Actinic-ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for producing electronic device, and compound

Abstract

Provided are: an actinic-ray-sensitive or radiation-sensitive resin composition containing a compound (A) represented by a specific formula, a photoacid generator (B) different from the compound (A), and a resin (C); a resist film formed using the actinic-ray-sensitive or radiation-sensitive resin composition; a pattern formation method using the actinic-ray-sensitive or radiation-sensitive resin composition; a method for producing an electronic device; and the compound (A).

Description

Photosensitive or radiation-sensitive resin compositions, resist films, pattern forming methods, methods for manufacturing electronic devices, and compounds

[0001] The present invention relates to photosensitive or radiation-sensitive resin compositions, resist films, pattern formation methods, methods for manufacturing electronic devices, and compounds. More specifically, the present invention relates to 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, and to photosensitive or radiation-sensitive resin compositions, resist films, pattern formation methods, methods for manufacturing electronic devices, and compounds that can be suitably used in these 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 currently under development. 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 compound represented by a specific general formula, a resin whose solubility in a developer containing an organic solvent decreases due to the action of an acid, and a compound that generates acid upon irradiation with active light or radiation.

[0005] Japanese Patent Application Publication No. 2014-26102

[0006] Recently, the performance requirements for resist compositions have been increasing. Resist compositions are sometimes stored for a certain period after preparation, and when patterns are formed after such storage, it is desirable that they exhibit excellent line width roughness (LWR) (low LWR). The LWR of a resist composition after a certain period has elapsed since preparation is also called the "LWR over time." Furthermore, when patterns are formed after such storage, it is desirable that the cross-sectional shape of the formed pattern be rectangular (excellent pattern shape). The shape of a pattern formed using a resist composition after a certain period has elapsed since preparation is also called the "pattern shape over time."

[0007] The present invention aims to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent LWR and pattern shape over time. Furthermore, the present invention aims to provide a resist film formed using the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Moreover, the present invention aims to provide a compound that can be used in 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 photosensitive or radiation-sensitive resin composition comprising a compound (A) represented by the following formula (1), a photoacid generator (B) different from compound (A), and a resin (C).

[0010]

[0011] In formula (1), Z＋ represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-a). However, the molecular volume of A-H formed by adding a proton to A － is 310 Å ３ or more.

[0012]

[0013] In the formula (1-a), X represents a halogen atom. L １ represents a divalent linking group. R Ｎ represents a group containing at least one nitrogen atom. m and n each independently represent an integer of 1 to 4, and the sum of m and n is 5 or less. When there are a plurality of X, the plurality of X may be the same or different. L １ When there are a plurality of L １ may be the same or different. R Ｎ When there are a plurality of R Ｎ may be the same or different. However, the monovalent anion represented by the above formula (1-a) satisfies at least one of the following (i) and (ii). (i) The pKa of the conjugate acid formed by adding a proton to at least one nitrogen atom contained in the above R Ｎ is 1 or more. (ii) A group that dissociates by the action of an acid is bonded to at least one nitrogen atom contained in the above R Ｎ , and the pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which a hydrogen atom is bonded after the group that dissociates by the action of the acid dissociates is 1 or more. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the above R Ｎ is represented by the following formula (N-1).

[0014]

[0015] In the formula (N-1), L ２ represents a divalent hydrocarbon group that may contain a hetero atom. Y Ｎ１ and Y Ｎ２ each independently represent a monovalent organic group or a hydrogen atom. L ２ , Y Ｎ１ and Y Ｎ２At least two selected from the group consisting of may combine to form a ring. * is L １ This indicates the bonding position with R. [3] The above R Ｎ A photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the following formula (N-2) is used.

[0016]

[0017] In formula (N-2), L ２ Y represents a divalent hydrocarbon group which may contain heteroatoms. Ｎ１ R represents a monovalent organic group or hydrogen atom. １ , R ２ and R ３ Each of these independently represents a monovalent hydrocarbon group. ２ and Y Ｎ１ They may combine to form a ring. * is L １ This indicates the bonding position with [4] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the benzene ring in formula (1-a) above is not bonded to a group represented by the following formula (W-1).

[0018]

[0019] In formula (W-1), R ４ * represents a monovalent organic group. １ represents the bond position with the benzene ring in formula (1-a). [5] Y in formula (N-1) above Ｎ１ and Y Ｎ２ The photosensitive or radiation-sensitive resin composition according to [2], wherein -L in formula (1-a) above is not selected from the group consisting of fluorine atoms and aromatic carbon rings. [6] １ -R Ｎ A photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the group represented by does not contain an aromatic ring. [7] -L in formula (1-a) above １ -R Ｎ A photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the group represented by is the group represented by the following formula (Q-1).

[0020]

[0021] In formula (Q-1), L １１ is -O-, -S-, or -SO ２ Represents -. R １１ and R １２ Each of these independently represents a hydrogen atom or a substituent. １１ If multiple R １１ They may be the same or different. １２ If multiple R １２ They may be the same or different. L １２ is -O-, -CO-, * ２ -COO-* ３ , * ２ -OCO-* ３ -S-, -SO-, or -SO ２ Represents -. L １３ Y represents a divalent hydrocarbon group. Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. １３ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group may be joined to form a ring. k1 represents an integer greater than or equal to 1. k2 represents 0 or 1. * １ * represents the bond position with the benzene ring in formula (1-a). ２ CR １１ R １２ This indicates the bonding position with the carbon atoms inside. ３ is L １３ This indicates the joint position with A above. － The molecular volume of A-H, formed by adding a proton to A, is 325 Å. ３ The above describes the photosensitive or radiation-sensitive resin composition according to any one of [1] to [7]. [9] The above resin (C) has a structure in which a polar group is protected by a group that is removed by the action of an acid, and the group that is removed by the action of the acid is represented by the following formula (Y10) or (Y20) The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8]. Formula (Y10): -C(Rx １０ ) (Rx ２０ ) (Rx ３０) Formula (Y20): -C(=O)OC(Rx １０ ) (Rx ２０ ) (Rx ３０ In equations (Y10) and (Y20), Rx １０ ~Rx ３０ Each of these independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, Rx １０ ~Rx ３０ Two of them are bonded together to form a monoring.

