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

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) including a repeating unit having at least one group selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group, and a repeating unit having an acid-decomposable group, a resin (B) satisfying a specific formula and not including a repeating unit having a fluorinated alkyl group, and a solvent; an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition; a pattern formation method; and a method for manufacturing 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 formation 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 formation 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 photosensitive or radiation-sensitive resin composition containing a resin having a group that decomposes upon the action of an acid to produce a polar group, and a specific compound.

[0005] Japanese Patent Application Publication No. 2014-149409

[0006] Recently, the performance requirements for resist compositions have been increasing. In particular, there is a demand for improved resolution when forming fine patterns. Furthermore, while resist compositions may be stored for a certain period after preparation, it is desirable that they exhibit excellent line width roughness (LWR) performance when patterns are formed after such storage. LWR performance refers to the ability to reduce the LWR of a pattern. The LWR performance of a resist composition immediately after preparation is also called "initial LWR performance," and the LWR performance of a resist composition after a certain period has elapsed since preparation is also called "LWR performance over time." In addition, due to manufacturing process requirements, it is desirable that resist compositions have minimal influence on performance due to the time elapsed from exposure to post-exposure baking (PEB), that is, excellent post-exposure time delay (PED) stability.

[0007] Therefore, the object of the present invention is to provide a photosensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance over time, and PED stability. Furthermore, the object of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above photosensitive or radiation-sensitive resin composition.

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

[0009] [1] A resin (A) containing at least one repeating unit selected from the group consisting of an aromatic ring group having a phenolic hydroxyl group and a carboxy group, and a repeating unit having an acid-decomposable group, a resin (B) satisfying the following formula (i-1) and not containing a repeating unit having a fluorinated alkyl group, and a solvent-containing photosensitive or radiation-sensitive resin composition. B Ｍｅ / B ｔｏｔａｌ ≥ 0.05 (i-1) In the formula (i-1), B ｔｏｔａｌ represents the sum of the values obtained by multiplying the molecular weight of the monomer corresponding to each repeating unit contained in the resin (B) by the molar fraction of the repeating unit contained in the resin (B). B Ｍｅ represents the sum of the values obtained by multiplying the number of methyl groups of the monomer corresponding to each repeating unit contained in the resin (B) by the formula weight of the methyl group and the molar fraction of the repeating unit contained in the resin (B). [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the resin (A) contains a repeating unit represented by the following formula (Ga1).

[0010]

[0011] In the formula (Ga1), R ａ１ R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ａ１ represents a single bond or a divalent linking group. Ar ｇ１ represents an aromatic ring group. X ａ１ represents -O- or -C(=O)O-. G ｚ１ represents a group represented by the following formula (G-1) or (G-2).

[0012]

[0013] In the formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ５ and R ａ６ each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. Rａ４ and R ａ５ may combine to form a ring. G ｚ１ When is a group represented by the formula (G-1), Ar ｇ１ is R ａ３ or R ａ４ may combine to form a ring. * represents the bonding position. In the formula (G-2), R ａ７ , R ａ８ and R ａ９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. Two of R ａ７ , R ａ８ and R ａ９ may combine to form a ring. * represents the bonding position. [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin (B) contains a repeating unit having an acid group. [4] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (B) contains a repeating unit having an acid-decomposable group. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (B) contains a repeating unit having an aromatic ring group. [6] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin (B) satisfies the following formula (i-2). B Ｍｅ / B ｔｏｔａｌ ≧0.10 (i-2) B in the formula (i-2) ｔｏｔａｌ and B Ｍｅ each represent the same meaning as B ｔｏｔａｌ and B Ｍｅ in the formula (i-1). [7] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the content of the resin (A) with respect to the content of the resin (B) in the photosensitive or radiation-sensitive resin composition is 100% by mass or more. [8] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (B) contains a repeating unit represented by the following formula (Gb1).

[0014]

[0015] In the formula (Gb1), R ｂ１, R ｂ２ and R ｂ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ｂ１ X represents a single bond or a divalent linking group. ｂ１ represents -O- or -C(=O)O-. G ｚ２ This represents a group represented by the following formula (G-3) or (G-4).

[0016]

[0017] In formula (G-3), R ｂ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ５ and R ｂ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ４ and R ｂ５ They may combine to form a ring. G ｚ２ If the group is represented by formula (G-3), then L ｂ１ is R ｂ３ or R ｂ４ It may combine with to form a ring. * indicates the bonding position. In formula (G-4), R ｂ７ , R ｂ８ and R ｂ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ７ , R ｂ８ and R ｂ９ Two of them may bond to form a ring. * indicates the bonding position. [9] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], further comprising a compound (C) that generates acid upon irradiation with active light or radiation.

[10] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], further comprising an acid diffusion control agent (D).

[11] The photosensitive or radiation-sensitive resin composition according to [9], wherein the compound (C) comprises an anion represented by the following formula (AN3).

[0018]

[0019] In formula (AN3), Ar represents an aromatic ring group. n represents an integer of 0 or more. D represents a single bond or a divalent linking group. B represents a hydrocarbon group.

[12] The photosensitive or radiation-sensitive resin composition according to

[10] , wherein the acid diffusion control agent (D) is an anion represented by the following formula (d1-1).

[0020]

[0021] In formula (d1-1), R ５１ ∫ represents a substituent.

[13] A photosensitive or radiation-sensitive film formed by a photosensitive or radiation-sensitive resin composition according to any one of [1] to

[12] .

[14] A pattern-forming method comprising the steps of: forming a photosensitive or radiation-sensitive film on a substrate with a photosensitive or radiation-sensitive resin composition according to any one of [1] to

[12] ; exposing the photosensitive or radiation-sensitive film; and developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern.

[15] A method for manufacturing an electronic device, comprising the pattern-forming method according to

[14] .

[0022] The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution, LWR performance over time, and PED stability. Furthermore, the present invention provides a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition.

[0023] The present invention will now be described in detail. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0024] 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.

[0025] 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.

[0026] 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).

[0027] 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.

[0028] (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.

[0029] 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".

[0030] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0031] 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 it by calculating 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.

[0032] In this specification, pKa refers to a 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 using 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.

[0033] 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.

[0034] <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 resin (A) containing repeating units having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group, and repeating units having an acid-degradable group, a resin (B) that satisfies formula (i-1) and does not contain repeating units having a fluorinated alkyl group, and a solvent. Ｍｅ / B ｔｏｔａｌ ≥ 0.05 (i-1) In equation (i-1), B ｔｏｔａｌ This represents the sum of the values ​​obtained by multiplying the molecular weight of the monomer corresponding to each repeating unit contained in resin (B) by the mole fraction of each repeating unit contained in resin (B). Ｍｅ This represents the sum of the values ​​obtained by multiplying the number of methyl groups in the monomer corresponding to each repeating unit contained in resin (B), the formula weight of the methyl groups, and the mole fraction of each repeating unit contained in resin (B).

[0035] Although the mechanism by which the above-mentioned effects are obtained by the composition of the present invention is not yet clear, the inventors have made the following hypothesis. However, the present invention is not limited in any way by the following hypothesis mechanism. The resin (B) contained in the composition of the present invention satisfies formula (i-1), and since the ratio of methyl groups to molecular weight is above a certain level, it is more hydrophobic than resin (A). Therefore, it is thought that resin (B) is unevenly distributed on the surface in the photosensitive or radiation-sensitive film formed from the composition of the present invention, improving resolution. Furthermore, since resin (B) does not contain repeating units having alkyl fluoride, hydrogen fluoride is not generated even when exposed to light, resulting in excellent aging stability and good LWR performance and PED stability over time.

[0036] 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.

