) ３ - group.

[0053] Rx１ ~Rx ３ As the alkyl group for, alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferred. Rx １ ~Rx ３ As the cycloalkyl group for, monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred. Rx １ ~Rx ３ The cycloalkyl group for may be a cycloalkyl group having 3 to 20 carbon atoms. Rx １ ~Rx ３ As the aryl group for, aryl groups having 6 to 14 carbon atoms are preferred, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. Rx １ ~Rx ３ As the alkenyl group for, a vinyl group is preferred. Rx １ ~Rx ３ As the cycloalkyl group formed by bonding of two of, monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group are preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. Rx １ ~Rx ３ In the cycloalkyl group formed by bonding of two of, for example, one methylene group constituting the ring may be replaced with a hetero atom such as an oxygen atom, a group containing a hetero atom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The repeating unit represented by formula (AI) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ are bonded to form the above cycloalkyl group, which is a preferred embodiment.

[0054] When each of the above groups has 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). The number of carbon atoms in the substituent is preferably 8 or less.

[0055] The repeating unit represented by formula (AI) is an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (Xa １ A repeating unit in which represents a hydrogen atom or a methyl group, and T represents a single bond, is preferred.

[0056] In a preferred embodiment, the resin (A) has an acid-degradable group, and it is preferable that the acid-degradable group contains a metal atom. An acid-degradable group containing a metal atom is also called an "acid-degradable group (Ma)".

[0057] The metal atoms included in the acid-degradable group (Ma) are not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, the same applies as above, and the preferred range is also the same. There may be one type of metal atom or two or more types. In a preferred embodiment, it is preferable that at least one of the metal atoms is selected from groups 13 to 16. It is preferable that the metal atoms are from the 4th to 6th period of the periodic table and from groups 13 to 16. The metal atoms included in the acid-degradable group (Ma) are preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, lead, indium, and antimony, more preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, and indium, even more preferably at least one selected from the group consisting of germanium, bismuth, and tin, and particularly preferably germanium. The metal atom contained in the acid-degradable group (Ma) is preferably chemically bonded to other atoms contained in the acid-degradable group (Ma), and more preferably covalently bonded. In the acid-degradable group (Ma), the metal atom is preferably contained in the group that is removed by the action of the acid (leaving group) as described above.

[0058] In one preferred embodiment, Rx in the above-mentioned formulas (Y1) and (Y2) １ ~Rx ３ Preferably, at least one of them contains a metal atom. In one preferred embodiment, R in the above formula (Y3) ３６ ~R ３８ Preferably, at least one of the atoms is a metal atom. In one preferred embodiment, it is preferable that at least one of the Ar and Rn atoms in the above formula (Y4) is a metal atom.

[0059] In one preferred embodiment, the resin (A) preferably contains repeating units having an acid-degradable group (Ma). The repeating units having an acid-degradable group (Ma) are preferably at least one selected from the group consisting of repeating units represented by the following formula (N1) and repeating units represented by the following formula (N2). The resin (A) preferably contains at least one selected from the group consisting of repeating units represented by the following formula (N1) and repeating units represented by the following formula (N2). The resin (A) more preferably contains repeating units represented by the following formula (N1). As will be described later, the P in formula (N1) Ｎ１ and P in formula (N2) Ｎ２ However, a preferred embodiment of resin (A) is that it is bonded to an oxygen atom with a secondary or tertiary carbon atom.

[0060]

[0061] In formula (N1), R Ｎ１ R represents a hydrogen atom, alkyl group, or halogen atom. Ｎ２ and R Ｎ３ Each of these independently represents a hydrogen atom or a substituent. Ｎ１ P represents a single bond or a divalent linking group. Ｎ１ R represents a group containing a metal atom. In formula (N2), R Ｎ４ R represents a hydrogen atom, alkyl group, or halogen atom. Ｎ５ and R Ｎ６ Each of these independently represents a hydrogen atom or a substituent. Ｎ２ P represents a single bond or a divalent linking group. Ｎ２ This represents a group containing a metal atom.

[0062] R in equation (N1) Ｎ１ R represents a hydrogen atom, alkyl group, or halogen atom. Ｎ１ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents. The substituents are not particularly limited, and examples include the substituent T mentioned above, which is preferably a halogen atom. That is, R Ｎ１ It is also preferable that this represents an alkyl halide. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0063] R Ｎ１ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0064] R Ｎ１ It is preferable that this represents a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

[0065] R in equation (N1) Ｎ２ and R Ｎ３ Each of these independently represents a hydrogen atom or a substituent. Ｎ２ and R Ｎ３ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. Ｎ２ and R Ｎ３ R preferably represents a hydrogen atom. Ｎ１ When R represents a hydrogen atom, Ｎ２ and R Ｎ３ It is also preferable that at least one of them represents a substituent. For example, R Ｎ１ When R represents a hydrogen atom, Ｎ２ and R Ｎ３ At least one of them may represent a substituent having an ester group or a phenol structure. Also, R Ｎ２ and R Ｎ３ At least one of them is "-L" in formula (N1)Ｎ１ -COO-P Ｎ１ The base or formula (N2) represented by "-L Ｎ２ -O-P Ｎ２ It may also represent a base expressed as ".

[0066] L in equation (N1) Ｎ１ L represents a single bond or a divalent linking group. Ｎ１ The divalent linking group represented by is not particularly limited, but examples include alkylene groups, cycloalkylene groups, arylene groups, and groups formed by combining two or more of these groups. The number of carbon atoms in the alkylene group is not particularly limited. The alkylene group is preferably a C1 to C20 alkylene group such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, or octylene group, and more preferably a C1 to C10 alkylene group. The alkylene group may have substituents. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, tetracyclodecanylene group, tetracyclododecanylene group, or adamantylene group. The cycloalkylene group may have substituents. The above arylene group may be either a monocyclic or polycyclic group. The number of carbon atoms in the above arylene group is not particularly limited. As the above arylene group, for example, arylene groups having 6 to 30 carbon atoms, such as phenylene, torylene, naphthylene, anthrylene, and biphenylene groups, are preferred. The above arylene group is more preferably an arylene group having 6 to 12 carbon atoms, and even more preferably a phenylene or naphthylene group. The above arylene group may have substituents. Ｎ１ It is preferable that this represents a single bond.

[0067] P in equation (N1) Ｎ１ P represents a group containing a metal atom. Ｎ１Preferably, the group is one that is eliminated by the action of an acid. The metal atom is not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, it is the same as above, and the preferred range is also the same. There may be one metal atom or two or more metal atoms. In a preferred embodiment, it is preferable that at least one of the metal atoms is an atom selected from groups 13 to 16. Preferably, the metal atom is from the 4th to 6th period of the periodic table and from groups 13 to 16.

[0068] P Ｎ１ It contains at least one of a secondary carbon atom and a tertiary carbon atom, and preferably a secondary carbon atom or a tertiary carbon atom is bonded to the oxygen atom in formula (N1). Ｎ１ It is preferable that this represents a group represented by the following formula (N3) or a group represented by the following formula (N4).

[0069]

[0070] In formula (N3), R Ｎ７ , R Ｎ８ , R Ｎ９ , R Ｎ１０ , R Ｎ１１ and R Ｎ１２ Each of these independently represents a substituent. Ｎ７ , R Ｎ８ , R Ｎ９ , R Ｎ１０ , R Ｎ１１ and R Ｎ１２ At least two of them may be joined to form a ring. Ｐ１ represents a metal atom. m represents 0 or 1. * represents a bond position. In formula (N4), R Ｎ１３ , R Ｎ１４ , R Ｎ１５ , R Ｎ１６ and R Ｎ１７ Each of these independently represents a substituent. Ｐ２ L represents a metal atom. Ｎ３ It contains two or more atoms, R Ｎ１３ and R Ｎ１４ From the atom bonded to the carbon atom to which it is bonded, M Ｐ２ This represents a divalent linking group where, when counting the number of atoms up to the bonded atom, the minimum number of atoms is 2 or greater.Ｎ１３ , R Ｎ１４ , R Ｎ１５ , R Ｎ１６ , R Ｎ１７ and L Ｎ３ At least two of these may be joined to form a ring. n represents 0 or 1. * indicates the bond position.

[0071] R in equation (N3) Ｎ７ , R Ｎ８ , R Ｎ９ , R Ｎ１０ , R Ｎ１１ and R Ｎ１２ (R Ｎ７ ~R Ｎ１２ It is also written as ". The same applies below. ) Each represents a substituent independently. R Ｎ７ ~R Ｎ１２ The substituent represented by is not particularly limited, and examples include the substituent T mentioned above, which preferably represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. Ｎ７ ~R Ｎ１２ The alkyl group represented by may be linear or branched. Preferably, the alkyl group is a C1-C10 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group, and more preferably a C1-C5 alkyl group. The alkyl group may have substituents. Ｎ７ ~R Ｎ１２ The number of carbon atoms in the cycloalkyl group represented by is preferably 3 to 20, and more preferably 4 to 15. The above cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. In the above cycloalkyl group, one or more methylene groups constituting the ring may be replaced with heteroatoms such as oxygen atoms or sulfur atoms, groups having heteroatoms such as carbonyl groups, or vinylidene groups. In addition, one or more ethylene groups constituting the cycloalkane ring of the above cycloalkyl group may be replaced with vinylene groups. The above cycloalkyl group may have substituents. Ｎ７ ~R Ｎ１２The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, or an anthyl group. The above aryl group may have substituents. Ｎ７ ~R Ｎ１２ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member atom. The number of ring member atoms of the heteroaryl group is preferably 4 to 20, and more preferably 5 to 15. Examples of the heteroaryl group include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, a benzothiophenyl group, and the like. The heteroaryl group may have substituents. Ｎ７ ~R Ｎ１２ The aralkyl group represented by the above-mentioned R Ｎ７ ~R Ｎ１２ A preferred group is one in which one hydrogen atom in the alkyl group represented by is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), for example, a benzyl group. The above aralkyl group may have substituents. Ｎ７ ~R Ｎ１２ Examples of alkenyl groups represented by include alkenyl groups having 2 to 20 carbon atoms, with alkenyl groups having 2 to 10 carbon atoms being preferred, for example, vinyl groups and allyl groups are preferred. The above alkenyl groups may have substituents.