[10] A resist film formed using the photosensitive or radiation-sensitive resin composition described in any one of [1] to [9].

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

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

[11] .

[13] A compound represented by the following formula (1).

[0022]

[0023] In formula (1), Z ＋ This represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-b). However, A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That's all.

[0024]

[0025] In equation (1-b), X represents a halogen atom. １ L represents a divalent linking group. ２ Y represents a divalent hydrocarbon group which may contain heteroatoms. Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. ２ , Y Ｎ１ and Y Ｎ２At least two selected from the group consisting of may combine to form a ring. m and n each independently represent an integer from 1 to 4, and the sum of m and n is 5 or less. When there are a plurality of Xs, the plurality of Xs may be the same or different. L １ When there are a plurality of Ls １ may be the same or different. L ２ When there are a plurality of Ls ２ may be the same or different. Y Ｎ１ When there are a plurality of Ys Ｎ１ may be the same or different. Y Ｎ２ When there are a plurality of Ys Ｎ２ may be the same or different. However, the monovalent anion represented by the above formula (1-b) satisfies at least one of the following (iii) and (iv). (iii) The pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which Y Ｎ１ and Y Ｎ２ are bonded is 1 or more. (iv) At least one of Y Ｎ１ and Y Ｎ２ represents a group that dissociates by the action of an acid, and the pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which a hydrogen atom is bonded after the group that dissociates by the action of the above acid dissociates is 1 or more.

[0026] According to the present invention, it is possible to provide a chemically amplified photosensitive or radiation-sensitive resin composition excellent in LWR after aging and pattern shape after aging. Further, according to the present invention, it is possible to provide a resist film formed using the above chemically amplified photosensitive or radiation-sensitive resin composition, a pattern forming method using the above chemically amplified photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Furthermore, according to the present invention, it is possible to provide a compound that can be used in the above chemically amplified photosensitive or radiation-sensitive resin composition.

[0027] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0028] 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, and X-rays, 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.

[0029] 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.

[0030] 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).

[0031] 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.

[0032] (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; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; Examples include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups (heteroaryl groups, aromatic heterocyclic groups); hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; cyano groups; nitro groups; cycloalkyloxycarbonyl groups; heteroaryloxycarbonyl groups; alkylcarbonyl groups; arylcarbonyl groups; heteroarylcarbonyl groups; cycloalkylcarbonyl groups; cycloalkyloxy groups; heteroaryloxy groups; alkylsulfonyl groups; arylsulfonyl groups; cycloalkylsulfonyl groups; heteroarylsulfonyl groups; alkylsulfinyl groups; arylsulfinyl groups; cycloalkylsulfinyl groups; heteroarylsulfinyl groups; and so on. Furthermore, if these substituents can have one or more further substituents, the group having one or more substituents selected from the substituents described above (for example, a monoalkylamino group, a dialkylamino group, an arylamino group, etc.) is also included as an example of substituent T.

[0033] 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".

[0034] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, specifically, a value calculated using the following software package 1, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described herein are calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0035] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated using, for example, the Density Functional Theory (DFT), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT, such as Gaussian 16.

[0036] 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.

[0037] In this specification, "solids" means components that form a film (preferably a resist film) using a photosensitive or radiation-sensitive resin composition, and does not include solvents. Furthermore, any component that forms a film (preferably a resist film) using a photosensitive or radiation-sensitive resin composition is considered a solid, even if its properties are liquid.

[0038] <Photosensitive or Radiation-Sensitive Resin Composition> The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is a photosensitive or radiation-sensitive resin composition containing a compound (A) represented by the following formula (1), a photoacid generator (B) different from compound (A), and a resin (C).

[0039]

[0040] In formula (1), Z ＋ This represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-a). However, A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That's all.

[0041]

[0042] In formula (1-a), X represents a halogen atom. １ R represents a divalent linking group. Ｎ X represents a group containing at least one nitrogen atom. m and n each independently represent integers from 1 to 4, and the sum of m and n is 5 or less. If there are multiple Xs, they may be the same or different. L １ If there are multiple L １ They may be the same or different. Ｎ If multiple R Ｎ They may be the same or different. However, the monovalent anion represented by the above formula (1-a) satisfies at least one of the following (i) and (ii). (i) The above R ＮThe pKa of the conjugate acid obtained by adding a proton to at least one nitrogen atom contained in is 1 or greater. (ii) The above R Ｎ A group that is removed by the action of an acid is bonded to at least one nitrogen atom contained in the acid, and when the group that is removed by the action of the acid is removed, a proton is added to the nitrogen atom to which a hydrogen atom is bonded, and the pKa of the conjugate acid is 1 or more.

[0043] The mechanism by which the composition of the present invention exhibits superior LWR and pattern shape over time is not clear, but the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism below. Compound (A) represented by formula (1) above has a nitrogen atom that exhibits basicity or a nitrogen atom that exhibits basicity due to the action of an acid, and therefore can function as an acid diffusion control agent. Furthermore, the monovalent anion (A) represented by formula (1-a) above is contained in compound (A) represented by formula (1) above. － It is thought that the molecular volume of (A-H) after proton addition is above a certain level, which suppresses aggregation over time. These properties of compound (A) are thought to improve the LWR and pattern shape over time.

[0044] The composition of the present invention is typically 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. Preferably, the composition of the present invention is a chemically amplified resist composition. A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. A photosensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. Below, the various components of the composition of the present invention will be described in detail.

[0045] [Compound (A) represented by formula (1)] The composition of the present invention contains compound (A) represented by formula (1) above (also simply referred to as "compound (A)"). Compound (A) may be in the form of a low molecular weight compound or a high molecular weight compound. In addition, compound (A) may be in the form of both a low molecular weight compound and a high molecular weight compound. When compound (A) is in the form of a low molecular weight compound, the molecular weight of compound (A) is preferably 3000 or less, and more preferably 2000 or less. There is no particular lower limit to the molecular weight of compound (A), but it is preferably 200 or more. It is more preferably 400 or more, and even more preferably 600 or more. When compound (A) is in the form of a high molecular weight compound, compound (A) and resin (C) described later may be the same compound, or compound (A) may be a high molecular weight compound different from resin (C). Compound (A) is preferably in the form of a low molecular weight compound.