[0037] [Resin (A) comprising repeating units having at least one selected from the group consisting of phenolic hydroxyl groups and aromatic ring groups having carboxyl groups, and repeating units having acid-degradable groups] The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") comprising repeating units having at least one selected from the group consisting of phenolic hydroxyl groups and aromatic ring groups having carboxyl groups, and repeating units having acid-degradable groups. It is preferable that resin (A) is a different resin from resin (B). That is, it is preferable that the value obtained by dividing the sum of the product of the number of methyl groups in each repeating unit contained in resin (A), the formula weight of the methyl groups, and the mole fraction of each repeating unit contained in resin (A), by the sum of the product of the molecular weight of the monomer corresponding to each repeating unit contained in resin (A) and the mole fraction of each repeating unit contained in resin (A), is less than 0.05.

[0038] (Repeating units having acid-degradable groups) Resin (A) contains repeating units having acid-degradable groups. It is preferable that resin (A) is an acid-degradable resin. Acid-degradable groups are groups that decompose and increase in polarity upon the action of an acid. Typically, acid-degradable groups are groups that decompose upon the action of an acid to produce polar groups. It is preferable that acid-degradable groups have a structure in which the polar group is protected by a group that is left behind upon the action of an acid (leaving group). Typically, resin (A) increases in polarity upon the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. Preferred polar groups include alkali-soluble groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups.

[0039] Examples of groups that are eliminated by the action of an acid (leaving groups) include those 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 ) (Caution ３７ ) ( OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0040] In equations (Y1) and (Y2), Rx １ ~Rx ３ Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched). １ ~Rx ３ If all of them are alkyl groups (linear or branched), then Rx １ ~Rx ３ It is preferable that at least two of them are methyl groups. In particular, Rx １ ~Rx ３ Each preferably independently represents a linear or branched alkyl group, and Rx １ ~Rx ３ It is more preferable that each of these independently represents a linear alkyl group. １ ~Rx ３ These two may bond to each other to form a ring (which may be monocyclic or polycyclic). Rx １ ~Rx ３ The alkyl group may be linear or branched. Preferred alkyl groups include C1-C10 groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, and C1-C5 groups are more preferred. １ ~Rx ３The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. Rx １ ~Rx ３ The cycloalkyl group of Rx~Rx 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. One or more of the methylene groups constituting the cycloalkyl group may be replaced by a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, a group having a hetero atom such as a carbonyl group or a vinylidene group. Further, one or more of the ethylene groups constituting the ring may be replaced by a vinylene group. Rx １ ~Rx ３ As the aryl group of Rx~Rx, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and examples thereof include a phenyl group, a naphthyl group, an anthryl group and the like. Rx １ ~Rx ３ As the aralkyl group of Rx~Rx, a group in which one hydrogen atom in the alkyl group of Rx~Rx described above is replaced by an aryl group having 6 to 10 carbon atoms (preferably a phenyl group) is preferable, and examples thereof include a benzyl group and the like. Rx １ ~Rx ３ As the alkenyl group of Rx~Rx, an alkenyl group having 2 to 20 carbon atoms is exemplified, an alkenyl group having 2 to 10 carbon atoms is preferable, and for example, a vinyl group and an allyl group are preferable. Rx １ ~Rx ３ As the alkynyl group of Rx~Rx, an alkynyl group having 2 to 20 carbon atoms is exemplified, an alkynyl group having 2 to 10 carbon atoms is preferable, and for example, an ethynyl group is preferable. Rx １ ~Rx ３ As the ring formed by bonding two of Rx~Rx, a cycloalkane ring is preferable. Rx １ ~Rx ３ As the ring formed by bonding two of Rx~Rx, a cycloalkane ring is preferable. Rx １ ~Rx ３The 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 ３ The 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 configuration in which the two are bonded together to form a cycloalkane ring is preferred.

[0041] 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 R be a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. Also, R ３８ R may bond with other substituents on the repeating main chain to form a ring. ３８A group formed by the bonding of another substituent having a main chain of a repeating unit to each other is preferably an alkylene group such as a methylene group.

[0042] 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 be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0043] The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (Ga1). Resin (A) preferably contains a repeating unit represented by formula (Ga1).

[0044]

[0045] In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ａ１ represents a single bond or a divalent linking group. Ar ｇ１ represents an aromatic ring group. X ａ１ represents -O- or -C(=O)O-. G ｚ１ represents a group represented by formula (G-1) or (G-2).

[0046]

[0047] In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ５ and R ａ６ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ４ and R ａ５ may be bonded to form a ring. When G ｚ１ is a group represented by formula (G-1), Ar ｇ１ may be bonded to R ａ３ or R ａ４ to form a ring. * represents the bonding position. In formula (G-2), R ａ７ , Rａ８ and R ａ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ７ , R ａ８ and R ａ９ Two of them may join to form a ring. * indicates the bonding position.

[0048] R in equation (Ga1) ａ１ , R ａ２ and R ａ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ , R ａ２ and R ａ３ 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. ａ１ , R ａ２ and R ａ３ 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 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. The above cycloalkyl group may have substituents. ａ１ , R ａ２ and R ａ３ Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms, with fluorine or iodine atoms being preferred. ａ１ , R ａ２ and R ａ３The alkyl group contained in the alkoxycarbonyl group represented by may be 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. R ａ１ , R ａ２ and R ａ３ Preferably, each of these independently represents a hydrogen atom or an alkyl group.

[0049] L in equation (Ga1) 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, -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. ａ２０ The substituent represented by is not particularly limited, and for example, the substituent T mentioned above can be cited, and it is preferably an organic group, and more preferably an alkyl group. The alkyl group may be linear or branched, and for example, alkyl groups having 1 to 20 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 can be cited, and alkyl groups having 1 to 8 carbon atoms are preferred. The alkyl group may have substituents.

[0050] L ａ１ The alkylene group and L represented by ａ１ The divalent linking group represented by may contain either a linear or branched alkylene group. The number of carbon atoms in the alkylene group is not particularly limited. Preferred alkylene groups include, for example, alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene groups. The alkylene group may have substituents. ａ１ A cycloalkylene group and L represented by ａ１The number of carbon atoms in the cycloalkylene group that may contain the divalent linking group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The above 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 above cycloalkylene group may have substituents. L ａ１ Arylene group and L represented by ａ１ The arylene group that may contain the divalent linking group represented by 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 groups, torylene groups, naphthylene groups, anthrylene groups, 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 group or a naphthylene group. The above arylene group may have substituents. L ａ１ A heteroarylene group and L represented by ａ１ The heteroarylene group that may contain the divalent linking group represented by can be either a monocyclic or polycyclic group. The number of ring member atoms and carbon atoms of the heteroarylene group are not particularly limited. The number of ring member atoms of the heteroarylene group may be 5 to 30. The number of carbon atoms of the heteroarylene group may be 2 to 29. As the heteroarylene group, for example, a heteroarylene group containing a heterocycle that contains at least one heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms, such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc., is preferred. The heteroarylene group may have substituents.

[0051] Ar in equation (Ga1) ｇ１ Ar represents an aromatic ring group, specifically a divalent aromatic ring group. ｇ１The divalent aromatic ring group represented by may be, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a torylene group, a naphthylene group, anthrylene group, or a biphenylene group. ｇ１ The divalent aromatic ring group represented by may also be a divalent aromatic heterocyclic group containing a heterocyclic ring that includes at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms, such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. The above aromatic ring group may have substituents. ｇ１ It is preferable that this represents an arylene group having 6 to 12 carbon atoms, and more preferably a phenylene group or a naphthylene group.

[0052] X in equation (Ga1) ａ１ represents -O- or -C(=O)O-.