[0072] R Ｎ７ ~R Ｎ１２ At least two of them may be joined to form a ring. Ｎ７ ~R Ｎ１２ At least two of these may be bonded by single bonds or by divalent linking groups. The divalent linking groups are not particularly limited, but for example, -O-, -CO-, -COO-, -CONR ａ２０- Examples include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these groups. ａ２０ R represents a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group. Ｎ７ ~R Ｎ１２ The ring formed by the bonding of at least two of these may be an aromatic ring or a non-aromatic ring. Ｎ７ ~R Ｎ１２ The ring formed by the bonding of at least two of these is preferably a cycloalkane ring. The cycloalkane ring may be a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, tetracyclodecane ring, tetracyclododecane ring, or adamantane ring. The cycloalkane ring is preferably a monocyclic or polycyclic cycloalkane ring having 3 to 10 carbon atoms, and more preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced by heteroatoms such as oxygen, nitrogen, or sulfur atoms, groups having heteroatoms such as carbonyl groups, or vinylidene groups. Furthermore, in the cycloalkane ring, one or more of the ethylene groups constituting the ring may be replaced by vinylene groups. Ｎ７ ~R Ｎ１２ The ring formed by the bonding of at least two of these elements may have substituents.

[0073] R Ｎ７ ~R Ｎ１２ R preferably represents an alkyl group, a cycloalkyl group, or an aryl group. Ｎ７ ~R Ｎ１２ It is also preferable that at least two of them bond to form a cycloalkane ring. Ｎ１０ ~R Ｎ１２ In M Ｐ１ The atom bonded to it is preferably a carbon atom.

[0074] M in equation (N3) Ｐ１ M represents a metal atom. Ｐ１The metal atoms represented by are atoms selected from groups 13 to 16 of the periodic table. Specifically, the atoms selected from groups 13 to 16 are, as described above, atoms from the 3rd to 7th periods of the periodic table and in group 13, atoms from the 4th to 7th periods of the periodic table and in group 14, atoms from the 5th to 7th periods of the periodic table and in group 15, atoms from the 6th to 7th periods of the periodic table and in group 16, or atoms from the 7th period of the periodic table and in group 17. Ｐ１ It is preferable that the atoms are from the 4th to the 6th period of the periodic table, and from groups 13 to 16. Ｐ１ It is preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, lead, indium, and antimony; more preferably at least one selected from the group consisting of germanium, bismuth, gallium, tin, and indium; even more preferably at least one selected from the group consisting of germanium, bismuth, and tin; and particularly preferably germanium. Ｐ１ If the metal atoms are bismuth, indium, and antimony, then m is 0.

[0075] R in equation (N4) Ｎ１３ , R Ｎ１４ , R Ｎ１５ , R Ｎ１６ and R Ｎ１７ Each of these independently represents a substituent. Ｎ１３ ~R Ｎ１７ The description, specific examples, and preferred range of substituents represented by R are as described above. Ｎ７ ~R Ｎ１２ This is the same as in the substituent represented by R. Ｎ１５ ~R Ｎ１７ In M Ｐ２ The atom bonded to it is preferably a carbon atom.

[0076] M in equation (N4) Ｐ２ M represents a metal atom. Ｐ２ The explanation, specific examples, and preferred range of M in formula (N3) above are given by Ｐ１ It is the same as the one in M. Ｐ２If the metal atoms are bismuth, indium, and antimony, then n is 0.

[0077] L in equation (N4) Ｎ３ It contains two or more atoms, R Ｎ１３ and R Ｎ１４ The atom bonded to the carbon atom to which it is bonded (this atom is called "A") Ｔ１ It is also called "M Ｐ２ The atom that bonds (this atom is called "A") Ｔ２ It is also called "n". ＡＴ It is also called "the number of atoms (n) when counting them." ＡＴ The minimum value of ("n ＡＴｍｉｎ It is also called a "divalent linking group". ) represents a divalent linking group with 2 or more n ＡＴ is, A Ｔ１ A Ｔ２ , and A Ｔ１ and A Ｔ２ It can be determined by counting the atoms that are covalently bonded between them. Ｎ３ n ＡＴｍｉｎ L is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. Ｎ３The divalent linking group represented by is not particularly limited, but examples include alkylene groups, alkenylene groups, alkylene groups, cycloalkylene groups, arylene groups, and groups formed by combining two or more of these groups. The number of carbon atoms in the alkylene group is not particularly limited. As the alkylene group, for example, alkylene groups having 1 to 20 carbon atoms, such as methylene groups, ethylene groups, propylene groups, butylene groups, hexylene groups, and octylene groups, are preferred, and alkylene groups having 1 to 10 carbon atoms are more preferred. The alkylene group may have substituents. The number of carbon atoms in the alkenylene group is not particularly limited, but 2 to 10 is preferred. The alkenylene group may have substituents. The number of carbon atoms in the alkylene group is not particularly limited, but 2 to 10 is preferred. The alkylene group may have substituents. The number of carbon atoms in the cycloalkylene group is not particularly limited, but 3 to 20 is preferred, and 5 to 15 is more preferred. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. The cycloalkylene group may have substituents. The arylene group may be either a monocyclic or polycyclic group. The number of carbon atoms in the arylene group is not particularly limited. As the arylene group, for example, arylene groups having 6 to 30 carbon atoms such as a phenylene group, a torylene group, a naphthylene group, anthrylene group, or a biphenylene group are preferred. The arylene group is more preferably an arylene group having 6 to 12 carbon atoms, and even more preferably a phenylene group or a naphthylene group. The arylene group may have substituents.

[0078] R Ｎ１３ ~R Ｎ１７ and L Ｎ３ At least two of them may be joined to form a ring. Ｎ１３ ~R Ｎ１７ and L Ｎ３ At least two of these may be bonded by single bonds or by divalent linking groups. The divalent linking groups are not particularly limited, but for example, -O-, -CO-, -COO-, -CONR ａ２０- Examples include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these groups. ａ２０ R represents a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group. Ｎ１３ ~R Ｎ１７ and L Ｎ３ A description, specific examples, and preferred range of the ring formed by the bonding of at least two of the above are given by R in formula (N3) above. Ｎ７ ~R Ｎ１２ It is the same as in the ring formed by the bonding of at least two of them. Ｎ１３ ~R Ｎ１７ and L Ｎ３ The ring formed by the bonding of at least two of these elements may have substituents.

[0079] R Ｎ１３ ~R Ｎ１７ R preferably represents an alkyl group, a cycloalkyl group, or an aryl group. Ｎ１３ ~R Ｎ１７ and L Ｎ３ It is also preferable that at least two of them combine to form a cycloalkane ring.

[0080] R in equation (N2) Ｎ４ R represents a hydrogen atom, alkyl group, or halogen atom. Ｎ４ The explanation, specific examples, and preferred range of R in formula (N1) above are given by Ｎ１ It is the same as the one in [location / place].

[0081] R in equation (N2) Ｎ５ and R Ｎ６ Each of these independently represents a hydrogen atom or a substituent. Ｎ５ and R Ｎ６ The explanation, specific examples, and preferred range of R in formula (N1) above are given by Ｎ２ and R Ｎ３ It is the same as the one in [location / place].

[0082] L in equation (N2) Ｎ２ L represents a single bond or a divalent linking group. Ｎ２ The explanation, specific examples, and preferred range of L in formula (N1) mentioned above are provided below. Ｎ１It is the same as the one in [location / place].

[0083] P in equation (N2) Ｎ２ P represents a group containing a metal atom. Ｎ２ The explanation, specific examples, and preferred range of P in formula (N1) mentioned above are provided below. Ｎ１ It is the same as the one in P. Ｎ２ It is preferable that the group is one that is removed by the action of an acid. Ｎ２ It contains at least one of a secondary carbon atom and a tertiary carbon atom, and preferably a secondary carbon atom or a tertiary carbon atom is bonded to the oxygen atom in formula (N2). Ｎ２ It is preferable that P represents a group represented by the above formula (N3) or a group represented by the above formula (N4). Also, P Ｎ２ It is also preferable that P represents the group represented by the above formula (Y3-1), Ｎ２ This represents the group represented by the above formula (Y3-1), and L in the above formula (Y3-1) Ｙ１ and L Ｙ２ It is also preferable that at least one of them contains a metal atom.

[0084] Specific examples of repeating units having an acid-degradable group (Ma) are shown below, but the present invention is not limited to these.