[0046] A in equation (1) － represents a monovalent anion represented by the above formula (1-a). In formula (1-a), X represents a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom.

[0047] In formula (1-a), m represents an integer from 1 to 4, preferably an integer from 2 to 4, more preferably 3 or 4, and even more preferably 4.

[0048] L in equation (1-a) １ L represents a divalent linking group. １ The divalent linking group represented by is not particularly limited, but for example, divalent hydrocarbon groups, -O-, -CO-, -S-, -SO-, -SO ２- and groups formed by combining two or more of these are examples. The above divalent hydrocarbon group may have substituents. Examples of the above divalent hydrocarbon group include alkylene group, cycloalkylene group, alkenylene group, cycloalkenylene group, alkylylene group, arylene group, and groups formed by combining two or more of these, with alkylene group, cycloalkylene group, alkenylene group, cycloalkenylene group or alkylylene group being preferred, and alkylene group being more preferred. The above alkylene group may be linear or branched, and is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms. The above cycloalkylene group may be monocyclic or polycyclic, and is preferably a cycloalkylene group having 3 to 20 carbon atoms, and more preferably a cycloalkylene group having 5 to 10 carbon atoms. The above alkenylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above cycloalkenylene group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, and more preferably having 5 to 10 carbon atoms. The above alkynylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above arylene group may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, and more preferably having 6 to 15 carbon atoms.

[0049] L １ These are divalent hydrocarbon groups, -O-, -COO-, -S-, -SO ２ - Preferably, it represents a group formed by combining two or more of these, such as an alkylene group, -O-, -COO-, -S-, -SO ２ - More preferably, it represents a group consisting of two or more of these, such as an alkylene group, -O-, -S-, -SO ２ - More preferably, it represents a group formed by combining two or more of these, such as -O-, -S-, or -SO ２It is especially preferable to represent it as -.

[0050] R in equation (1-a) Ｎ R represents a group containing at least one nitrogen atom. Ｎ The monovalent anion represented by formula (1-a) is not particularly limited as long as it satisfies at least one of the following (i) and (ii). (i) R Ｎ The pKa of the conjugate acid, which is formed by adding a proton to at least one nitrogen atom contained in the compound, is 1 or greater. (ii) R Ｎ At least one nitrogen atom contained in the compound has a group that is removed by the action of an acid bonded to it, and when the group that is removed by the action of the acid is removed, a proton is added to the nitrogen atom to which a hydrogen atom is bonded, and the pKa of the conjugate acid is 1 or greater.

[0051] R Ｎ This may be an aliphatic group containing at least one nitrogen atom, or an aromatic group containing at least one nitrogen atom. The aromatic group containing at least one nitrogen atom may be a nitrogen-containing aromatic heterocyclic group, for example, a group obtained by removing one or more hydrogen atoms from pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc.

[0052] R Ｎ It is preferable that it is represented by the following formula (N-1).

[0053]

[0054] In formula (N-1), L ２ Y represents a divalent hydrocarbon group which may contain heteroatoms. Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. ２ , Y Ｎ１ and Y Ｎ２ At least two selected from the group consisting of may combine to form a ring. * is L １ This indicates the connection point with [the other element].

[0055] L in equation (N-1) ２L represents a divalent hydrocarbon group which may contain heteroatoms. ２ The divalent hydrocarbon group represented by may have substituents. ２ The divalent hydrocarbon group represented by is not particularly limited, but examples include alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, alkylylene groups, arylene groups, and groups formed by combining two or more of these. Alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, or alkylylene groups are preferred, alkylene groups or cycloalkylene groups are more preferred, and alkylene groups are even more preferred. The alkylene group may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, and even more preferably having 1 to 5 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, and more preferably having 5 to 10 carbon atoms. The above alkenylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above cycloalkenylene group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, and more preferably having 5 to 10 carbon atoms. The above alkynylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above arylene group may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, and more preferably having 6 to 15 carbon atoms.

[0056] L ２ The divalent hydrocarbon group represented by may contain heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. ２ Divalent hydrocarbon groups represented by these are, for example, -O-, -CO-, -S-, -SO-, -SO ２ - and groups formed by combining two or more of these may also be included.

[0057] Y in equation (N-1) Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. Ｎ１ and Y Ｎ２ The monovalent organic group represented by is not particularly limited, but is preferably an organic group having 1 to 30 carbon atoms. Ｎ１ and Y Ｎ２ The monovalent organic group represented by is preferably an alkyl group, alkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, heteroaryl group, heteroaryloxy group, heteroaryloxycarbonyl group, or formyl group, more preferably an alkyl group, cycloalkyl group, alkoxycarbonyl group, or cycloalkyloxycarbonyl group, and even more preferably an alkyl group or alkoxycarbonyl group. These groups may have one or more substituents.

[0058] Y Ｎ１ and Y Ｎ２ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited; for example, 1 to 30 is preferred, 1 to 20 is more preferred, and 1 to 15 is even more preferred. The alkyl group may have substituents. The alkyl group may also contain at least one of an ether bond (-O-) and a thioether bond (-S-) in the chain. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like.

[0059] Y Ｎ１ and Y Ｎ２The descriptions, specific examples, and preferred ranges of alkyl groups included in the alkoxy group, alkylthio group, and alkoxycarbonyl group represented by the above-mentioned Y are as follows: Ｎ１ and Y Ｎ２ This is the same as in the alkyl group represented by .

[0060] Y Ｎ１ and Y Ｎ２ The alkenyl group represented by may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited; for example, 2 to 20 is preferred, 2 to 15 is more preferred, and 2 to 10 is even more preferred. The alkenyl group may have substituents. The alkenyl group may also contain at least one of an ether bond (-O-) and a thioether bond (-S-) in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0061] Y Ｎ１ and Y Ｎ２ The alkynyl group represented by may be linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited; for example, 2 to 20 is preferred, 2 to 15 is more preferred, and 2 to 10 is even more preferred. The alkynyl group may have substituents. The alkynyl group may also contain at least one of an ether bond (-O-) and a thioether bond (-S-) in the chain. Examples of alkynyl groups include the ethynyl group.