[0053] G in equation (Ga1) ｚ１ R represents a group represented by formula (G-1) or (G-2). ａ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ４ 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. ａ４The 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. ａ４ The 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. ａ４ 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. ａ４ The aralkyl group represented by the above-mentioned R ａ４ 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. ａ４Examples 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. R ａ４ Preferably, represents a hydrogen atom, an alkyl group, or a cycloalkyl group.

[0054] R in equation (G-1) ａ５ and R ａ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ５ and R ａ６ The descriptions, specific examples, and preferred ranges for alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, and alkenyl groups represented by the above R are as follows: ａ４ This is the same as for alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, and alkenyl groups represented by R. ａ５ and R ａ６ Preferably, each of these independently represents an alkyl group or a cycloalkyl group.

[0055] R in equation (G-1) ａ４ and R ａ５ They may bond to form a ring. ａ４ and R ａ５ A cycloalkane ring is preferred as the ring formed by the bonding of these groups. 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. A monocyclic or polycyclic cycloalkane ring having 3 to 10 carbon atoms is preferred, and a monocyclic cycloalkane ring having 5 to 6 carbon atoms is more preferred. 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, one or more of the ethylene groups constituting the ring may be replaced by vinylene groups. ａ４ and R ａ５The ring formed by the bonding may have substituents.

[0056] G in equation (Ga1) ｚ１ If the group is represented by formula (G-1), then Ar ｇ１ is R ａ３ or R ａ４ It may combine with Ar to form a ring. ｇ１ and R ａ３ or R ａ４ A description, specific examples, and preferred range of the ring formed by the bonding of the two is given above. ａ４ and R ａ５ This is similar to what happens in a ring formed by the bonding of elements.

[0057] R in equation (G-2) ａ７ , R ａ８ and R ａ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ７ , R ａ８ and R ａ９ The descriptions, specific examples, and preferred ranges for alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, and alkenyl groups represented by the above R are as follows: ａ４ This is the same as the alkyl, cycloalkyl, aryl, heteroaryl, aralkyl, and alkenyl groups represented by R. ａ７ , R ａ８ and R ａ９ Preferably, each of these independently represents an alkyl group or a cycloalkyl group.

[0058] R in equation (G-2) ａ７ , R ａ８ and R ａ９ Two of them may combine to form a ring. ａ７ , R ａ８ and R ａ９ The description, specific examples, and preferred range of the ring formed by the bonding of two of these is as described above in R ａ４ and R ａ５ This is similar to what happens in a ring formed by the bonding of elements.

[0059] Specific examples of repeating units having acid-degradable groups are shown below, but the present invention is not limited to these. Rx is H, CH ３ CF ３ or CH ２ Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. p represents an integer of 0 or more. Z represents a substituent. If there are multiple Zs, they may be the same or different. Me represents a methyl group.

[0060]

[0061]

[0062]

[0063]

[0064] The content of repeating units having acid-degradable groups is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having acid-degradable groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to the total repeating units in resin (A). Resin (A) may contain one type of repeating unit having acid-degradable groups or two or more types. If 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.

[0065] (Repeating unit having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group) The resin (A) contains a repeating unit having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group. The repeating unit having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group may be a repeating unit having a phenolic hydroxyl group, a repeating unit having an aromatic ring group having a carboxyl group, or a repeating unit having a phenolic hydroxyl group and an aromatic ring group having a carboxyl group.

[0066] The aromatic ring group having a carboxyl group is preferably an aromatic ring group having 6 to 30 carbon atoms, more preferably an aromatic ring group having 6 to 18 carbon atoms, even more preferably a benzene ring group or a naphthalene ring group, and particularly preferably a benzene ring group. The above aromatic ring group has one or more carboxyl groups. That is, the above aromatic ring group is substituted with one or more carboxyl groups. The number of carboxyl groups in the above aromatic ring group is preferably 1 to 5, and more preferably 1 to 3. In addition to carboxyl groups, the above aromatic ring group may also have substituents other than carboxyl groups.

[0067] The resin (A) preferably contains at least repeating units having phenolic hydroxyl groups. The repeating units having phenolic hydroxyl groups are preferably different from the repeating units having acid-degradable groups described above. The repeating units having phenolic hydroxyl groups are preferably repeating units represented by the following formula (Pa1). The resin (A) preferably contains repeating units represented by the formula (Pa1).

[0068]

[0069] In formula (Pa1), R ａ１０ , R ａ１１ and R ａ１２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１１ Ar ａ１ It may also bond with to form a ring, in which case R ａ１１ L represents a single bond or an alkylene group. ａ２ Ar represents a single bond or a divalent linking group. ａ１ represents an aromatic ring group with (k+1) valency, R ａ１１ When it combines with another compound to form a ring, it represents a (k+2) valence aromatic ring group. k represents an integer from 1 to 5.

[0070] R in equation (Pa1) ａ１０ , R ａ１１ and R ａ１２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.ａ１０ , R ａ１１ and R ａ１２ The explanation, specific examples, and preferred range of R in the above formula (Ga1) are given by ａ１ , R ａ２ and R ａ３ It is similar to the one in [location / place].

[0071] L in equation (Pa1) ａ２ L represents a single bond or a divalent linking group. ａ２ The description, specific examples, and preferred range of the divalent linking group represented by the above formula (Ga1) is given by L ａ１ This is the same as the one in the divalent linking group represented by .

[0072] Ar in equation (Pa1) ａ１ represents an aromatic ring group with (k+1) valency, R ａ１１ When it combines with to form a ring, it represents an (k+2) valency aromatic ring group. k represents an integer from 1 to 5. When k is 1, Ar ａ１represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a torylene group, a naphthylene group, anthrylene group, or a biphenylene group. Alternatively, the divalent aromatic ring group may be a heteroarylene group containing a heterocycle that includes at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The above aromatic ring group may have substituents. Specific examples of a (k+1) valent aromatic ring group when k is an integer of 2 or more include groups obtained by removing (k-1) arbitrary hydrogen atoms from the above specific examples of divalent aromatic ring groups. The (k+1) valent aromatic ring group may further have substituents. The substituents that a (k+1) valent aromatic ring group may have are not particularly limited, but examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl. ａ１ It is preferable that represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.

[0073] The repeating unit represented by formula (Pa1) preferably has a hydroxystyrene structure. That is, Ar ａ１ k preferably represents a benzene ring group. k preferably represents an integer from 1 to 3, and more preferably represents 1 or 2.

[0074] 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.

[0075]

[0076] The content of repeating units having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group is not particularly limited, but it is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group 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 at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group may be one type or two or more types. If resin (A) contains two or more types of repeating units having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group, it is preferable that their total content is within the range of the above preferred content.

[0077] (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.

[0078] 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.

[0079] Resin (A) preferably has 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.

[0080] 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. ＬThey may join together to form a ring.

[0081]

[0082] 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).

[0083]

[0084] In formula (AI-2), Rb ０ Rb represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ The alkyl group may have substituents. Rb ０ Examples 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).

[0085] 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.

[0086] (Repeating units having photoacid generating groups) Resin (A) may have 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 generating agent. An example of a repeating unit having a photoacid generating group is the repeating unit represented by formula (4).

[0087]

[0088] 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.

[0089] L ４１ represents a single bond or a divalent linking group, preferably a single bond or an ester bond (-COO-).

[0090] 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.

[0091] R ４０ Preferably, the group is represented by the following formula (S4-1).

[0092]

[0093] 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 － ), 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. ＋ The explanation, specific examples, and preferred ranges are described in the description of compound (C) below. ＋ It is the same as this.

[0094] 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.

[0095] 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.

[0096] When resin (A) contains repeating units having photoacid-generating groups, the content of repeating units having photoacid-generating groups is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units having photoacid-generating groups is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 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.

[0097] (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.

[0098]

[0099] 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.

[0100] (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.).