[0085]

[0086]

[0087] The content of repeating units having acid-degradable groups is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having acid-degradable groups is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, relative to the total repeating units in resin (A). The repeating units having acid-degradable groups contained in resin (A) may be one type or two or more types. When resin (A) contains two or more types of repeating units having acid-degradable groups, it is preferable that their total content is within the range of the above preferred content.

[0088] (Repeating units having acidic groups) Resin (A) preferably contains repeating units having acidic groups. Preferred acidic groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. One or more (preferably 1 to 2) fluorine atoms in the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As for the acidic group, the -C(CF) formed in this way is preferred. ３ ) (OH)-CF ２ - is also preferable. In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom, -C(CF ３ ) (OH)-CF ２ A ring containing a - may be formed. The repeating unit having an acidic group may be the same as or different from the repeating unit having the aforementioned acid-degradable group (Ma). The repeating unit having an acidic group may have a fluorine atom or an iodine atom. The repeating unit having an acidic group may have a metal atom. The metal atom is not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, it is the same as above, and the preferred range is also the same. Specific examples of repeating units having an acidic group include, for example, the repeating units described in

[0088] to

[0089] and

[0103] to

[0110] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0089] The repeating unit having an acidic group is preferably a repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group may be the same as or different from the repeating unit having the aforementioned acid-degradable group (Ma).

[0090] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa1). The resin (A) preferably contains the repeating unit represented by the following formula (Pa1).

[0091]

[0092] In formula (Pa1), Rａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ Ar represents a single bond or a divalent linking group. ａ１ Ar represents an aromatic ring group. ａ１ And, R ａ２ or L ａ１ The bonds may be single bonds or via linking groups. Ｘ represents a substituent other than a hydroxyl group. n represents an integer between 1 and 9 (inclusive). m represents an integer between 0 and 8 (inclusive).

[0093] R in equation (Pa1) ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituent represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ and R ａ２ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents. ａ１ and R ａ２ The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have substituents. ａ１ and R ａ２ Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms, with fluorine or iodine atoms being preferred. ａ１ and R ａ２The alkyl group contained in the alkoxycarbonyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. The alkoxycarbonyl group may have substituents.

[0094] L in equation (Pa1) ａ１ L represents a single bond or a divalent linking group. ａ１ The divalent linking group represented by is not particularly limited, but for example, -COO-, -CONR ａ３ -, alkylene groups, or groups formed by combining two or more of these groups. ａ３ R represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but C1-C8 alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, and octylene are preferred. The alkylene group may have substituents. ａ３ Examples of alkyl groups that represent an alkyl group include alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or fewer carbon atoms being preferred.

[0095] Ar in equation (Pa1) ａ１ Ar represents an aromatic ring group, specifically an aromatic ring group with (m+n+1) valency. ａ１ The aromatic ring group represented by may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferably, the aromatic hydrocarbon group is a group containing aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. Preferably, the aromatic heterocyclic group contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as a ring member. Preferably, the aromatic heterocyclic group is a group containing aromatic heterocyclic rings with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0096] Ar ａ１ And, R ａ２ or L ａ１ These may be bonded by a single bond or via a linking group. Examples of linking groups include -O-, -S-, -CO-, and -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have substituents.

[0097] R in equation (Pa1) Ｘ R represents substituents other than hydroxyl groups. Ｘ Examples of substituents represented by include carboxyl groups, sulfo groups, cyano groups, halogen atoms, hydrocarbon groups, amino groups, nitro groups, and groups formed by combining two or more of these. Ｘ Examples of hydrocarbon groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 5 to 15 carbon atoms), and alkenyl groups (preferably having 2 to 10 carbon atoms). Ｘ The hydrocarbon group represented by may have substituents. Also, R Ｘ The hydrocarbon group represented is -CH ２ If it contains -, -CH ２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - May be replaced by at least one selected from the group consisting of -. Ｘ The substituent represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom.

[0098] In formula (Pa1), n ​​represents an integer between 1 and 9, preferably between 1 and 5, and more preferably between 1 and 4.

[0099] In formula (Pa1), m represents an integer between 0 and 8, preferably between 0 and 4, and more preferably between 0 and 3.

[0100] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa2). The resin (A) preferably contains the repeating unit represented by the following formula (Pa2).

[0101]

[0102] In formula (Pa2), R ａ４ L represents a hydrogen atom or an alkyl group. ａ２ R represents a single bond or -COO-. Ｘ１ represents a halogen atom, haloalkyl group, or hydrocarbon group. n1 represents an integer between 1 and 5. m1 represents an integer between 0 and 4. r represents an integer between 0 and 3.

[0103] R in equation (Pa2) ａ４ R represents a hydrogen atom or an alkyl group. ａ４ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents.

[0104] L in equation (Pa2) ａ２ The symbol represents a single bond or a -COO-, and it is preferable that it represents a single bond.

[0105] In formula (Pa2), r represents an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 0. In formula (Pa2), the aromatic ring is benzene when r is 0, naphthalene when r is 1, anthracene when r is 2, and naphthacene when r is 3.

[0106] R in equation (Pa2) Ｘ１ R represents a halogen atom, haloalkyl group, or hydrocarbon group. Ｘ１ The halogen atom represented by is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Ｘ１The haloalkyl group represented by is preferably a haloalkyl group having 1 to 10 carbon atoms, and more preferably a haloalkyl group having 1 to 5 carbon atoms. The haloalkyl group may be one in which some of the hydrogen atoms of the alkyl group are substituted with halogen atoms, or it may be a perhaloalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. The haloalkyl group is preferably a fluoroalkyl group. Ｘ１ Examples of hydrocarbon groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 5 to 15 carbon atoms), and alkenyl groups (preferably having 2 to 10 carbon atoms). Ｘ１ The hydrocarbon group and haloalkyl group represented by may have substituents. Also, R Ｘ１ The hydrocarbon group and haloalkyl group represented by are -CH ２ If it contains -, -CH ２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - may be replaced by at least one selected from the group consisting of -.

[0107] In formula (Pa2), n1 represents an integer between 1 and 5, preferably an integer between 1 and 4.

[0108] In formula (Pa2), m1 represents an integer between 0 and 4, preferably an integer between 0 and 3.

[0109] Specific examples of repeating units having phenolic hydroxyl groups are shown below, but the present invention is not limited to these. In the following structural formulas, G １ and G ２ Each of these independently represents a hydrogen atom, a methyl group, a cyano group, a hydroxyl group, or a hydroxymethyl group. f1 represents an integer from 1 to 3.

[0110]

[0111] When resin (A) contains repeating units having acidic groups, the content of repeating units having acidic groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having acidic groups is preferably 90 mol% or less, and more preferably 80 mol% or less, relative to the total repeating units in resin (A). When resin (A) contains repeating units having acidic groups, there may be one type of repeating unit having acidic groups or two or more types. When resin (A) contains two or more types of repeating units having acidic groups, it is preferable that their total content is within the range of the above preferred content.

[0112] (Repeating units having lactone groups, sultone groups, or carbonate groups) Resin (A) may have repeating units having lactone groups, sultone groups, or carbonate groups (hereinafter also referred to as "unit Y"). It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0113] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferred. The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in International Publication No. 2022 / 024928

[0127] to

[0133] . The above description is incorporated herein by reference.

[0114] Resin (A) preferably contains repeating units having lactone groups, sultone groups, or carbonate groups obtained by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2), and the lactone groups, sultone groups, or carbonate groups may be directly bonded to the main chain. For example, the ring member atoms of the lactone groups, sultone groups, or carbonate groups may constitute the main chain of resin (A). The lactone groups, sultone groups, and carbonate groups may have substituents.

[0115] R in the following structural formula Ｌ R represents a substituent. Ｌ If multiple R Ｌ They can be the same or they can be different. Ｌ Examples include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. If there are multiple e1s, they may be the same or different. If e1 is 2 or more, there may be multiple R Ｌ The Rs may be the same or different, and there may be multiple Rs. Ｌ They may join together to form a ring.

[0116]

[0117] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include the repeating unit represented by the following formula (AI-2).

[0118]

[0119] In formula (AI-2), Rb ０ Rb represents a hydrogen atom, a halogen atom, or an alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 4 is preferred. ０ The alkyl group may have substituents. Rb ０Examples of substituents that the alkyl group may have include a hydroxyl group and a halogen atom. Rb ０ Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ０ Ab is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group combining these. In particular, Ab can be a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. Ab １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate ester structure represented by any of formulas (CC1-1) to (CC1-2).

[0120] If resin (A) contains unit Y, the content of unit Y may be 1 mol% or more, or 10 mol% or more, relative to the total repeating units in resin (A). Alternatively, the content of unit Y may be 80 mol% or less, or 70 mol% or less, relative to the total repeating units in resin (A). It is also preferable that resin (A) does not contain unit Y.

[0121] (Repeating units having photoacid-generating groups) Resin (A) may contain repeating units having groups that generate acid upon irradiation with active light or radiation (also called "photoacid-generating groups"). If resin (A) contains repeating units having photoacid-generating groups, resin (A) can also function as a photoacid generator. Examples of repeating units having photoacid-generating groups include the repeating unit represented by formula (4). The repeating units having photoacid-generating groups may have metal atoms. The metal atoms are not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, the same applies as above, and the preferred range is also the same.

[0122]

[0123] R ４１ L represents a hydrogen atom or a methyl group. ４１ L represents a single bond or a divalent linking group. ４２ R represents a divalent linking group. ４０ This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain.

[0124] L ４１ represents a single bond or a divalent linking group, preferably a single bond or an ester bond (-COO-).