[0062] Y Ｎ１ and Y Ｎ２The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited; for example, 3 to 30 is preferred, 4 to 20 is more preferred, and 5 to 15 is even more preferred. The cycloalkyl group may have substituents. For example, in the cycloalkyl group, one or more methylene groups constituting the cycloalkane ring may be replaced with heteroatoms such as oxygen atoms or sulfur atoms, or with groups having heteroatoms such as carbonyl groups. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with vinylene groups. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0063] Y Ｎ１ and Y Ｎ２ The descriptions, specific examples, and preferred ranges of the cycloalkyl groups included in the cycloalkyloxy group, cycloalkylthio group, and cycloalkyloxycarbonyl group represented by the above-mentioned Y are as follows: Ｎ１ and Y Ｎ２ This is the same as in the cycloalkyl group represented by .

[0064] Y Ｎ１ and Y Ｎ２The number of carbon atoms in the aryl group represented by is not particularly limited, for example, 6 to 30 is preferred, 6 to 20 is more preferred, and 6 to 15 is even more preferred. The aryl group may have substituents. The aryl group may be a monocyclic or polycyclic group. The aryl group may be an aromatic hydrocarbon (e.g., monocyclic or polycyclic aromatic hydrocarbons with 6 to 15 carbon atoms such as benzene and naphthalene), a cycloalkane (e.g., monocyclic or polycyclic cycloalkanes with 3 to 12 carbon atoms such as cyclopentane and cyclohexane, which may have one or more carbonyl groups as ring groups), a cycloalkene (e.g., monocyclic or polycyclic cycloalkenes with 3 to 12 carbon atoms such as cyclohexene, which may have one or more carbonyl groups as ring groups), or a non-aromatic heterocyclic compound (e.g., pyrrolidine, pyrroline, 2 - Examples include five-membered non-aromatic heterocyclic compounds such as oxazolidone, tetrahydrofuran, 1,3-dioxolane, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring may have at least one group selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group.) It may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure fused with at least one group selected from the group consisting of ) Examples of aryl groups include phenyl group, naphthyl group, anthryl group, fluorenyl group, and phenanthryl group, with phenyl group or naphthyl group being preferred, and phenyl group being more preferred.

[0065] Y Ｎ１ and Y Ｎ２ The descriptions, specific examples, and preferred ranges of the aryl groups included in the aryloxy group, arylthio group, and aryloxycarbonyl group represented by the above-mentioned Y are as follows: Ｎ１ and Y Ｎ２ This is the same as the case with the aryl group represented by .

[0066] Y Ｎ１ and Y Ｎ２The heteroaryl group (aromatic heterocyclic group) represented by preferably contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have substituents. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, as well as groups obtained by removing one hydrogen atom from six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. Furthermore, the heteroaryl group is the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound, the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, aromatic hydrocarbons (for example, monocyclic or polycyclic aromatic hydrocarbons with 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (for example, monocyclic or polycyclic cycloalkanes with 3 to 12 carbon atoms such as cyclopentane and cyclohexane, which may have one or more carbonyl groups as ring-forming groups), cycloalkenes (for example, cyclohexene, etc. 3 to 12 monocyclic or polycyclic cycloalkenes. These may have one or more carbonyl groups as ring groups.), non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. These may have at least one group selected from the group consisting of carbonyl groups, sulfonyl groups, and ethylene groups as ring groups.)It may also be a group obtained by removing one hydrogen atom from a condensed ring compound having a structure condensed with at least one selected from the group consisting of ) (for example, indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, sinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.).

[0067] Y Ｎ１ and Y Ｎ２ The acyl group represented by R Ｃ１ It is represented as -C (=O)-, R Ｃ１ It is preferable that R represents a monovalent organic group. Ｃ１ The monovalent organic group represented is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. Ｃ１ The description, specific examples, and preferred range of the monovalent organic group represented by are as described above in Y. Ｎ１ and Y Ｎ２ It is the same as the one in [location].

[0068] Y Ｎ１ and Y Ｎ２ The heteroaryloxy group represented by R Ｃ２ It is a group represented by -O-. Ｃ２ R represents a heteroaryl group. Ｃ２ The description, specific examples, and preferred range of the heteroaryl group represented by the above Y Ｎ１ and Y Ｎ２ It is the same as the one in [location].

[0069] Y Ｎ１ and Y Ｎ２ The description, specific examples, and preferred range of the heteroaryl group contained in the heteroaryloxycarbonyl group represented by Y are as described above. Ｎ１ and Y Ｎ２ This is the same as the case of the heteroaryl group represented by .

[0070] L in equation (N-1) ２ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of L may be joined together to form a ring. ２ , Y Ｎ１ and YＮ２ A configuration in which at least two selected from the group consisting of are joined together to form a ring is L ２ and Y Ｎ１ or Y Ｎ２ A configuration in which they combine to form a ring, and Y Ｎ１ and Y Ｎ２ A configuration in which the elements combine to form a ring is preferred, L ２ and Y Ｎ１ or Y Ｎ２ A configuration in which the elements combine to form a ring is more preferable.

[0071] Y in equation (N-1) Ｎ１ and Y Ｎ２ It is preferable that it does not contain at least one selected from the group consisting of fluorine atoms and aromatic carbon rings. That is, Y Ｎ１ and Y Ｎ２ It is preferable that it does not contain fluorine atoms. Ｎ１ and Y Ｎ２ It is preferable that it does not contain aromatic carbon rings. Ｎ１ and Y Ｎ２ It is preferable that it does not contain fluorine atoms and aromatic carbon rings.

[0072] R Ｎ It is also preferable that this be expressed by the following formula (N-2).

[0073]

[0074] In formula (N-2), L ２ Y represents a divalent hydrocarbon group which may contain heteroatoms. Ｎ１ R represents a monovalent organic group or hydrogen atom. １ , R ２ and R ３ Each of these independently represents a monovalent hydrocarbon group. ２ and Y Ｎ１ They may combine to form a ring. * is L １ This indicates the connection point with [the other element].

[0075] L in equation (N-2) ２ The explanation, specific examples, and preferred range of L in formula (N-1) above are given by ２ It is the same as the one in [location].

[0076] Y in equation (N-2)Ｎ１ The explanation, specific examples, and preferred range of Y in formula (N-1) above are given by Ｎ１ It is the same as the one in [location].