[0101] For repeating units that reduce the mobility of the main chain, refer to the contents of International Publication No. 2022 / 024928, paragraphs

[0144] to

[0160] .

[0102] (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>.

[0103] 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.

[0104] 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.

[0105] (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.

[0106] (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.

[0107]

[0108] 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.

[0109] (Other Repeating Units) Furthermore, resin (A) may also contain other repeating units other than 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.

[0110] 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.

[0111] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). 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 4,000 to 15,000. The degree of dispersion of resin (A), also called "molecular weight distribution," "Pd," or "Mw / Mn," 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.

[0112] The content of resin (A) in the composition of the present invention is preferably 40.0 to 99.9% by mass, more preferably 50.0 to 95.0% by mass, and even more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. Only one type of resin (A) may be used, or two or more types may be used. When two or more types of resin (A) are used, it is preferable that their total content is within the above preferred content range.

[0113] [Resin (B) satisfying formula (i-1) and not containing repeating units having a fluoride alkyl group] The composition of the present invention contains resin (B) (also simply referred to as "resin (B)") that satisfies formula (i-1) and does not contain repeating units having a fluoride alkyl group. B Ｍｅ / B ｔｏｔａｌ ≥ 0.05 (i-1) In equation (i-1), B ｔｏｔａｌ This represents the sum of the values ​​obtained by multiplying the molecular weight of the monomer corresponding to each repeating unit contained in resin (B) by the mole fraction of each repeating unit contained in resin (B). Ｍｅ This represents the sum of the values ​​obtained by multiplying the number of methyl groups in the monomer corresponding to each repeating unit contained in resin (B), the formula weight of the methyl groups, and the mole fraction of each repeating unit contained in resin (B).

[0114] To satisfy formula (i-1), one method is to use a monomer having a methyl group as the monomer corresponding to the repeating unit constituting the resin (B), and to adjust the molecular weight of the monomer and the number of methyl groups. For example, it is preferable to use a monomer with a molecular weight of 85 to 300 and having 1 to 6 methyl groups.

[0115] If n is the number of types of repeating units contained in resin (B), then B ｔｏｔａｌ This can be expressed by the following formula (F1). In formula (F1), M ｉ t represents the molecular weight of the monomer corresponding to each repeating unit. ｉ represents the mole fraction of each repeating unit in resin (B). n is an integer greater than or equal to 1, and i is an integer from 1 to n. ｉ This also represents the content of each repeating unit relative to the total number of repeating units contained in resin (B) (molal fraction, in units of mol%). １３ It can be measured using C-NMR (Nuclear Magnetic Resonance).

[0116]

[0117] A monomer corresponding to a repeating unit is one whose structure, when its polymerizable group undergoes a polymerization reaction, is the same as the structure of the repeating unit. It is not necessary for the repeating unit to have been actually obtained using that monomer (for example, the repeating unit may be obtained by performing a polymerization reaction using another monomer and then changing its structure through a chemical reaction). Examples of polymerizable groups of monomers include groups containing carbon-carbon double bonds, such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups. An example of a polymerization reaction is addition polymerization. An example of a repeating unit and its corresponding monomer is the repeating unit represented by the following formula (RM-1) and the monomer represented by the following formula (RM-2).

[0118]

[0119] In formulas (RM-1) and (RM-2), R １００R represents a hydrogen atom or substituent. １０１ * represents a substituent. １ and * ２ The symbol indicates the connection position.

[0120] If n is the number of types of repeating units contained in resin (B), then B Ｍｅ This can be expressed by the following formula (F2). In formula (F2), M Ｍｅ This represents the formula weight of the methyl group. The formula weight of the methyl group is 15.03. ｉ t represents the number of methyl groups in the monomer corresponding to each repeating unit. ｉ This represents the mole fraction of each repeating unit contained in resin (B). n is an integer greater than or equal to 1, and i is an integer from 1 to n.

[0121]

[0122] The resin B-1 described in the examples below ｔｏｔａｌ 120.15 × 70 + 220.31 × 30 = 15019.8, B Ｍｅ Since 15.03 × 0 × 70 + 15.03 × 4 × 30 = 1803.6, B Ｍｅ / B ｔｏｔａｌ This becomes 0.12.

[0123] B of resin (B) Ｍｅ / B ｔｏｔａｌ It is preferable that the ratio is 0.10 or higher. That is, it is preferable that resin (B) satisfies formula (i-2). When resin (B) satisfies formula (i-2), the surface segregation of resin (B) is increased, and the resolution is further improved. Ｍｅ / B ｔｏｔａｌ ≥ 0.10 (i-2) B in equation (i-2) ｔｏｔａｌ and B Ｍｅ These are B in equation (i-1), respectively. ｔｏｔａｌ and B Ｍｅ It expresses the same meaning.

[0124] B of resin (B) Ｍｅ / B ｔｏｔａｌ It is even more preferable that the ratio of resin (B) is 0.15 or higher. Ｍｅ / B ｔｏｔａｌ It is preferably 0.60 or less, and more preferably 0.55 or less.

[0125] (Repeating units having acid groups) It is preferable that the resin (B) contains repeating units having acid groups. It is believed that the inclusion of repeating units having acid groups in the resin (B) improves its solubility in the developer and makes the pattern surface more easily soluble, thereby suppressing the occurrence of bridges and further improving resolution. Examples of acid groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, isopropanol groups, etc., with carboxyl groups or phenolic hydroxyl groups being preferred.

[0126] Resin (B) preferably contains repeating units having phenolic hydroxyl groups. The description, specific examples, and preferred range of repeating units having phenolic hydroxyl groups that resin (B) may contain are the same as those described above for repeating units having phenolic hydroxyl groups contained in resin (A). However, the repeating units having phenolic hydroxyl groups that resin (B) may contain do not have fluorinated alkyl groups.

[0127] When resin (B) contains repeating units having acidic groups, the content of repeating units having acidic groups in resin (B) is not particularly limited, but it is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to the total repeating units in resin (B). Furthermore, the content of repeating units having acidic 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 (B). When resin (B) contains repeating units having acidic groups, there may be one type of repeating unit having acidic groups or two or more types. When resin (B) 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.

[0128] (Repeating units having acid-degradable groups) It is preferable that resin (B) contains repeating units having acid-degradable groups. It is believed that by resin (B) containing repeating units having acid-degradable groups, the solubility in the developer is improved and the pattern surface becomes more easily soluble, thereby suppressing the occurrence of bridges and other defects and further improving resolution. The description, specific examples, and preferred range of repeating units having acid-degradable groups that resin (B) may contain are the same as those described above for repeating units having acid-degradable groups that resin (A) contains. However, the repeating units having acid-degradable groups that resin (B) may contain do not have fluoride alkyl groups.

[0129] The resin (B) preferably contains repeating units represented by formula (Gb1).

[0130]

[0131] In formula (Gb1), R ｂ１ , R ｂ２ and R ｂ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ｂ１ X represents a single bond or a divalent linking group. ｂ１ represents -O- or -C(=O)O-. G ｚ２ represents a group expressed by formula (G-3) or (G-4).

[0132]

[0133] In formula (G-3), R ｂ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ５ and R ｂ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ４ and R ｂ５ They may combine to form a ring. G ｚ２ If the group is represented by formula (G-3), then L ｂ１ is R ｂ３ or R ｂ４ It may combine with to form a ring. * indicates the bonding position. In formula (G-4), Rｂ７ , R ｂ８ and R ｂ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ７ , R ｂ８ and R ｂ９ Two of them may join to form a ring. * indicates the bonding position.