[0125] L ４２ These are alkylene groups, cycloalkylene groups, arylene groups, -O-, -CO-, -S-, -SO-, -SO ２It is preferable that the linking group consists of at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, cycloalkyl group, or aryl group). The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred. The cycloalkylene group may be a monocyclic or polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but 3 to 20 is preferred, and 5 to 15 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. The alkylene group, cycloalkylene group and arylene group may have substituents, and the substituent T mentioned above is an example of a substituent.

[0126] R ４０ Preferably, the group is represented by the following formula (S4-1).

[0127]

[0128] In equation (S4-1), Q － represents an acid residue, M ＋ * represents a cation. * represents L ４１ This indicates the bonding position. An acid residue is a group formed when a proton dissociates from an acid. Q － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), borate anion group, or sulfonamide group (N － -SO ２ R Ｎ１ It is represented by R Ｎ１ represents an organic group, and examples include organic groups having 1 to 10 carbon atoms, with alkyl groups, fluoroalkyl groups, or aryl groups being preferred. A sulfonate anion group is more preferred. ＋ For further explanation, specific examples, and preferred ranges, please refer to the description of compound (S) below. ＋ It is the same as this.

[0129] Specific examples of repeating units having photoacid generating groups include, for example, the repeating units described in

[0094] to

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

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

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

[0130] Examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

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

[0131] If resin (A) contains repeating units having photoacid-generating groups, the content of repeating units having photoacid-generating groups may be 1 mol% or more, 3 mol% or more, or 5 mol% or more relative to the total repeating units in resin (A). Alternatively, the content of repeating units having photoacid-generating groups may be 40 mol% or less, 30 mol% or less, or 20 mol% or less relative to the total repeating units in resin (A). It is also preferable that resin (A) does not contain repeating units having photoacid-generating groups.

[0132] (Repeating units represented by formula (V-1) or formula (V-2)) The resin (A) may have repeating units represented by the following formula (V-1) or formula (V-2). It is also preferable that the repeating units represented by formula (V-1) and formula (V-2) are different from the repeating units described above.

[0133]

[0134] In equations (V-1) and (V-2), R ６ and R ７Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ n represents an integer between 0 and 6. ４ X represents an integer between 0 and 4. ４ is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0135] (Repeating units to reduce the mobility of the main chain) Resin (A) may have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern breakdown during development. Tg may be greater than 90°C, greater than 100°C, greater than 110°C, or greater than 125°C. In order to have a good dissolution rate in the developer, Tg may be 400°C or less, or 350°C or less. In this specification, the glass transition temperature (Tg) of polymers such as resin (A) (hereinafter referred to as "Tg of repeating units") is calculated by the following method. First, the Tg of homopolymers consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated. Next, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Biceranno method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). The calculation of Tg using the Biceranno method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0136] For repeating units that reduce the mobility of the main chain, refer to paragraphs

[0144] to

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

[0137] (Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) Resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0138] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. The repeating units having hydroxyl groups or cyano groups are preferably repeating units having an alicyclic hydrocarbon structure substituted with hydroxyl groups or cyano groups. The repeating units having hydroxyl groups or cyano groups are preferably not acid-degradable groups. Examples of repeating units having hydroxyl groups or cyano groups are those described in paragraphs

[0081] to

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

[0139] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in the resin (A) improves resolution, particularly in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

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

[0140] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0141] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0142]

[0143] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or -CH ２ -O-Ra ２ It represents the base. In the formula, Ra ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group are those described in paragraphs

[0087] to

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

[0144] (Other Repeating Units) Furthermore, resin (A) may have other repeating units besides those described above. Resin (A) may have repeating units selected from the group consisting of, for example, repeating units having an oxatian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in

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

[0145] With respect to resin (A), further reference can be made to the contents of

[0112] to

[0118] and

[0171] to

[0172] of International Publication No. 2022 / 024928.

[0146] The synthesis examples of resin (A) are not particularly limited, but one example is described in the examples below. According to the GPC method, the weight-average molecular weight (Mw) of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Pd, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. A lower degree of dispersion results in better resolution and resist shape, smoother sidewalls of the resist pattern, and superior roughness.

[0147] The content of resin (A) in the composition of the present invention is preferably 30.0 to 100.0% by mass, and more preferably 40.0 to 100.0% by mass, based on the total solid content of the composition of the present invention. The type of resin (A) in the composition of the present invention may be one type or two or more types. If the composition of the present invention contains two or more types of resin (A), it is preferable that their total content is within the range of the above preferred content.

[0148] The composition of the present invention preferably contains at least one selected from the group consisting of triarylsulfonium salts and diaryliodonium salts.

[0149] <Photoacid Generator> The composition of the present invention may contain a photoacid generator (also referred to as "compound (S)"). Compound (S) is a compound that generates acid upon irradiation with active light or radiation. Preferably, compound (S) is a compound that generates acid with a pKa of less than 0 upon irradiation with active light or radiation. The pKa of the acid generated from compound (S) upon irradiation with active light or radiation is preferably -0.1 or less, and more preferably -0.2 or less.

[0150] Compound (S) may be in the form of a low molecular weight compound or a high molecular weight compound such as a resin. When compound (S) is in the form of a low molecular weight compound, the molecular weight of compound (S) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000. When compound (S) is in the form of a high molecular weight compound, compound (S) and resin (A) may be the same compound, or compound (S) may be a different high molecular weight compound from resin (A). When resin (A) does not contain the repeating units having the photoacid generating group described above, it is preferable that the composition of the present invention contains compound (S) as a compound different from resin (A). When resin (A) contains repeating units having the photoacid generating group, the composition of the present invention may or may not contain compound (S) as a compound different from resin (A).

[0151] Compound (S) is preferably a compound having an anion and a cation.

[0152] Compound (S) preferably contains a metal atom. The metal atom is not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, it is the same as above, and the preferred range is also the same. There may be one metal atom or two or more metal atoms. In a preferred embodiment, it is preferable that at least one of the metal atoms is selected from groups 13 to 16. It is preferable that the metal atom is from the 4th to 6th period of the periodic table and from groups 13 to 16. If compound (S) is a compound having an anion and a cation, it is preferable that at least one of the anion and cation contains a metal atom.

[0153] Compound (S) more preferably has at least one selected from the group consisting of aluminum, gallium, indium, germanium, tin, antimony, and bismuth. Compound (S) even more preferably has at least one selected from the group consisting of gallium, indium, germanium, tin, and bismuth. Compound (S) particularly preferably has at least one selected from the group consisting of gallium, indium, and bismuth.

[0154] For example, the compound (S) is "M ＋ X － Examples of compounds represented by '' (onium salts) include compounds that generate organic acids upon exposure. Examples of organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imide acid, and tris(alkylsulfonyl)methidic acid.

[0155] "M ＋ X － In the compound represented by ", M ＋ represents a cation. The cation is not particularly limited. The valency of the cation may be 1 or 2 or higher. In particular, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred. It is preferable that cation (ZaI) and cation (ZaII) are cations that decompose upon irradiation with active light or radiation.

[0156]

[0157] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ Each of these independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH ２ -CH ２-O-CH ２ -CH ２ - is one example.

[0158] The cation in formula (ZaI) is an organic cation, and preferred embodiments of the organic cation include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0159] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ It is an arylsulfonium cation in which at least one of the groups is an aryl group. ２０１ ~R ２０３ All of them may be aryl groups, or R ２０１ ~R ２０３ A portion of it may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ One of them is an aryl group, R ２０１ ~R ２０３ The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH ２ -CH ２ -O-CH ２ -CH ２ Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0160] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may 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 arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, with methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group being more preferred.

[0161] R ２０１ ~R ２０３ Preferred substituents on the aryl group, alkyl group, and cycloalkyl group include alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. The above substituents may also form an acid-degradable group in any combination. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a group that leaves upon the action of an acid. The polar group and leaving group are as described above.

[0162] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). ２０１ ~R ２０３ However, each of these independently represents a cation that does not have an aromatic ring. The term "aromatic ring" also includes aromatic rings containing heteroatoms. R ２０１ ~R ２０３ The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0163] R ２０１ ~R ２０３ Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). ２０１ ~R ２０３ R may be further substituted with halogen atoms, alkoxy groups (e.g., C1-C5), hydroxyl groups, cyano groups, or nitro groups. ２０１ ~R ２０３ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0164] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0165]

[0166] In formula (ZaI-3b), R １ｃ ~R ５ｃEach of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0167] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ These elements may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3 to 10-membered rings, 4 to 8-membered rings are preferred, and 5 or 6-membered rings are more preferred.

[0168] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙExamples of groups formed by the bonding include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0169] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and also, R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The rings formed by the bonding of these elements to each other may have substituents.

[0170] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0171]

[0172] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. １３ R represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. １４R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. １４ If multiple instances exist, each independently represents one of the above groups, such as a hydroxyl group. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The above alkyl group, the above cycloalkyl group, and the above naphthyl group, and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0173] In equation (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. １３ ~R １５ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0174] Next, we will explain equation (ZaII). In equation (ZaII), R ２０４ and R ２０５ Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. ２０４ and R ２０５ The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0175] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ２０４ and R ２０５ Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0176] Specific examples of cations are shown below, but the present invention is not limited to these.

[0177]

[0178]

[0179]

[0180] Bismuth cations can be cited as an example of cations.

[0181] The bismuth cation is preferably a cation represented by the following formula (A5).