[0077] R in equation (N-2) １ , R ２ and R ３ Each of these independently represents a monovalent hydrocarbon group. １ , R ２ and R ３ The monovalent hydrocarbon group represented by is not particularly limited, but is preferably a hydrocarbon group having 1 to 20 carbon atoms. １ , R ２ and R ３ The monovalent hydrocarbon group represented is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group or a cycloalkyl group. These groups may have one or more substituents.

[0078] R １ , R ２ and R ３ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited; for example, 1 to 20 is preferred, 1 to 15 is more preferred, and 1 to 10 is even more preferred. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl groups.

[0079] R １ , R ２ and R ３ The alkenyl group represented by may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited; for example, 2 to 20 is preferred, 2 to 15 is more preferred, and 2 to 10 is even more preferred. The alkenyl group may have substituents. Examples of alkenyl groups include vinyl groups and allyl groups.

[0080] R １ , R ２ and R ３The alkynyl group represented by may be linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited; for example, 2 to 20 is preferred, 2 to 15 is more preferred, and 2 to 10 is even more preferred. The alkynyl group may have substituents. Examples of alkynyl groups include the ethynyl group.

[0081] R １ , R ２ and R ３ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited; for example, 3 to 20 is preferred, 4 to 15 is more preferred, and 5 to 10 is even more preferred. The cycloalkyl group may have substituents. In the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

[0082] R １ , R ２ and R ３ The number of carbon atoms in the aryl group represented by is not particularly limited, for example, 6 to 20 is preferred, 6 to 15 is more preferred, and 6 to 10 is even more preferred. The aryl group may have substituents. The aryl group may be a monocyclic or polycyclic group. Examples of aryl groups include phenyl, naphthyl, anthryl, fluorenyl, and phenanthryl groups, with phenyl or naphthyl groups being preferred, and phenyl groups being more preferred.

[0083] The group represented by formula (N-2-1) in formula (N-2) is a group that is eliminated by the action of an acid.

[0084]

[0085] In formula (N-2-1), R １ , R ２ and R ３ Each of these independently represents a monovalent hydrocarbon group. # indicates the bond position with the nitrogen atom.

[0086] R in equation (N-2-1) １ , R２ and R ３ The explanation, specific examples, and preferred range of R in formula (N-2) above are given by １ , R ２ and R ３ It is the same as the one in [location].

[0087] R Ｎ It is preferable that it contains at least one nitrogen atom selected from the group consisting of nitrogen atoms not bonded to a sulfonyl group and nitrogen atoms not bonded to an aromatic ring to which a halogen atom is bonded, and more preferably that it contains at least one nitrogen atom that is not bonded to a sulfonyl group and is not bonded to an aromatic ring to which a halogen atom is bonded.

[0088] A － The molecular volume of A-H, formed by adding a proton to , is 310 Å. ３ From the above perspective, R Ｎ It is preferable that the sum of the number of carbon atoms, nitrogen atoms, and oxygen atoms contained in the material is 11 or more.

[0089] In formula (1-a), n represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0090] A monovalent anion represented by formula (1-a) satisfies at least one of the following conditions (i) and (ii): (i) R Ｎ The pKa of the conjugate acid, which is formed by adding a proton to at least one nitrogen atom contained in the compound, is 1 or greater. (ii) R ＮAt least one nitrogen atom in the compound has a group that is eliminated by the action of an acid attached to it, and when the group that is eliminated by the action of the acid is eliminated, a proton is added to the nitrogen atom to which a hydrogen atom is attached, resulting in a conjugate acid whose pKa is 1 or greater. As mentioned above, the pKa of the conjugate acid is determined in principle using "Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)". Compound (A) can function as an acid diffusion control agent if the monovalent anion represented by formula (1-a) satisfies at least one of the above (i) and (ii).

[0091] The above (i) will be explained with a specific example. For example, the compound represented by A-1 below is compound (A). The nitrogen atom of the compound represented by A-1 does not have a group attached to it that is eliminated by the action of an acid. The monovalent anion contained in the compound represented by A-1 is the anion represented by A-1-a below. The conjugate acid obtained by adding a proton to the nitrogen atom contained in the anion represented by A-1-a is represented by A-1-b below. Since the pKa of the conjugate acid represented by A-1-b is 5.15, the anion represented by A-1-a satisfies the above (i).

[0092]

[0093] Next, we will explain the above (ii) with a specific example. For example, the compound represented by A-2 below is compound (A). The nitrogen atom of the compound represented by A-2 has a group that is eliminated by the action of an acid attached to it. The monovalent anion contained in the compound represented by A-2 is the anion represented by A-2-a below. The conjugate acid formed when the group that is eliminated by the action of an acid attached to the nitrogen atom contained in the anion represented by A-2-a is eliminated and a proton is added to the nitrogen atom to which a hydrogen atom is attached is represented by A-2-b below. The pKa of the conjugate acid represented by A-2-b is 9.30, so the anion represented by A-2-a satisfies the above (ii).

[0094]

[0095] The pKa of the conjugate acids in (i) and (ii) above is preferably 2 to 14, more preferably 3 to 13, and even more preferably 4 to 12.

[0096] A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That is all. 325 Å ３ Preferably, it is 330 Å or more. ３ It is more preferable that the above conditions are met. The upper limit of the molecular volume of A-H is 1000 Å. ３ Preferably, it is 800 Å. ３ The following is more preferable: The molecular volume of A-H is the value obtained during structural optimization using the PM3 Hamiltonian implemented in MOPAC7 included with Winmostar v11.7.4 and calculated by the EF (Eigen Vector Following) method. A-H is a compound represented by the following formula (1-a-H).

[0097]

[0098] X, L in equation (1-a-H) １ , R Ｎ The definitions, explanations, specific examples, and preferred ranges of m and n are given by X and L in formula (1-a) above, respectively. １ , R Ｎ , it is the same as in m and n.

[0099] It is preferable that the benzene ring in formula (1-a) is not bonded to the group represented by the following formula (W-1).

[0100]

[0101] In formula (W-1), R ４ * represents a monovalent organic group. １ R represents the bond position with the benzene ring in formula (1-a). ４ The monovalent organic group represented by is not particularly limited, but for example, Y in formula (N-1) above Ｎ１ and Y Ｎ２ Examples include monovalent organic groups similar to those represented by .