[0134] R in equation (Gb1) ｂ１ , R ｂ２ and R ｂ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ｂ１ , R ｂ２ and R ｂ３ The explanation, specific examples, and preferred range of R in formula (Ga1) above are given by ａ１ , R ａ２ and R ａ３ It is the same as in R. ｂ１ , R ｂ２ and R ｂ３ This does not represent an alkyl fluoride. Also, R ｂ１ , R ｂ２ and R ｂ３ It does not have alkyl fluoride as a substituent.

[0135] L in equation (Gb1) ｂ１ L represents a single bond or a divalent linking group. ｂ１ The description, specific examples, and preferred range of the divalent linking group represented by the above formula (Ga1) is given by L ａ１ It is the same as in L. ｂ１ It does not have alkyl fluoride as a substituent.

[0136] X in equation (Gb1) ｂ１ represents -O- or -C(=O)O-.

[0137] G in equation (Gb1) ｚ２ R represents a group represented by formula (G-3) or (G-4). ｂ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group.ｂ４ The explanation, specific examples, and preferred range of R in formula (G-1) above are given by ａ４ It is the same as in R. ｂ４ This does not represent an alkyl fluoride. Also, R ｂ４ It does not have alkyl fluoride as a substituent.

[0138] R in equation (G-3) ｂ５ and R ｂ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ５ and R ｂ６ The explanation, specific examples, and preferred range of R in formula (G-1) above are given by ａ５ and R ａ６ It is the same as in R. ｂ５ and R ｂ６ This does not represent an alkyl fluoride. Also, R ｂ５ and R ｂ６ It does not have alkyl fluoride as a substituent.

[0139] R in equation (G-3) ｂ４ and R ｂ５ They may bond to form a ring. ｂ４ and R ｂ５ The description, specific examples, and preferred range of the ring formed by the bonding of R in formula (G-1) above is given by R ａ４ and R ａ５ This is the same as in the ring formed by the bonding of R. ｂ４ and R ｂ５ The ring formed by the bonding of these atoms does not have alkyl fluoride as a substituent.

[0140] G in equation (G-3) ｚ２ If the group is represented by formula (G-3), then L ｂ１ is R ｂ３ or R ｂ４ It may combine with L to form a ring. ｂ１ and R ｂ３ or R ｂ４ A description, specific examples, and preferred range of the ring formed by the bonding of the two is given above. ｂ４ and R ｂ５This is similar to what happens in a ring formed by the bonding of elements.

[0141] R in equation (G-4) ｂ７ , R ｂ８ and R ｂ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ７ , R ｂ８ and R ｂ９ The explanation, specific examples, and preferred range of R in formula (G-2) above are given by ａ７ , R ａ８ and R ａ９ It is the same as in R. ｂ７ , R ｂ８ and R ｂ９ This does not represent an alkyl fluoride. Also, R ｂ７ , R ｂ８ and R ｂ９ It does not have alkyl fluoride as a substituent.

[0142] R in equation (G-4) ｂ７ , R ｂ８ and R ｂ９ Two of them may combine to form a ring. ｂ７ , R ｂ８ and R ｂ９ The description, specific examples, and preferred range of the ring formed by the bonding of two of these is as described above in R ｂ４ and R ｂ５ This is similar to what happens in a ring formed by the bonding of elements.

[0143] When resin (B) contains repeating units having acid-degradable groups, the content of repeating units having acid-degradable groups in resin (B) is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total repeating units in resin (B). Furthermore, the content of repeating units having acid-degradable groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to the total repeating units in resin (B). When resin (B) contains repeating units having acid-degradable groups, there may be one type of repeating unit having acid-degradable groups or two or more types. When resin (B) 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.

[0144] (Repeating units having aromatic ring groups) It is preferable that resin (B) contains repeating units having aromatic ring groups. By resin (B) containing repeating units having aromatic ring groups, compatibility with resin (A) containing aromatic ring groups is increased, making aggregation and the like less likely to occur in the composition of the present invention, and thus improving the LWR performance over time. The aromatic ring groups of the repeating units having aromatic ring groups that resin (B) may contain are preferably aromatic ring groups having 6 to 30 carbon atoms, more preferably aromatic ring groups having 6 to 18 carbon atoms, even more preferably benzene ring groups or naphthalene ring groups, and particularly preferably benzene ring groups. The above aromatic ring groups may have substituents. However, the above aromatic ring groups may not have alkyl fluoride as substituents. The repeating units having aromatic ring groups that resin (B) may contain may be repeating units having the acidic group described above, or repeating units having an acid-degradable group.

[0145] When resin (B) contains repeating units having aromatic ring groups, the content of repeating units having aromatic ring groups in resin (B) is not particularly limited, but it 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 (B). Furthermore, the content of repeating units having aromatic ring groups is 100 mol% or less relative to the total repeating units in resin (B). When resin (B) contains repeating units having aromatic ring groups, there may be one type or two or more types of repeating units having aromatic ring groups in resin (B). When resin (B) contains two or more types of repeating units having aromatic ring groups, it is preferable that their total content is within the range of the above preferred content.

[0146] (Other Repeating Units) Furthermore, resin (B) may contain other repeating units other than those described above (repeating units having acidic groups, repeating units having acid-degradable groups, and repeating units having aromatic ring groups). The content of other repeating units in resin (B) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (B).

[0147] Resin (B) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight (Mw) of resin (B), 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 4,000 to 15,000. The degree of dispersion of resin (B), also called "molecular weight distribution," "Pd," or "Mw / Mn," 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.

[0148] The content of resin (B) in the composition of the present invention is preferably 0.1 to 30.0% by mass, more preferably 1.0 to 20.0% by mass, and even more preferably 3.0 to 10.0% by mass, based on the total solid content of the composition of the present invention. Only one type of resin (B) may be used, or two or more types may be used. When two or more types of resin (B) are used, it is preferable that their total content is within the range of the above preferred content.

[0149] The content of resin (A) relative to the content of resin (B) in the composition of the present invention is preferably 100% by mass or more, more preferably 150% by mass or more, and even more preferably 200% by mass or more. Furthermore, the content of resin (A) relative to the content of resin (B) in the composition of the present invention is preferably 3000% by mass or less, and more preferably 2500% by mass or less. The content of resin (A) relative to the content of resin (B) in the composition of the present invention (Z ＡＢ It is also called ". ) The content of resin (A) in the composition of the present invention is W Ａ (Assuming mass%), the content of resin (B) in the composition of the present invention is W Ｂ (Assuming mass %), Z ＡＢ = 100 × W Ａ / W Ｂ It is represented as follows.

[0150] [Compound (C) that generates acid upon irradiation with active light or radiation] The composition of the present invention preferably further contains compound (C) (also simply referred to as "compound (C)") that generates acid upon irradiation with active light or radiation. Compound (C) is a photoacid generator. Compound (C) is preferably a compound that generates an acid with a pKa of less than 0 upon irradiation with active light or radiation. The pKa of the acid generated from compound (C) upon irradiation with active light or radiation is preferably -0.1 or less, and more preferably -0.2 or less. Furthermore, the pKa of the acid generated from compound (C) upon irradiation with active light or radiation is preferably -1.5 or more, and more preferably -1.0 or more.

[0151] Compound (C) may be in the form of a low molecular weight compound or a high molecular weight compound such as a resin. When compound (C) is in the form of a low molecular weight compound, the molecular weight of compound (C) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000. When compound (C) is in the form of a high molecular weight compound, compound (C) and resin (A) may be the same compound, or compound (C) 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 (C), which is a different compound 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 (C), which is a different compound from resin (A).

[0152] For example, compound (C) 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.

[0153] "M ＋ X － In the compound represented by ", M ＋ represents an organic cation. The organic cation is not particularly limited. The valency of the organic cation may be 1 or 2 or more. In particular, the organic 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.

[0154]

[0155] 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.

[0156] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0157] 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 ２０３Examples 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.