[0182]

[0183] In formula (A5), R ａ１４ ~R ａ１７ Each of these independently represents an alkyl group or an aryl group. ａ１４ ~R ａ１７ These may be joined together to form a ring. ａ１４ ~R ａ１７ The alkyl group represented by is R in the above formula (A1). ａ１ ~R ａ４ Examples of alkyl groups represented by R include: ａ１４ ~R ａ１７ The aryl group represented is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.

[0184] R ａ１４ ~R ａ１７ It may further have substituents.

[0185] R ａ１４ ~R ａ１７ Preferably, all of them are aryl groups having 6 to 14 carbon atoms, and more preferably, all of them are phenyl groups.

[0186] Compound (S) may contain cations that do not decompose upon irradiation with active light or radiation. Examples of cations that do not decompose upon irradiation with active light or radiation include alkali metal cations, ammonium cations, pyridinium cations, imidazolium cations, phosphonium cations, carbocations, bismuthonium cations, stivonium cations, stanonium cations, and the like.

[0187] Examples of alkali metal cations include sodium cations, lithium cations, potassium cations, rubidium, and cesium.

[0188] The ammonium cation is preferably a cation represented by the following formula (A1).

[0189]

[0190] In formula (A1), R ａ１ ~R ａ４ Each of these independently represents an alkyl group or an alkoxy group. ａ１ ~R ａ４ The alkyl group represented is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a methyl group, an ethyl group, or a butyl group, and even more preferably a methyl group. ａ１ ~R ａ４ The alkoxy group represented is not particularly limited, but a linear or branched alkoxy group having 1 to 8 carbon atoms is preferred, and a methoxy group is an example.

[0191] R ａ１ ~R ａ４ It may further have substituents.

[0192] R ａ１ ~R ａ４ Preferably, all of them are alkyl groups having 1 to 4 carbon atoms, and more preferably, all of them are methyl groups.

[0193] The pyridinium cation is preferably a cation represented by the following formula (A2).

[0194]

[0195] In formula (A2), R ａ５ R represents a hydrogen atom, an alkyl group, or an alkynyl group. ａ６ R represents an alkyl group or an alkynyl group. p1 represents an integer from 0 to 5. If p1 represents an integer from 2 to 5, multiple R ａ６ They may be the same or they may be different.

[0196] R ａ５ and R ａ６ The alkyl group represented by is R in the above formula (A1). ａ１ ~R ａ４ Examples of alkyl groups represented by R ａ５ and R ａ６ Examples of alkynyl groups represented by this include alkynyl groups having 2 to 6 carbon atoms.

[0197] R ａ５ and R ａ６ It may further have substituents.

[0198] R ａ５ R is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group. ａ６ It is preferable that it is an alkyl group having 1 to 4 carbon atoms.

[0199] p1 represents an integer between 0 and 5, preferably between 0 and 2, and more preferably 0.

[0200] The imidazolium cation is preferably a cation represented by the following formula (A3).

[0201]

[0202] In formula (A3), R ａ７ and R ａ８ Each of these independently represents a hydrogen atom, an alkyl group, or an alkoxy group. ａ９ R represents an alkyl group or alkoxy group. p2 represents an integer from 0 to 3. If p2 represents an integer from 2 to 3, multiple R ａ９ They may be the same or they may be different.

[0203] R ａ７ ~R ａ９ The alkyl group and alkoxy group represented by are R in the above formula (A1). ａ１ ~R ａ４ Examples include alkyl groups and alkoxy groups represented by , and preferred examples are similar.

[0204] R ａ７ ~R ａ９ It may further have substituents.

[0205] R ａ７ and R ａ８ R is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group. ａ９ It is preferable that it is an alkyl group having 1 to 4 carbon atoms.

[0206] p2 represents an integer between 0 and 4, preferably between 0 and 2, and more preferably 0.

[0207] The phosphonium cation is preferably a cation represented by the following formula (A4).

[0208]

[0209] In formula (A4), R ａ１０ ~R ａ１３ Each of these independently represents an alkyl group or an alkoxy group. ａ１０ ~R ａ１３ The alkyl group and alkoxy group represented by are R in the above formula (A1). ａ１ ~R ａ４ Examples include alkyl groups and alkoxy groups represented by .

[0210] R ａ１０ ~R ａ１３ It may further have substituents.

[0211] R ａ１０ ~R ａ１３ Preferably, all of them are alkyl groups having 1 to 8 carbon atoms, and more preferably, all of them are methyl groups.

[0212] Compound (S) preferably contains a cation that decomposes upon irradiation with active light or radiation, more preferably a sulfonium cation, an iodonium cation, or a bismuth cation, and even more preferably a triarylsulfonium cation or a diaryliodonium cation.

[0213] "M ＋ X － In the compound represented by ", X － represents an organic anion. The organic anion is not particularly limited, and examples include 1-valent or 2-valent or higher organic anions. The organic anion is preferably one with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0214] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0215] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group may be, for example, a fluoroalkyl group (which may have substituents other than fluorine atoms; it may also be a perfluoroalkyl group).

[0216] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0217] The alkyl groups, cycloalkyl groups, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0218] In aralkyl carboxylate anions, aralkyl groups having 7 to 14 carbon atoms are preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl groups.

[0219] An example of a sulfonylimid anion is the saccharin anion.

[0220] In bis(alkylsulfonyl)imido anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or fluorine-substituted alkyl groups being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imido anion may bond to each other to form a ring structure. This increases the acid strength.

[0221] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF). ６ － ), fluorinated boron (for example, BF ４ － ), and fluorinated antimony (e.g., SbF ６ － ) are some examples.

[0222] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably having 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0223] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0224]

[0225] In formula (AN1), R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', and -NH. ２ ,-NR' ２ -NHR' or -NHCOR' are preferred. R' is a monovalent hydrocarbon group.

[0226] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. １ and R ２ Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0227] L represents a divalent linking group. If there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of divalent linking groups include alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining multiples thereof. Among these, examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ２ - or -COO-alkylene group- is more preferred.

[0228] For L, a group represented by the following formula (AN1-1) is preferred. * ａ - (CR２ａ ２ ) Ｘ -Q- (CR ２ｂ ２ ) Ｙ - * ｂ (AN1-1)

[0229] In formula (AN1-1), * ａ R in equation (AN1) ３ This indicates the connection point with [the other element]. ｂ This is -C(R) in equation (AN1). １ ) (Caution ２ ) - Represents the connection position with . X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3. R ２ａ and R ２ｂ Each of these independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ If there are multiple instances of each, then there are multiple instances of R ２ａ and R ２ｂ These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) １ ) (Caution ２ )- and CR that bind directly ２ｂ ２ In R ２ｂ is anything other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents the condition where X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) ２ａ and R ２ｂ If all of them are hydrogen atoms, then Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-*Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents. * Ａ R in equation (AN1) ３ This indicates the connection position on the side, * Ｂ This is -SO in equation (AN1). ３ － This indicates the connection point on the side.

[0230] In formula (AN1), R ３ represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0231] Among them, R ３Preferably, the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have substituents. Preferably, the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). The heteroatoms may be substituted for one or more carbon atoms forming the cyclic structure. Preferably, the organic group having a cyclic structure is a cyclic hydrocarbon group, a lactone ring group, and a sultone ring group. Among these, a cyclic hydrocarbon group is preferred. Preferably, the cyclic hydrocarbon group is a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.) and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone structure or sultone structure in any of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0232] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0233] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0234]

[0235] 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.

[0236] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. As 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, and fluorine atom or CF ３ It is more preferable that both Xf atoms are fluorine atoms.

[0237] R ４ and R ５ Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If multiple instances exist, R ４ and R ５ These may be the same or different. ４ and R ５ The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. ４ and R ５ A hydrogen atom is preferred as the element.

[0238] L represents a divalent linking group. The definition of L is the same as the L in formula (AN1).

[0239] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0240] The aryl group may be monocyclic or polycyclic. Examples of the above aryl group include phenyl, naphthyl, phenanthryl, and anthryl groups. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic non-aromatic groups include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0241] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0242] Anions represented by formula (AN2) include SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W, or SO ３ － -CF ２ -CH(CF ３ )-OCO-(L) ｑ’ -W is preferred. Here, L, q, and W are the same as in formula (AN2). q' represents an integer from 0 to 10.

[0243] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0244]

[0245] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have substituents other than a sulfonic acid anion and a -(D-B) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0246] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations thereof.

[0247] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group).

[0248] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions include, for example, N － (SO ２ -R ｑ ) ２ This is an anion represented by R. Here, R ｑ R represents an alkyl group which may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. ｑ They may be joined to each other to form a ring. Two R ｑ The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0249] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0250]

[0251] In formula (d1-1), R ５１represents a hydrocarbon group (e.g., an aryl group such as a phenyl group) which may have substituents (e.g., a hydroxyl group).

[0252] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). ２ｃ The hydrocarbon group in formula (d1-2) may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member carbon atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have substituents. The carbon atoms forming the norbornyl group may be carbonyl carbons. In formula (d1-2), "Z ２ｃ -SO ３ － It is preferable that the anion is different from the anion represented by the aforementioned formulas (AN1) to (AN3). For example, Z ２ｃ The group other than an aryl group is preferable. For example, Z ２ｃ In, -SO ３ － For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z ２ｃ is, -SO ３ － In relation to this, the atom at the α position and / or the atom at the β position are preferably ring member atoms in the cyclic group.