[0102] -L in equation (1-a) １ -RＮ It is preferable that the group represented by does not contain an aromatic ring. The above aromatic rings include aromatic carbocyclic rings and aromatic heterocyclic rings.

[0103] -L in equation (1-a) １ -R Ｎ It is preferable that the group represented by is the group represented by the following formula (Q-1).

[0104]

[0105] In formula (Q-1), L １１ is -O-, -S-, or -SO ２ Represents -. R １１ and R １２ Each of these independently represents a hydrogen atom or a substituent. １１ If multiple R １１ They may be the same or different. １２ If multiple R １２ They may be the same or different. L １２ is -O-, -CO-, * ２ -COO-* ３ , * ２ -OCO-* ３ -S-, -SO-, or -SO ２ Represents -. L １３ Y represents a divalent hydrocarbon group. Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. １３ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group may be joined to form a ring. k1 represents an integer greater than or equal to 1. k2 represents 0 or 1. * １ * represents the bond position with the benzene ring in formula (1-a). ２ CR １１ R １２ This indicates the bonding position with the carbon atoms inside. ３ is L １３ This indicates the connection point with [the other element].

[0106] R in equation (Q-1) １１ and R １２ Each of these independently represents a hydrogen atom or a substituent.１１ and R １２ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. １１ and R １２ The substituent represented is preferably a monovalent organic group. １１ and R １２ The description, specific examples, and preferred range of the monovalent organic group represented by the above formula (N-1) are as follows: Ｎ１ and Y Ｎ２ This is the same as that for a monovalent organic group represented by .

[0107] L in equation (Q-1) １３ L represents a divalent hydrocarbon group. １３ The divalent hydrocarbon group represented by may have substituents. １３The divalent hydrocarbon group represented by is not particularly limited, but examples include alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, alkylylene groups, arylene groups, and groups formed by combining two or more of these. Alkylene groups, cycloalkylene groups, alkenylene groups, cycloalkenylene groups, or alkylylene groups are preferred, alkylene groups or cycloalkylene groups are more preferred, and alkylene groups are even more preferred. The alkylene group may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, and even more preferably having 1 to 5 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, and more preferably having 5 to 10 carbon atoms. The above alkenylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above cycloalkenylene group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, and more preferably having 5 to 10 carbon atoms. The above alkynylene group may be linear or branched, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. The above arylene group may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, and more preferably having 6 to 15 carbon atoms.

[0108] Y in equation (Q-1) Ｎ１ and Y Ｎ２ The explanation, specific examples, and preferred range of Y in formula (N-1) above are given by Ｎ１ and Y Ｎ２ It is the same as the one in [location].

[0109] L in equation (Q-1) １３ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of L may be joined together to form a ring. １３ , Y Ｎ１ and Y Ｎ２A configuration in which at least two selected from the group consisting of are joined together to form a ring is L １３ and Y Ｎ１ or Y Ｎ２ A configuration in which they combine to form a ring, and Y Ｎ１ and Y Ｎ２ A configuration in which the elements combine to form a ring is preferred, L １３ and Y Ｎ１ or Y Ｎ２ A configuration in which the elements combine to form a ring is more preferable.

[0110] In formula (Q-1), k1 represents an integer of 1 or more, preferably an integer between 1 and 10, and more preferably an integer between 1 and 5.

[0111] Z in equation (1) ＋ Z represents a monovalent cation. ＋ Z preferably represents a monovalent organic cation, and more preferably a sulfonium cation or an iodonium cation. ＋ Preferably, represents a cation represented by the following formula (ZaI) (also called "cation (ZaI)") or a cation represented by the following formula (ZaII) (also called "cation (ZaII)").

[0112]

[0113] 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.

[0114] 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.

[0115] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ It is an arylsulfonium cation in which at least one of the groups is an aryl group. ２０１ ~R ２０３ All of them may be aryl groups, or R ２０１ ~R ２０３ A portion of it may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ One of them is an aryl group, R ２０１ ~R ２０３ The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH ２ -CH ２ -O-CH ２ -CH ２ Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0116] 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.

[0117] R ２０１ ~R ２０３ The substituents that the aryl group, alkyl group, and cycloalkyl group may have are preferably 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 (preferably chlorine, bromine, or iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The substituents may have further substituents if possible. The substituents may also form an acid-degradable group in any combination.

[0118] 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 ２０３The 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.

[0119] R ２０１ ~R ２０３ Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, 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.

[0120] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0121]

[0122] 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 ７ｃEach 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.

[0123] 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.

[0124] 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 ｘThe 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.

[0125] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and also, R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The rings formed by the bonding of these elements to each other may have substituents.

[0126] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0127]

[0128] 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 (preferably a chlorine atom, a bromine atom, or 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 (preferably a chlorine atom, a bromine atom, or 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. １４If multiple instances exist, each independently represents one of the above groups, such as a hydroxyl group. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The above alkyl group, the above cycloalkyl group, and the above naphthyl group, and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0129] In equation (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. １３ ~R １５ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0130] 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 ２０５The 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).

[0131] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ２０４ and R ２０５ Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0132] Below Z ＋ Specific examples are given, but the work is not limited to these.

[0133]

[0134]

[0135] The content of compound (A) is not particularly limited, but is preferably 0.01 to 30.0% by mass, more preferably 0.05 to 20.0% by mass, and even more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention. The composition of the present invention may contain one type of compound (A) or two or more types. If the composition of the present invention contains two or more types of compound (A), it is preferable that their total content is within the range of the above preferred content.

[0136] Specific examples of compound (A) include, but are not limited to, A-1 to A-15 described in the examples below.

[0137] An example of the synthesis of compound (A) will be described in the examples below.

[0138] [Photoacid Generator (B)] The composition of the present invention contains a photoacid generator (B) (also referred to as "compound (B)") different from compound (A) described above. Compound (B) is a compound that generates acid upon irradiation with active light or radiation, and is preferably a compound that generates acid with a pKa of less than 1. The pKa of the acid generated from compound (B) upon irradiation with active light or radiation is preferably 0 or less, more preferably -0.1 or less, and even more preferably -0.2 or less. Furthermore, there is no particular lower limit to the pKa of the acid generated from compound (B) upon irradiation with active light or radiation, but for example it may be -3 or more, or -2 or more.