[0158] 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.

[0159] R ２０１ ~R ２０３Preferred 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.

[0160] 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.

[0161] R ２０１ ~R ２０３Examples 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.

[0162] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0163]

[0164] In formula (ZaI-3b), R １ｃ ~R ５ｃ Each 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.

[0165] 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.

[0166] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples 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.

[0167] 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 ｙThe rings formed by the bonding of these elements to each other may have substituents.

[0168] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0169]

[0170] 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. １４ R 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 alkyl group, cycloalkyl group and naphthyl group and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0171] In equation (ZaI-4b), R １３ , R１４ , 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.

[0172] 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 ２０５ The 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).

[0173] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ２０４ and R ２０５Examples 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.

[0174] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0175]

[0176]

[0177] "M ＋ X － In the compound represented by ", X － represents an organic anion. The organic anion is not particularly limited and can be a monovalent or divalent or more organic anion. The organic anion is preferably one that has a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0178] 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.

[0179] 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).

[0180] 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.

[0181] 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).

[0182] 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.

[0183] An example of a sulfonylimid anion is the saccharin anion.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0188]

[0189] In formula (AN1), R１ 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.

[0190] 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.

[0191] 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 ２Examples 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.

[0192] For L, a group represented by the following formula (AN1-1) is preferred. * ａ - (CR ２ａ ２ ) Ｘ -Q- (CR ２ｂ ２ ) Ｙ - * ｂ (AN1-1)

[0193] In formula (AN1-1), * ａ R in equation (AN1) ３ This indicates the connection point with [the other element]. * ｂ -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.

[0194] 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.).

[0195] 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.

[0196] 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.

[0197] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0198]

[0199] 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.

[0200] 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.

[0201] 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.

[0202] L represents a divalent linking group. The definition of L is the same as the L in formula (AN1).

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] As a non-nucleophilic anion, an anion represented by the following formula (AN3) (aromatic sulfonic acid anion) is also preferred. Compound (C) preferably contains an anion represented by the following formula (AN3).

[0208]

[0209] 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.

[0210] 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.

[0211] 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).

[0212] 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.

[0213] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0214]

[0215] 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).

[0216] 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.

[0217] 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.

[0218] 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.

[0219] Organic anions may be used individually or in combination of two or more.

[0220] Compound (C) is also preferably at least one selected from the group consisting of compounds (I) to (II).

[0221] (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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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 － As such, those that can form an acidic moiety with a small acid dissociation constant are preferred, and among these, those that are any of formulas (AA-1) to (AA-3) are more preferred, and those that are either formulas (AA-1) or (AA-3) are even more preferred. 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.

[0230]

[0231]

[0232] Cation site M １ ＋ and cation site M ２ ＋ This refers to a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the aforementioned M. ＋ Examples of organic cations represented by the following are given.

[0233] (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

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238]

[0239] 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.

[0240] Examples of non-cationic sites that compound (I) and compound (II) may have are given below.

[0241]

[0242]

[0243] When the composition of the present invention contains compound (C), the content of compound (C) 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 (C) is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition of the present invention. Only one type of compound (C) may be used, or two or more types may be used. When two or more types of compound (C) are used, it is preferable that their total content is within the range of the above preferred content.

[0244] [Acid Diffusion Control Agent (D)] The composition of the present invention preferably further contains an acid diffusion control agent (D) (also referred to as "compound (D)"). Compound (D) 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. The type of compound (D) 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 acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compound (DC) include onium salt compounds (DD) of acids that are relatively weak acids with respect to the acid generated from a photoacid generator, and basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation.

[0245] (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.

[0246]

[0247] 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.

[0248] R in formulas (O-1) and (O-5) ３００ , R ３０１ , R ３０２ , R ３０３ , R ３０４ , R３０５ 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.

[0249] 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.

[0250] 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.

[0251] (Onium salt compound (DD) of an acid that is a weak acid relative to the acid generated from the photoacid generator) Compound (DD) may be a compound that generates acid upon irradiation with active light or radiation. Preferably, compound (DD) is a compound that generates an acid whose pKa is 1.00 or greater than 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 (the 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 greater, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. Furthermore, the pKa of the acid generated from the compound (DD) varies depending on the type of photoacid generator used, but for example, 0.50 to 10.00 is preferred, 0.80 to 5.00 is more preferred, and 1.00 to 5.00 is even more preferred.

[0252] Compound (DD) is preferably an onium salt compound consisting of an anion and a cation. For example, compound (DD) is "M ＋ X － Examples include compounds represented by " (onium salts). ＋ X represents an organic cation. － M represents an organic anion. ＋ As for the M mentioned in the description of compound (C) ＋ The same thing can be cited as X － Examples include the anions represented by formulas (d1-1) to (d1-4) described in the description of compound (C), with the anion represented by formula (d1-1) or formula (d1-2) being preferred, and the anion represented by formula (d1-1) being more preferred. The acid diffusion control agent (D) preferably contains the anion represented by formula (d1-1).

[0253] 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.

[0254] 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.

[0255] The molecular weight of compound (D) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0256] Compound (D) is also preferably a compound that generates an acid with a pKa of 0 or greater upon irradiation with active light or radiation.

[0257] When the composition of the present invention contains compound (D), the content of compound (D) 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 compound (D) 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 compound (D) 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.

[0258] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin different from resin (A) and resin (B). 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.

[0259] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 atoms 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.

[0260] 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. It is preferable that the composition of the present invention does not contain hydrophobic resins other than resin (A) and resin (B).

[0261] [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.

[0262] 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.

[0263] [Solvent] The composition of the present invention contains a solvent. Preferably, the solvent 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).

[0264] 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.

[0265] 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.

[0266] 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.

[0267] [Other Additives] The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound 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.

[0268] 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.

[0269] [Photosensitive or Radiation-Sensitive Film, Pattern Forming Method] The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive or radiation-sensitive film of the present invention is preferably a resist film. The present invention also relates to a pattern forming method. The pattern forming method of the present invention is preferably a pattern forming method comprising the steps of: forming a photosensitive or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention; exposing the photosensitive or radiation-sensitive film; and developing the exposed photosensitive or radiation-sensitive film using a developer. The procedure for a pattern forming 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.

[0270] (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.

[0271] 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.

[0272] 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 (rotations per minute). After applying the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various underlayer films (inorganic films, organic films, anti-reflective films) may be formed beneath the resist film.

[0273] 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.

[0274] 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, 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.

[0275] Furthermore, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of 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 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. 2013-61648, 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.

[0276] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film. The 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, with wavelengths of 250 nm or less being preferred, more preferably 220 nm or less, and far ultraviolet light with wavelengths of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams are particularly preferred.

[0277] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape. Post-exposure baking is also called PEB (Post Exposure Bake). 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 carried out using means provided in a normal exposure machine and / or developing machine, and may also be done using a hot plate or the like. This process is also called post-exposure baking.

[0278] (Step 3: Development Step) Step 3 is the process 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).

[0279] Examples of development methods include immersing the substrate in a tank filled with developer for a certain period of time (dip method), puddling the developer onto the substrate surface using surface tension and letting it stand for a certain period of time (paddle method), spraying the developer onto the substrate surface (spray method), and continuously dispensing the developer while scanning a developer 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 of stopping the development while replacing the solvent with another solvent may be performed. 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 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0280] 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.

[0281] 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.

[0282] 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.

[0283] (Other steps) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0284] 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.

[0285] 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.

[0286] The rinsing process is not particularly limited and includes methods such as 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), and spraying rinsing solution onto the substrate surface (spray method). The pattern formation method may also 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).

[0287] 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.

[0288] The various materials used in the compositions and pattern forming methods of the present invention (for example, solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred. 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.