[0253] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0254] In formula (d1-4), R ５３ and R ５４ Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４They may be joined to each other to form a ring.

[0255] Organic anions may be used individually or in combination of two or more.

[0256] Compound (S) is preferably at least one selected from the group consisting of compounds (I) to (II).

[0257] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural site X: Anionic site A １ － and cation site M １ ＋ It consists of and is irradiated with active light or radiation, HA １ Structural site that forms the first acidic site represented by Structural site Y: Anionic site A ２ － and cation site M ２ ＋ It consists of and is irradiated with active light or radiation, HA ２ The structural site (I) that forms the second acidic site represented by satisfies the following condition I.

[0258] Condition I: In the above compound (I), the above cation site M in the above structural site X. １ ＋ and the cation portion M in the structural portion Y. ２ ＋ to H ＋ The compound PI obtained by replacing the above structural site X is the cation site M １ ＋ to H ＋ HA is obtained by replacing it with １ The acid dissociation constant a1 originates from the acidic site represented by the above structure site Y, and the cation site M in the above structural site Y. ２ ＋ to H ＋ HA is obtained by replacing it with ２It has an acid dissociation constant a2 derived from the acidic site represented by the above, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0259] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "HA １ and HA ２ This falls under the category of "compounds having the above characteristics". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, compound PI is "A １ － and HA ２ The pKa at which the compound becomes "a compound having " is the acid dissociation constant a1, and the above "A １ － and HA ２ Compounds having "A" １ － and A ２ － The pKa value at which the compound becomes "a compound having the above characteristics" is the acid dissociation constant a2.

[0260] If compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "two HA １ and one HA ２ This falls under the category of "compounds having one A". When the acid dissociation constant of compound PI is determined, compound PI is "a compound having one A １ － and one HA １ and one HA ２ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２ The acid dissociation constant when a compound having the two A's is obtained corresponds to the aforementioned acid dissociation constant a1. １－ and one HA ２ Compounds having "two A １ － and A ２ － The acid dissociation constant when a compound has the above-mentioned structure corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the above-mentioned cation site M in the above-mentioned structural site X. １ ＋ to H ＋ HA is obtained by replacing it with １ When a compound has multiple acid dissociation constants originating from the acidic site represented by , the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1. １ － and one HA １ and one HA ２ Let aa be the acid dissociation constant when a compound having " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２ When the acid dissociation constant for a compound having the above is denoted as ab, the relationship between aa and ab satisfies aa < ab.

[0261] The acid dissociation constants a1 and a2 are determined by the acid dissociation constant measurement method described above. The compound PI mentioned above corresponds to the acid generated when compound (I) is irradiated with active light or radiation. If compound (I) has two or more structural sites X, the structural sites X may be the same or different. Also, two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different. In compound (I), the above A １ － and A above ２ － , and the above M １ ＋ and the above M ２ ＋These may be the same or different, but A above １ － and A above ２ － It is preferable that they are all different.

[0262] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. There is no particular upper limit to the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2, but for example, it is 16 or less.

[0263] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0264] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0265] Anion part A １ － and anion part A ２ － This is a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion site A １ － Preferably, it is an acidic moiety that can form an acidic moiety with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion moiety A ２ － For example, Anion part A １ －It is preferable that the acidic site can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6) below, * represents the bond position. In formula (AA-2), R Ａ R represents a monovalent organic group. Ａ The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0266]

[0267]

[0268] Cation site M １ ＋ and cation site M ２ ＋ This is a structural site containing a positively charged atom or group of atoms, for example, a cation with a monovalent charge. As an example of a cation, see the aforementioned M ＋ Examples of cations represented by the following are given.

[0269] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acid

[0270] Definition of structural site X in compound (II), and A １ － and M １ ＋ The definition of is the definition of structural site X in compound (I) as described above, and A １ － and M １ ＋ This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0271] In the above compound (II), the above cation moiety M in the above structural moiety X. １＋ to H ＋ In compound PII, which is obtained by replacing the above structural site X, the above cation site M １ ＋ to H ＋ HA is obtained by replacing it with １ The preferred range for the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in compound PI. Note that if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, then compound PII is "two HA １ This falls under the category of "a compound having one A". When the acid dissociation constant of this compound PII is determined, compound PII is "a compound having one A １ － and one HA １ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ Compounds having "two A １ － The acid dissociation constant when the compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0272] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. Compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. The two or more structural sites X may be the same or different. Two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different.

[0273] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, and is preferably a site containing a group that can electrostatically interact with a proton, or a functional group having electrons. Examples of groups that can electrostatically interact with a proton, or functional groups having electrons, include functional groups having a macrocyclic structure such as a cyclic polyether, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0274]

[0275] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0276] Examples of non-cationic sites that compound (I) and compound (II) may have are given below.

[0277]

[0278]

[0279] Furthermore, it is also preferable that compound (S) has an anion containing a group 13 or group 14 element. In this embodiment, it is more preferable that compound (S) has an anion containing boron, silicon, or aluminum, and even more preferable that it has an anion containing boron or silicon. Examples of anion forms in compound (S) include borate anions, gallate anions, and indate anions.

[0280] When the composition of the present invention contains compound (S), the content of compound (S) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the content of compound (S) is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 50.0% by mass or less, relative to the total solid content of the composition of the present invention. Only one type of compound (S) may be used, or two or more types may be used. When two or more types of compound (S) are used, it is preferable that their total content is within the range of the above preferred content.

[0281] [Acid Diffusion Control Agent] Preferably, the composition of the present invention further contains an acid diffusion control agent. The acid diffusion control agent can act as a quencher that traps the acid generated from, for example, a photoacid generator during exposure, and suppresses the reaction of the resin (A) in the unexposed area due to excess generated acid.

[0282] The acid diffusion control agent preferably contains metal atoms. The metal atoms are not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, the same applies as above, and the preferred range is also the same. There may be one type of metal atom or two or more types. In a preferred embodiment, it is preferable that at least one of the metal atoms is selected from groups 13 to 16. It is preferable that the metal atoms are from the 4th to 6th period of the periodic table and from groups 13 to 16.

[0283] When the acid diffusion control agent is a compound having an anion and a cation, it is preferable that at least one of the anion and the cation has a metal atom.

[0284] The acid diffusion control agent more preferably comprises at least one selected from the group consisting of aluminum, gallium, indium, germanium, tin, and bismuth. It is even more preferable that the acid diffusion control agent comprises at least one selected from the group consisting of gallium, indium, germanium, tin, and bismuth. It is particularly preferable that the acid diffusion control agent comprises at least one selected from the group consisting of germanium, tin, and bismuth.

[0285] The type of acid diffusion control agent is not particularly limited, and examples include basic compounds (DA), low molecular weight compounds (DB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (DC) include onium salt compounds (DD) of acids that are relatively weak acids with respect to the acid generated from the photoacid generator, and basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation.

[0286] (Basic compound (DA)) As the basic compound (DA), a compound having a structure represented by any of the following formulas (O-1) to (O-5) is preferred.

[0287]

[0288] In formulas (O-1) and (O-5), R ３００ , R ３０１ and R ３０２ These may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 20 carbon atoms). ３０１ and R ３０２ These may be joined together to form a ring. ３０３ , R ３０４ , R ３０５ and R ３０６ These may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms. In formulas (O-2), (O-3), (O-4), and (O-5), * represents a bond position.

[0289] R in formulas (O-1) and (O-5)３００ , R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ and R ３０６ The alkyl group or cycloalkyl group represented by may have substituents or be unsubstituted. As for the alkyl group, preferred substituents are C1-C20 aminoalkyl groups, C1-C20 hydroxyalkyl groups, or C1-C20 cyanoalkyl groups. In formulas (O-1) and (O-5), R ３００ , R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ and R ３０６ The alkyl group or cycloalkyl group represented by is more preferably unsubstituted.

[0290] Examples of basic compounds (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (DA) may also be a compound having at least one selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (DA) may also be an alkylamine derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond.

[0291] The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (DA)) is preferably 1.00 or higher, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. Furthermore, the pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator used, but for example, it is preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0292] (Onium salt compound (DD) of an acid that is a relatively weak acid with respect to the acid generated from a photoacid generator) Compound (DD) may be a compound that generates an acid upon irradiation with an actinic ray or radiation. Compound (DD) is preferably a compound that generates an acid having a pKa that is 1.00 or more larger than the pKa of the acid generated from the photoacid generator. The difference between the pKa of the acid generated from compound (DD) and the pKa of the acid generated from the photoacid generator (value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from compound (DD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, still more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. Further, although the pKa of the acid generated from compound (DD) varies depending on the type of photoacid generator used, for example, it is preferably 0.50 to 10.00, more preferably 0.80 to 5.00, still more preferably 1.00 to 5.00.

[0293] Compound (DD) is preferably an onium salt compound composed of an anion and a cation. Examples of compound (DD) include "M ＋ X － " which is a compound (onium salt) represented thereby. M ＋ represents a cation, and X － represents an organic anion. Examples of M ＋ include the same ones as M ＋ described in the explanation of compound (S). Examples of X － include anions represented by formulas (d1-1) to (d1-4) described in the explanation of compound (S), and an anion represented by formula (d1-1) or an anion represented by formula (d1-2) is preferable.