[0139] Compound (B) may be in the form of a low molecular weight compound or a high molecular weight compound. Furthermore, compound (B) may be a combination of both low molecular weight and high molecular weight compounds. When compound (B) is in the form of a low molecular weight compound, its molecular weight is preferably 3000 or less, and more preferably 2000 or less. The lower limit of the molecular weight of compound (B) is not particularly limited, but 100 or more is preferred. When compound (B) is in the form of a high molecular weight compound, compound (B) and the resin (C) described later may be the same compound, or compound (B) may be a different high molecular weight compound from resin (C). If resin (C) does not contain repeating units having photoacid-generating groups, the composition of the present invention preferably contains compound (B) as a compound different from resin (C). If resin (C) contains repeating units having photoacid-generating groups, the composition of the present invention may or may not contain compound (B) as a compound different from resin (C). Compound (B) is preferably in the form of a low molecular weight compound.

[0140] For example, compound (B) is "M ＋ X －Examples of compounds represented by '' (onium salts) include compounds that generate organic acids upon exposure to light. Examples of the above 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.

[0141] "M ＋ X － In the compound represented by ", M ＋ M represents a cation. ＋ The valency of the cation represented by is 1 or greater. ＋ It is preferable that represents an organic cation. ＋ When M represents a monovalent cation ＋ The explanation, specific examples, and preferred range of Z in formula (1) above are given by ＋ It is similar to the one in [location / place].

[0142] "M ＋ X － In the compound represented by ", X － The symbol represents an anion, preferably an organic anion. The organic anion is not particularly limited, and examples include 1-valent or 2-valent or higher organic anions. The organic anion is preferably one with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0143] 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.

[0144] 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).

[0145] 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.

[0146] 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).

[0147] 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.

[0148] An example of a sulfonylimid anion is the saccharin anion.

[0149] 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.

[0150] 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.

[0151] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0152]

[0153] In formula (AN1), R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', and -NH. ２ ,-NR' ２ -NHR' or -NHCOR' are preferred. R' is a monovalent hydrocarbon group.

[0154] 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.

[0155] L represents a divalent linking group. If there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of divalent linking groups include alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining multiples thereof. Among these, examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ２ - or -COO-alkylene group- is more preferred.

[0156] For L, a group represented by the following formula (AN1-1) is preferred. * ａ - (CR２ａ ２ ) Ｘ -Q- (CR ２ｂ ２ ) Ｙ - * ｂ (AN1-1)

[0157] In formula (AN1-1), * ａ R in equation (AN1) ３ This indicates the connection point with [the other element]. * ｂ This is -C(R) in equation (AN1). １ ) (Caution ２ ) - Represents the connection position with . X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3. R ２ａ and R ２ｂ Each of these independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ If there are multiple instances of each, then there are multiple instances of R ２ａ and R ２ｂ These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) １ ) (Caution ２ )- and CR that bind directly ２ｂ ２ In R ２ｂ is anything other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents the condition where X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) ２ａ and R ２ｂ If all of them are hydrogen atoms, then Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-*Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents. * Ａ R in equation (AN1) ３ This indicates the connection position on the side, * Ｂ This is -SO in equation (AN1). ３ － This indicates the connection point on the side.

[0158] 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.).

[0159] 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 (LC1-22) and (SL1-1) to (SL1-3), as described later.

[0160] 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.

[0161] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0162]

[0163] 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.

[0164] 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.

[0165] 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.

[0166] L represents a divalent linking group. The definition of L is the same as the L in formula (AN1).

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0172]

[0173] 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.

[0174] 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.

[0175] 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).

[0176] 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, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0177] Compound (B) preferably contains at least one selected from the group consisting of the anion represented by the following formula (AN4), the anion represented by the following formula (AN5), and the anion represented by the following formula (AN6).

[0178]

[0179] In formula (AN4), R４ , R ５ and R ６ Each of these independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. However, R ４ When R represents a fluorine atom, ５ and R ６ R does not represent a fluorine atom. In formula (AN5), ７ R represents a monovalent organic group. ７ If there are multiple values, they may be the same or different. p represents an integer from 1 to 5. q represents an integer from 0 to 5. The sum of p and q is 5 or less. In equation (AN6), R ８ and R ９ Each of these independently represents a hydrogen atom or a monovalent organic group. ８ and R ９ They may bond to form a ring. ４ , R ５ , R ６ , R ７ , R ８ and R ９ The monovalent organic group represented by R is not particularly limited. ４ , R ５ , R ６ , R ７ , R ８ and R ９ The explanation, specific examples, and preferred range of the monovalent organic group represented by the above formula (N-1) is Y Ｎ１ and Y Ｎ２ It may be the same as that in a monovalent organic group represented by .

[0180] Compound (B) is also preferably at least one selected from the group consisting of compounds (I) to (II).

[0181] (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.

[0182] 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 ２ It 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.

[0183] 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 ２Compounds 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.

[0184] 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 the compound becomes "a compound having the two A's" corresponds to the above-mentioned 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 HA１ 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] Anion part A １ － and anion part A ２ － This is a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion site A １ － Preferably, it is an acidic moiety that can form an acidic moiety with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion moiety A ２ － For example, Anion part A １ － It is preferable that the acidic site can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6) below, * represents the bond position. In formula (AA-2), R Ａ R represents a monovalent organic group. Ａ The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0190]

[0191]

[0192] Cation site M １ ＋ and cation site M ２ ＋ This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. ＋Examples of organic cations represented by the following are given.

[0193] (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

[0194] 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) 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198]

[0199] 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.

[0200] Examples of non-cationic sites that compound (I) and compound (II) may have are given below.

[0201]

[0202]

[0203] Specific examples of compound (B) include, for example, the compounds described in

[0320] to

[0321] of International Publication No. 2022 / 172715. The above description is incorporated herein by reference.

[0204] The content of compound (B) 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 (B) is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% by mass or less, relative to the total solid content of the composition of the present invention. The composition of the present invention may contain one type of compound (B) or two or more types. If the composition of the present invention contains two or more types of compound (B), it is preferable that their total content is within the range of the above preferred content.