[0289] 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.

[0290] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as constituent materials for various materials, filtering the constituent materials of various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon (registered trademark).

[0291] 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 by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0292] To prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge in organic treatment solutions such as rinsing solutions, a conductive compound 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. There is no particular lower limit, but 0.01% by mass or more is preferred. As 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.

[0293] [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.).

[0294] 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.

[0295] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0296] <Resin (A)> A-1 to A-10 are used as resin (A). In addition, AX-1 is used as an acid-degradable resin that is not resin (A). However, in Table 3 below, AX-1 is listed in the "Resin (A)" column for convenience. The structural formulas of the repeating units contained in A-1 to A-10 and AX-1, the content of each repeating unit, the weight-average molecular weight (Mw), and the degree of dispersion (Pd = Mw / Mn) are shown below. The content of each repeating unit is indicated by a subscript to the right of the parentheses of the repeating unit. The content of each repeating unit is the mole fraction of each repeating unit relative to the total number of repeating units contained in each resin, and the unit is mol%. Me represents a methyl group. The weight-average molecular weight and degree of dispersion of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). Also, the content of the repeating units is １３ Measurements are taken using 1C-NMR (nuclear magnetic resonance). The same procedure is used for resin (B), which will be described later.

[0297]

[0298]

[0299]

[0300] <Resin (B)> B-1 to B-26 are used as resin (B). In addition, BX-1 and BX-2 are used as resins that are not resin (B). However, in Tables 1 and 3 below, BX-1 and BX-2 are listed in the "Resin (B)" column for convenience. B-1 to B-26 and BX-2 contain the repeating units listed in the "Type" column of the repeating unit (1), repeating unit (2), and repeating unit (3) shown in Table 1 below, in the amount listed in the "Content" column. If "-" is written in the "Type" and "Content" columns, it means that the repeating unit is not included. The type of repeating unit is indicated by the structure of the corresponding monomer. The content of each repeating unit is the mole fraction of each repeating unit relative to the total repeating units contained in each resin, and the unit is mol%. Also, Table 1 shows the weight-average molecular weight (Mw), dispersion (Pd = Mw / Mn), and B for each resin. Ｍｅ / B ｔｏｔａｌ I also included this. B ｔｏｔａｌ This represents the sum of the values ​​obtained by multiplying the molecular weight of the monomer corresponding to each repeating unit contained in resin (B) by the mole fraction of each repeating unit contained in resin (B). Ｍｅ This represents the sum of the values ​​obtained by multiplying the number of methyl groups in the monomer corresponding to each repeating unit contained in resin (B), the formula weight of the methyl groups, and the mole fraction of each repeating unit contained in resin (B).

[0301]

[0302] The structures of the monomers corresponding to the repeating units listed in the "Type" column of Table 1 are shown below. Me represents a methyl group.

[0303]

[0304]

[0305]

[0306] The structural formulas of the repeating units constituting BX-1, the content of each repeating unit, the weight-average molecular weight (Mw), and the degree of dispersion (Pd = Mw / Mn) are shown below. The content of each repeating unit is indicated by a subscript to the right of the parentheses of the repeating unit. The content of each repeating unit is the mole fraction of each repeating unit relative to the total number of repeating units contained in each resin, and the unit is mol%.

[0307]

[0308] <Compound (C)> C-1 and C-2 are used as compound (C) (photoacid generator). The structural formulas of C-1 and C-2 are shown below.

[0309]

[0310] <Acid Diffusion Control Agent (D)> D-1 and D-2 are used as the acid diffusion control agent (D). The structural formulas of D-1 and D-2 are shown below.

[0311]

[0312] <Solvents> The solvents to be used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: γ-Butyrolactone

[0313] <Preparation of Resist Compositions> Dissolve the components shown in Tables 2 and 3 below in the solvents shown in the tables to prepare a solution with a solid content concentration of 3.0% by mass. Filter this solution through a polyethylene filter with a pore size of 0.02 μm to prepare the resist compositions (R-1 to R-30, XR-1 to XR-4). In the tables, the "mass%" column indicates the content (mass%) of each component relative to the total solid content in the resist composition. Solid content refers to components other than the solvent. The table lists the type of solvent used and its mass ratio (mass%). In the table, if two or more types of each component are used, the type and amount are separated by " / ". The order in which the types and amounts separated by " / " are listed corresponds to each other. In addition, the table lists the content of resin (A) relative to the content of resin (B) in each resist composition (Z ＡＢ ) was also described. The content of resin (A) in the resist composition is W Ａ(Assuming mass %), the content of resin (B) in the resist composition is W Ｂ (Assuming mass %), Z ＡＢ = 100 × W Ａ / W Ｂ It is represented as follows.

[0314]

[0315]

[0316] [Examples 1-1 to 1-30, Comparative Examples X1-1 to X1-4] <Pattern Formation Method (1): EB Exposure, Alkaline Development (Positive)> The resist composition shown in Table 4 below is applied to a 6-inch Si wafer that has been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by changing the Si wafer to a chromium substrate. Pattern irradiation is performed on the wafer having the resist film obtained above using an electron beam lithography system (Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, drawing is performed so that a 1:1 line and space pattern is formed. After electron beam lithography, the wafer is heated on a hot plate at 100°C for 60 seconds as a PEB treatment. Then, it is developed by immersing in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds. Next, rinse with water for 30 seconds. Then, rotate the wafer at 4000 rpm for 30 seconds. Finally, dry by heating at 95°C for 60 seconds to obtain a 1:1 line-and-space pattern.

[0317] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi, Ltd. S-4300). The exposure amount (electron beam irradiation amount) required to resolve a 1:1 line-and-space pattern with a line width of 50 nm is defined as the sensitivity (Eopt). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure amount that shows the above sensitivity (Eopt) is defined as the resolution (nm). The smaller the resolution (nm) value, the better the resolution. The resolution (nm) value is evaluated according to the following criteria: A: 20-25 nm B: 26-30 nm C: 31-36 nm D: 37 nm or higher The results shown in the "Resolution" column of Table 4 below are obtained.

[0318] [LWR Performance Over Time] Using each resist composition, a 1:1 line-and-space pattern with a line width of 50 nm is obtained using the pattern formation method (1) described above. The obtained pattern is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi S-9380II)). The line width of the pattern is observed at arbitrary points (160 points), and its standard deviation (σ) is determined, with 3σ (nm) being taken as the initial LWR value (unit: nm). Next, each resist composition is stored at 23°C for 6 months, and a pattern is formed using the same method as above, except that the stored resist composition is used. The standard deviation (σ) of the line width of the pattern is determined, and 3σ is taken as the LWR value (unit: nm). The LWR change rate is calculated using the following formula and is used as an indicator of the LWR performance over time. LWR change rate (%) = 100 × (LWR value after time - initial LWR value) / (initial LWR value) A smaller LWR change rate indicates better LWR performance over time. The LWR change rate is evaluated according to the following criteria. A or B is preferred, with A being more preferred. A: LWR change rate less than 2% B: LWR change rate 2% or more and less than 5% C: LWR change rate 5% or more The results shown in the "LWR performance over time" column of Table 4 below are obtained.

[0319] [PED Stability] For a 1:1 line-and-space pattern with a line width of 50 nm and a space width of 50 nm, the line width (L0h) (unit: nm) is measured when PEB treatment is performed immediately after exposure, and when PEB treatment is performed 1 hour after exposure, and the line width (L1h) (unit: nm) is measured. PEB treatment is performed by heating at 100°C for 60 seconds. The line width change rate is calculated using the following formula and is used as an indicator of PED stability. Line width change rate (%) = 100 × (L1h - L0h) / 50 A smaller line width change rate indicates better PED stability. The line width change rate is evaluated according to the following criteria. A or B is preferred, and A is more preferred. A: Line width change rate is less than 2% B: Line width change rate is 2% or more and less than 5% C: Line width change rate is 5% or more The results shown in the "PED Stability" column of Table 4 below are obtained.