[0294] Specific examples of basic compounds (DA) include, for example, those described in paragraphs

[0132] to

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

[0137] to

[0155] and paragraph

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

[0156] to

[0163] of International Publication No. 2020 / 066824. Specific examples of onium salt compounds (DDs) that are relatively weak acids to the acids generated from photoacid generators, etc., include, for example, those described in paragraphs

[0305] to

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

[0295] In addition to the above, 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 can be suitably used as acid diffusion control agents.

[0296] The molecular weight of the acid diffusion control agent is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0297] The acid diffusion control agent is also preferably a compound that generates an acid with a pKa of 0 or higher upon irradiation with active light or radiation.

[0298] When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the acid diffusion control agent is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, based on the total solid content of the composition of the present invention. Only one type of acid diffusion control agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0299] <Hydrophobic Resin> The composition of the present invention may further contain a hydrophobic resin different from resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances.

[0300] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 contained in the side chain portion of the resin. ３ It is preferable to have one or more of the substructures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306. The hydrophobic resin preferably has a metal atom. The metal atom is not particularly limited, but examples include metal atoms from groups 1 to 16 of the periodic table. Specifically, it is the same as above, and the preferred range is also the same.

[0301] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, based on the total solid content of the composition of the present invention. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0302] <Surfactants> The compositions of the present invention may contain surfactants. The inclusion of surfactants allows for better adhesion and the formation of patterns with fewer development defects. Fluorine-based and / or silicone-based surfactants are preferred. Examples of fluorine-based and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

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

[0303] When the composition of the present invention contains a surfactant, the surfactant content 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, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0304] <Solvent> The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0305] Combining the aforementioned solvent with the aforementioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The aforementioned solvent has a good balance of solubility, boiling point, and viscosity with the aforementioned resin, and can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0306] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0307] Bio-derived solvents can also be used as solvents. Examples of bio-derived solvents include those described in Japanese Patent Publication No. 2002-363135, U.S. Patent Application Publication No. 2015 / 0004664A1, International Publication No. 2025 / 106697, etc., as well as commercially available products such as the PURASOLV® ELECT series (see https: / / www.corbion.com / solutions / biochemical-specialties / electronics and https: / / www.corbion.com / - / media / Corbion / Files / PLA-PDFs-7-of-24 / brch-electronics-purasolv-eng-0421_940879.ashx). The bio-derived solvents described above can be purified using methods such as distillation and filtration as appropriate to achieve the purity required in the technical field of the present invention.

[0308] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably so that it is 1 to 20% by mass. This further improves the applicability of the composition of the present invention.

[0309] <Other Additives> The composition of the present invention may further contain at least one selected from the group consisting of dissolution inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in a developer (for example, phenol compounds with a molecular weight of 1000 or less, or alicyclic or aliphatic compounds containing a carboxyl group). The above-mentioned "dissolution inhibitor" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer.

[0310] The content of other additives is not particularly limited, but may be 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, relative to the total solid content of the composition of the present invention. Only one type of other additive may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0311] Furthermore, the composition of the present invention may contain water as an impurity. When water is present as an impurity, a smaller amount of water is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total composition of the present invention. Furthermore, the composition of the present invention may contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of resin (A)). When residual monomers are present as impurities, a smaller amount of residual monomers is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total solid content of the composition of the present invention.

[0312] [Reactive light-sensitive or radiation-sensitive film, and pattern formation method] The present invention also relates to a reactive light-sensitive or radiation-sensitive film (preferably a resist film) formed by the composition of the present invention. The present invention also relates to a pattern formation method comprising the steps of: forming a resist film on a substrate using the composition of the present invention; exposing the resist film; and developing the exposed resist film using a developer.

[0313] The procedure for a pattern formation method using the composition of the present invention is not particularly limited, but it is preferable to have the following steps: Step 1: A step of forming a resist film on a substrate using the composition of the present invention. Step 2: A step of exposing the resist film. Step 3: A step of developing the exposed resist film using a developer. The procedure for each of the above steps will be described in detail below.

[0314] <Step 1: Resist Film Formation Step> Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0315] One method for forming a resist film on a substrate using the composition of the present invention is to coat the substrate with the composition of the present invention. It is preferable to filter the composition of the present invention before coating, if necessary. 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.

[0316] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed in the layer below the resist film.

[0317] As for drying methods, for example, a method of drying by heating can be used. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0318] The thickness of the resist film is not particularly limited, but 10 to 120 nm is preferred in order to form finer patterns with higher precision. In particular, when using EUV exposure and EB exposure, the thickness of the resist 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 resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0319] Furthermore, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition can be applied uniformly to the upper layer of the resist film without being mixed with the resist film. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods. For example, a topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Application Publication No. 2013-061648, on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be contained in the composition of the present invention. It is also preferable that the topcoat contains a compound that includes at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0320] <Step 2: Exposure Step> Step 2 is a step of exposing the resist film. One method of exposure is to irradiate the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer lasers (157 nm), EUV (13 nm), X-rays, and electron beams.

[0321] It is preferable to perform a post-exposure heat treatment (also called post-exposure baking) after exposure and before development. Post-exposure heat treatment promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a normal exposure machine and / or developer machine, and may also be done using a hot plate or the like.

[0322] <Step 3: Development Step> Step 3 is the step of developing the exposed resist film using a developer to form a pattern. The developer may be an alkaline developer, or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0323] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and leaving it still for a certain period of time (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). In addition, after the development process, a step may be performed to stop development while replacing the solvent with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0324] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0325] 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.

[0326] Bio-derived solvents can also be used as organic solvents in organic developing solutions. Examples of bio-derived solvents include those described in U.S. Patent Application Publication 2025 / 0068079A1, Proceedings of SPIE, 12957, 1295719 (2024), etc. The above-mentioned bio-derived solvents can be purified using methods such as distillation and filtration as appropriate to achieve the purity required in the technical field of the present invention.

[0327] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0328] The following embodiments (OD1) and (OD2) are preferred embodiments of the organic developer: (OD1) An embodiment in which the organic developer is n-butyl acetate (OD2) An embodiment in which the organic developer is a mixed solvent of n-butyl acetate and a hydrocarbon having 11 or more carbon atoms The mixed solvent of (OD2) described above is also called the mixed solvent (OD2). The hydrocarbon having 11 or more carbon atoms in the mixed solvent (OD2) is preferably an alkane, more preferably an alkane having 11 to 15 carbon atoms, even more preferably an alkane having 11 to 13 carbon atoms, particularly preferably undecane or dodecane, and most preferably undecane. If structural isomers exist for the hydrocarbon having 11 or more carbon atoms, such as undecane or dodecane, the mixed solvent (OD2) may contain only one type of hydrocarbon having 11 or more carbon atoms, or two or more types. The content of hydrocarbons having 11 or more carbon atoms in the mixed solvent (OD2) (or the total amount if multiple types of hydrocarbons having 11 or more carbon atoms are included) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire mixed solvent (OD2).

[0329] The content of n-butyl acetate in the mixed solvent (OD2) is preferably 65% ​​to 99% by mass, more preferably 70% to 95% by mass, and even more preferably 75% to 90% by mass, based on 100% by mass of the entire mixed solvent (OD2).

[0330] A particularly preferred embodiment of the mixed solvent (OD2) is one in which n-butyl acetate and undecane are contained, and the mass ratio of "n-butyl acetate / undecane" is "90 / 10".

[0331] The developer may contain other components in addition to the components described above. Examples of other components include surfactants, antioxidants, and basic compounds. The content of other components in the developer is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, even more preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass (i.e., no other components are present), based on 100% by mass of the entire developer.

[0332] <Other steps> The pattern forming method described above preferably includes a step of washing with a rinsing solution after step 3.

[0333] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may also be added to the rinsing solution.

[0334] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent 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. Bio-derived solvents can also be used as the rinsing solution. Examples of bio-derived solvents include the bio-derived solvents presented above as organic solvents in the organic developer.

[0335] The rinsing process is not particularly limited and can be performed by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or spraying rinsing solution onto the substrate surface (spray method). Furthermore, the pattern formation method of the present invention may include a heating process (post bake) after the rinsing process. This process removes developer and rinsing solution remaining between and inside the patterns due to baking. This process also has the effect of softening the resist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0336] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate. The method of processing the substrate (or the underlying film and substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask is preferred. For dry etching, oxygen plasma etching is preferred.

[0337] In the pattern forming method of the present invention, it is preferable that the various materials used (for example, solvents, developers, rinse solutions, anti-reflective film forming compositions, topcoat forming compositions, etc.) do not contain impurities such as metals. The impurity content in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0338] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

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

[0339] Furthermore, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as lining the inside of the apparatus with Teflon (registered trademark).

[0340] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above 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 equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the manufacturing equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less.

[0341] To prevent malfunctions of chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge in organic treatment solutions such as rinsing solutions, conductive compounds may be added. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. For chemical piping, for example, various pipes made of SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) coated with antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) coated with antistatic treatment can be used.

[0342] [Method for Manufacturing Electronic Devices] This specification relates to a method for manufacturing electronic devices, including the pattern forming method described above, and to electronic devices manufactured by this manufacturing method. Preferred embodiments of the electronic devices described herein include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0343] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0344] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0345] <Resin> As resin (A), A-1 to A-28 are used. The structures of A-1 to A-28 (the structure of the repeating units in each resin and their content) are shown below. The content of each repeating unit is indicated by a subscript to the right of the parentheses of each repeating unit. The content of each repeating unit (the ratio of its content to the total repeating units in the resin) is expressed as a molar ratio (mol%). The composition ratio (mol% ratio), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in each resin are also shown. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). The content of the repeating units is １３ Measurement is performed using C-NMR (nuclear magnetic resonance).