[0320]

[0321] [Examples 2-1 to 2-30, Comparative Examples X2-1 to X2-4] <Pattern Formation Method (2): EUV Exposure, Alkali Development (Positive)> The resist composition shown in Table 5 below is applied to a 6-inch Si wafer that has been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by changing the Si wafer to a chromium substrate. Pattern exposure is performed on the wafer having the resist film obtained above using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) with an exposure mask (line / space = 1 / 1). After exposure, the wafer is heated on a hot plate at 100°C for 60 seconds as a PEB treatment. The wafer is then developed by immersing it in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds. After that, it is rinsed with water for 30 seconds. Then the wafer is rotated at a speed of 4000 rpm for 30 seconds. Finally, it is dried by heating at 95°C for 60 seconds to obtain a 1:1 line-and-space pattern.

[0322] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi, Ltd. S-4300). The exposure amount (EUV irradiation amount) required to resolve a 1:1 line-and-space pattern with a line width of 50 nm is defined as the sensitivity (Eopt). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure amount that shows the above sensitivity (Eopt) is defined as the resolution (nm). A smaller resolution (nm) value indicates better resolution. The resolution (nm) value is evaluated according to the following criteria: A: 20-25 nm B: 26-30 nm C: 31-36 nm D: 37 nm or higher The results shown in the "Resolution" column of Table 5 below are obtained.

[0323] [LWR Performance Over Time] Using each resist composition, a 1:1 line-and-space pattern with a line width of 50 nm is obtained using the pattern formation method (2) described above. The obtained pattern is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi S-9380II)). The line width of the pattern is observed at arbitrary points (160 points), and its standard deviation (σ) is determined, with 3σ (nm) being taken as the initial LWR value (unit: nm). Next, each resist composition is stored at 23°C for 6 months, and a pattern is formed using the same method as above, except for using each resist composition after storage. The standard deviation (σ) of the line width of the pattern is determined, and 3σ is taken as the LWR value (unit: nm). The LWR change rate is calculated using the following formula and is used as an indicator of the LWR performance over time. LWR change rate (%) = 100 × (LWR value after time - initial LWR value) / (initial LWR value) A smaller LWR change rate indicates better LWR performance over time. The LWR change rate is evaluated according to the following criteria. A or B is preferred, with A being more preferred. A: LWR change rate less than 2% B: LWR change rate 2% or more and less than 5% C: LWR change rate 5% or more The results shown in the "LWR performance over time" column of Table 5 below are obtained.

[0324] [PED Stability] For a 1:1 line-and-space pattern with a line width of 50 nm and a space width of 50 nm, the line width (L0h) (unit: nm) is measured when PEB treatment is performed immediately after exposure, and when PEB treatment is performed 1 hour after exposure, and the line width (L1h) (unit: nm) is measured. PEB treatment is performed by heating at 100°C for 60 seconds. The line width change rate is calculated using the following formula and is used as an indicator of PED stability. Line width change rate (%) = 100 × (L1h - L0h) / 50 A smaller line width change rate indicates better PED stability. The line width change rate is evaluated according to the following criteria. A or B is preferred, and A is more preferred. A: Line width change rate is less than 2% B: Line width change rate is 2% or more and less than 5% C: Line width change rate is 5% or more The results shown in the "PED Stability" column of Table 5 below are obtained.

[0325]

[0326] From the table above, it can be seen that the resist compositions of the examples exhibit excellent resolution, LWR performance over time, and PED stability.

[0327] The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution, LWR performance over time, and PED stability. Furthermore, the present invention provides a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition.

[0328] 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. 2024-170463 filed on 30 September 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin (A) comprising a repeating unit having at least one selected from the group consisting of a phenolic hydroxyl group and an aromatic ring group having a carboxyl group, and a repeating unit having an acid-degradable group; a resin (B) satisfying the following formula (i-1) and not containing a repeating unit having a fluorinated alkyl group; and a solvent-containing photosensitive or radiation-sensitive resin composition. B Ｍｅ / B ｔｏｔａｌ ≥ 0.05 (i-1) In equation (i-1), B ｔｏｔａｌ This represents the sum of the values ​​obtained by multiplying the molecular weight of the monomer corresponding to each repeating unit contained in the resin (B) by the mole fraction of each repeating unit contained in the resin (B). Ｍｅ This represents the sum of the values ​​obtained by multiplying the number of methyl groups in the monomer corresponding to each repeating unit contained in the resin (B), the formula weight of the methyl groups, and the mole fraction of each repeating unit contained in the resin (B).

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit represented by the following formula (Ga1). In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ａ１ represents a single bond or a divalent linking group. Ar ｇ１ represents an aromatic ring group. X ａ１ represents -O- or -C(=O)O-. G ｚ１ represents a group represented by the following formula (G-1) or (G-2). In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ５ and R ａ６ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ４ and R ａ５ may combine to form a ring. When G ｚ１ is a group represented by formula (G-1), Ar ｇ１ may combine with R ａ３ or R ａ４ to form a ring. * represents the bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. Two of R ａ７ , R ａ８ and R ａ９ may combine to form a ring. * represents the bonding position.

3. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) comprises repeating units having acid groups.

4. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) comprises repeating units having acid-degradable groups.

5. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) comprises repeating units having aromatic ring groups.

6. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) satisfies the following formula (i-2). B Ｍｅ / B ｔｏｔａｌ ≥ 0.10 (i-2) B in equation (i-2) ｔｏｔａｌ and B Ｍｅ These are B in equation (i-1), respectively. ｔｏｔａｌ and B Ｍｅ It expresses the same meaning.

7. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the content of resin (A) relative to the content of resin (B) in the photosensitive or radiation-sensitive resin composition is 100% by mass or more.

8. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) comprises a repeating unit represented by the following formula (Gb1). In formula (Gb1), R ｂ１ , R ｂ２ and R ｂ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ｂ１ X represents a single bond or a divalent linking group. ｂ１ represents -O- or -C(=O)O-. G ｚ２ This represents a group represented by the following formula (G-3) or (G-4). In formula (G-3), R ｂ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ５ and R ｂ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ４ and R ｂ５ They may combine to form a ring. G ｚ２ If the group is represented by formula (G-3), then L ｂ１ is R ｂ３ or R ｂ４ It may combine with to form a ring. * indicates the bonding position. In formula (G-4), R ｂ７ , R ｂ８ and R ｂ９ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ｂ７ , R ｂ８ and R ｂ９ Two of them may join to form a ring. * indicates the bonding position.

9. The photosensitive or radiation-sensitive resin composition according to claim 1, further comprising a compound (C) that generates acid upon irradiation with active light or radiation.

10. The photosensitive or radiation-sensitive resin composition according to claim 1, further comprising an acid diffusion control agent (D).

11. The photosensitive or radiation-sensitive resin composition according to claim 9, wherein the compound (C) comprises an anion represented by the following formula (AN3). In formula (AN3), Ar represents an aromatic ring group. n represents a non-negative integer. D represents a single bond or a divalent linking group. B represents a hydrocarbon group.

12. The photosensitive or radiation-sensitive resin composition according to claim 10, wherein the acid diffusion control agent (D) comprises an anion represented by the following formula (d1-1). In formula (d1-1), R ５１ represents a substituent.

13. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 12.

14. A pattern forming method comprising the steps of: forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 12; exposing the active photosensitive or radiation-sensitive film; and developing the exposed active photosensitive or radiation-sensitive film using a developer to form a pattern.

15. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 14.

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