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353] [Synthesis Example of Resin (A-2)] An example of the synthesis of resin (A-2) is shown below. Cyclohexanone (8 g) is heated to 80°C under a nitrogen stream. While stirring this solution, a mixed solution of parahydroxystyrene (2.9 g), 1-(2-(trimethylgermyl)ethyl)cyclopentyl methacrylate (7.1 g), cyclohexanone (32 g), and 2,2'-dimethyl azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (0.5 g) is added dropwise over 6 hours to obtain the reaction solution. After the dropwise addition is complete, the reaction solution is stirred at 80°C for a further 2 hours. After the obtained reaction solution is allowed to cool, it is reprecipitated with a large amount of heptane, filtered, and the resulting solid is vacuum dried to obtain 6.5 g of resin (A-2). Other resins can be synthesized in the same manner as resin (A-2).

[0354] <Photoacid Generator> S-1 to S-10 are used as the photoacid generator (compound (S)). Me represents a methyl group.

[0355]

[0356]

[0357]

[0358] <Acid Diffusion Control Agents> Q-1 to Q-10 are used as acid diffusion control agents.

[0359]

[0360]

[0361] <Solvent> As the solvent, use MSL-1 to MSL-6, which are obtained by mixing at least two of the following SL-1, SL-2, SL-4, SL-5, and SL-6 in the proportions shown in Table 1 below, or SL-3 below. The values ​​in Table 1 below represent the mass ratio (mass%) of SL-1, SL-2, SL-4, SL-5, and SL-6 contained in MSL-1 to MSL-6. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether (PGME) SL-3: Cyclohexanone SL-4: γ-butyrolactone SL-5: Ethyl lactate SL-6: Diacetone alcohol

[0362]

[0363] <Preparation of Resist Composition> The components shown in Table 2 below are used in the amounts shown in the table and mixed with the solvent shown in the table. The resulting mixture is then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm to prepare the resist compositions (R-1 to R-32, HR-1 to HR-2). The solid content concentration of the resist composition is 1.5% by mass. In the table, the "Content" column shows the percentage (by mass) of each component relative to the total solid content in the resist composition. In the resist composition, solid content refers to all components other than the solvent.

[0364] Table 2 also shows the number of components containing metal atoms, and the total amount of metal atoms relative to the total solid content of the resist composition. The total amount of metal atoms is determined from the content values ​​of each compound in the formulation of the present invention.

[0365]

[0366] [Examples 1 to 32, Comparative Examples 1 to 2] <Pattern Forming Method (1): EUV Exposure, Alkali Development (Positive)> A composition for forming an underlayer film, AL412 (manufactured by Brewer Science), is applied onto a silicon wafer having a diameter of 300 mm, and baked at 205°C for 60 seconds to form an underlayer film having a film thickness of 20 nm. The resist composition shown in Table 3 is applied onto the underlayer film, and pre-exposure bake (Post Applied Bake; PAB) is performed at 120°C to form a resist film having a film thickness of 50 nm. Thus, a silicon wafer having a resist film is formed. Pattern irradiation was performed on the silicon wafer having the resist film obtained by the above procedure while changing the exposure amount using an EUV scanner NXE3400 (NA 0.33) manufactured by ASML. As a reticle, a hexagonal array contact hole mask (dark field mask) with a pitch of 36 nm and an opening dimension of 20 nm is used. Then, only when described, post-exposure bake (Post Exposure Bake; PEB) is performed at the temperature shown in Table 3 for 60 seconds, followed by development with a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 30 seconds, rinsing by pouring pure water over the wafer for 10 seconds while rotating the wafer at a rotation speed of 1000 rpm, and then rotating the wafer at a rotation speed of 4000 rpm for 30 seconds, whereby a positive contact hole pattern with a pitch of 36 nm is obtained.

[0367] [Evaluation] The obtained pattern is evaluated for sensitivity and LCDU by the following method. The results shown in Table 3 are obtained.

[0368] <Sensitivity> The irradiation energy for resolving a contact hole pattern having a hole diameter of 18 nm and a pitch of 36 nm is defined as sensitivity (Eop) (mJ / cm ２ ).

[0369] <LCDU> A contact hole pattern with a hole diameter of 18 nm and a pitch of 36 nm is formed at the exposure dose that shows the above sensitivity (Eop). 2000 holes in the resulting pattern are observed using a scanning electron microscope (SEM: Hitachi High-Technologies Corporation CG6300), and the CD variation of the hole CD (Critical Dimension) is defined as the LCDU (unit: nm). A smaller LCDU value is preferable.

[0370] Furthermore, the remaining film thickness after etching is evaluated as follows. The results shown in Table 3 are obtained.

[0371] <Etching Resistance> Etching resistance is evaluated by the remaining film thickness after etching, as follows: A resist composition shown in Table 3 is applied to a silicon wafer with a diameter of 100 mm, and baked at 120°C to form a resist film with a thickness of 50 nm. This forms a silicon wafer having a resist film. The silicon wafer having the resist film obtained by the above procedure is subjected to an ICP-RIE (Inductively Coupled Plasma-Reactive Ion Etching) apparatus (Spica, manufactured by Sumitomo Precision Products Co., Ltd.) and Gas:O ２ After RIE treatment under the conditions of 10 sccm / Ar 90 sccm, Pressure: 1 Pa, Source: 200 W, Bias: 0 W, Time: 20 s, the thickness of the resist film (remaining thickness (nm)) is measured. A larger resist film thickness after treatment indicates superior etching resistance.

[0372] The evaluation results are shown in Table 3.

[0373]

[0374] [Examples 33-64, Comparative Examples 3-4] <Pattern Formation Method (2): EUV Exposure, Organic Solvent Development (Negative)> An underlayer film formation composition AL412 (manufactured by Brewer Science, Inc.) is applied to a silicon wafer with a diameter of 300 mm and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 4 is applied on top of the underlayer film and pre-exposure bake (Post Applied Bake; PAB) is performed at 120°C to form a resist film with a thickness of 30 nm. This forms a silicon wafer having a resist film. Pattern irradiation was performed on the silicon wafer having a resist film obtained by the above procedure using an ASML EUV scanner NXE3400 (NA 0.33) while changing the exposure amount. A hexagonal array contact hole mask (dark field mask) with a pitch of 36 nm and an aperture size of 20 nm was used as the reticle. Subsequently, if specified, the wafer is exposed to light for 60 seconds at the temperatures shown in Table 4 and then baked (Post Exposure Bake; PEB). This is followed by development for 30 seconds in a mixed solvent of 90% by mass butyl acetate and 10% by mass n-undecane, and the wafer is rotated at 4000 rpm for 30 seconds to obtain a negative-type pillar pattern with a pitch of 36 nm.

[0375] [Evaluation] The obtained patterns are evaluated for sensitivity and LCDU using the following method. The results shown in Table 4 are obtained.

[0376] <Sensitivity> Sensitivity (Eop) (mJ / cm) is the irradiation energy required to resolve a pillar pattern with a pillar diameter of 18 nm and a pitch of 36 nm. ２ )

[0377] <LCDU> Pillars with a diameter of 18 nm and a pitch of 36 nm are formed at the exposure dose that shows the above sensitivity (Eop). 2000 pillars are observed in the resulting pattern using a scanning electron microscope (SEM: Hitachi High-Technologies Corporation CG6300), and the CD variation of the pillar CD (Critical Dimension) is defined as the LCDU (unit: nm). A smaller LCDU value is preferable.

[0378] The evaluation results are shown in Table 4.

[0379]

[0380] From the table above, it can be seen that the resist composition of the example makes it possible to form a pattern with excellent sensitivity and LCDU, and also to form a resist film with excellent etching resistance.

[0381] The present invention provides a photosensitive or radiation-sensitive resin composition that can form patterns with excellent sensitivity and LCDU, and can also form a resist film with excellent etching resistance. Furthermore, the present invention provides a photosensitive or radiation-sensitive film formed using the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0382] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2025-053624 filed on 27 March 2025, the contents of which are incorporated herein by reference.

Claims

A photosensitive or radiation-sensitive resin composition containing a resin whose polarity increases due to the action of an acid, and a photoacid generator, The aforementioned composition contains two or more components, each having a metal atom. The total amount of metal atoms in the two or more components is 4.0% by mass or more relative to the total solid content of the composition. Actinic ray-sensitive or radiation-sensitive resin composition. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the two or more components include a first component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony, and a second component having a metal atom that is germanium, bismuth, gallium, tin, indium, or antimony. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the total amount of metal atoms is 6.0% by mass or more with respect to the total solid content of the composition. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the total amount of metal atoms is 8.0% by mass or more with respect to the total solid content of the composition. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein at least one metal atom is selected from groups 13 to 16. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of the metal atoms is an organometallic atom. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin has metal atoms in its side chains. 　 A photosensitive or radiation-sensitive film formed using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 7. 　 A step of forming a resist film on a substrate using the photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, The steps include: exposing the resist film, A pattern forming method comprising the step of developing the exposed resist film using a developer. 　 The pattern forming method according to claim 9, wherein the developing solution is an alkaline developing solution or a developing solution containing an organic solvent. 　 A method for manufacturing an electronic device, comprising the pattern formation method described in claim 9.

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