[0205] [Resin (C)] The composition of the present invention contains resin (C). Preferably, resin (C) is a resin whose polarity increases by the action of an acid. Preferably, resin (C) contains a group that decomposes and increases in polarity by the action of an acid (also called an "acid-degradable group"), and more preferably contains a repeating unit having an acid-degradable group. When resin (C) has an acid-degradable group, in a pattern forming method using the composition of the present invention, if an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and if an organic developer is used as the developer, a negative-type pattern is suitably formed.

[0206] (Repeating units having acid-degradable groups) The acid-degradable groups are preferably groups that decompose upon the action of an acid to produce polar groups. The acid-degradable groups are preferably in a structure in which the polar groups are protected by groups that leave upon the action of an acid (leaving groups). The resin (C) preferably has repeating units having groups that decompose upon the action of an acid to produce polar groups, thereby increasing polarity upon the action of an acid, increasing solubility in alkaline developers, and decreasing solubility in organic solvents. Preferred polar groups are 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. Preferred polar groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0207] Examples of groups that are eliminated by the action of an acid include the groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (Caution ３７ ) ( OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0208] In equations (Y1) and (Y2), Rx １ ~Rx ３Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). 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. １ ~Rx ３ Each of these preferably independently represents a linear or branched alkyl group, and more preferably a linear alkyl group. １ ~Rx ３ These two may combine to form a monocycle or polycycle. Rx １ ~Rx ３ Preferred alkyl groups include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. １ ~Rx ３ The cycloalkyl group may be a cycloalkyl group having 3 to 20 carbon atoms. Rx １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ A cycloalkyl group is preferred as the ring formed by the bonding of these two. Rx １ ~Rx ３The cycloalkyl group formed by the bonding of these two groups is preferably 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, with a monocyclic cycloalkyl group having 5 to 6 carbon atoms being more preferred. １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups may have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded to form the above-mentioned cycloalkyl group. When the composition of the present invention is, for example, an EUV lithography resist composition, Rx １ ~Rx ３ Alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and Rx are represented by １ ~Rx ３ The ring formed by the bonding of these two elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0209] 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. ３６It is also preferable that the atom is a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. ３８ R may bond with other substituents on the repeating main chain to form a ring. ３８ The group formed by the bonding of the repeating unit's main chain with another substituent is preferably an alkylene group such as a methylene group. When the composition of the present invention is, for example, an EUV lithography resist composition, R ３６ ~R ３８ A monovalent organic group represented by, and R ３７ and R ３８ The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0210] The base represented by formula (Y3-1) below is preferred for formula (Y3).

[0211]

[0212] Here, L Ｙ１ and L Ｙ２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). Ｙ１ This represents a single bond or a divalent linking group. Q Ｙ１ This represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which may contain a heteroatom such as a carbonyl group which may contain a heteroatom.Ｙ１ and L Ｙ２ Preferably, one of the groups is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group. Ｙ１ M Ｙ１ , and L Ｙ１ At least two of these may be joined to form a ring (preferably a five-membered or six-membered ring). In terms of pattern refinement, L Ｙ２ It is preferable that the group is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, which ensures film strength and suppresses fogging.

[0213] If the composition of the present invention is, for example, an EUV lithography resist composition, then L Ｙ１ and L Ｙ２ The alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by the above preferably also have a fluorine atom or an iodine atom as a substituent. In addition to fluorine atoms and iodine atoms, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups also preferably contain heteroatoms such as oxygen atoms. Specifically, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the composition of the present invention is, for example, an EUV lithography resist composition, Q Ｙ１ In alkyl groups, cycloalkyl groups, aryl groups, amino groups, ammonium groups, mercapto groups, cyano groups, aldehyde groups, and combinations thereof, which may contain heteroatoms, it is also preferable that the heteroatom is selected from the group consisting of fluorine, iodine, and oxygen atoms. In formula (Y3-1), * represents the bond position.

[0214] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. If the composition of the present invention is, for example, an EUV lithography resist composition, it is also preferable that the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0215] The resin (C) has a structure in which polar groups are protected by groups that are removed by the action of an acid, and it is preferable that the groups that are removed by the action of an acid are represented by the following formula (Y10) or (Y20). Formula (Y10): -C(Rx １０ ) (Rx ２０ ) (Rx ３０ ) Formula (Y20): -C(=O)OC(Rx １０ ) (Rx ２０ ) (Rx ３０ In equations (Y10) and (Y20), Rx １０ ~Rx ３０ Each of these independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, Rx １０ ~Rx ３０ Two of them are joined together to form a monoring.

[0216] From the standpoint of excellent acid decomposition properties of repeating units, in a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0217] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0218] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (HA) is also preferred.

[0219]

[0220] L １Ｈ R represents a divalent linking group which may have a fluorine atom or an iodine atom. １Ｈ R represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. ２Ｈ This represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. However, L １Ｈ , R １Ｈ , and R ２Ｈ At least one of them has a fluorine atom or an iodine atom. １Ｈ Divalent linking groups that may have a fluorine atom or an iodine atom, represented by -CO-, -O-, -S-, -SO-, -SO ２ - Hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linked groups formed by linking multiple thereof. Among these, L １Ｈ The alkylene group is preferably -CO-, an arylene group, or an -arylene group-an alkylene group having a fluorine or iodine atom, and more preferably -CO-, or an -arylene group-an alkylene group having a fluorine or iodine atom. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine and iodine atoms in the alkylene group having a fluorine or iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0221] R １ＨThe alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. １Ｈ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １Ｈ The alkyl group represented by may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0222] R ２Ｈ Examples of leaving groups that may have a fluorine atom or an iodine atom, as represented by the formulas (Y1) to (Y4) above, include the leaving groups that may have a fluorine atom or an iodine atom.

[0223] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0224]

[0225] In equation (AI), Xa １ Rx represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. １ ~Rx ３ Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, Rx 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. １ ~Rx ３ These two may combine to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0226] Xa １ Examples of alkyl groups that may have substituents, represented by , include a methyl group or -CH ２ -R １１The group represented by R is an example. １１ R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. １ Preferably, the group is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0227] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ - group, -(CH ２ ) ２ - group, or - (CH ２ ) ３ - The base is more preferable.

[0228] Rx １ ~Rx ３ Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ The preferred cycloalkyl group is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. １ ~Rx ３ The cycloalkyl group may be a cycloalkyl group having 3 to 20 carbon atoms. Rx １ ~Rx ３The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by vinylene groups. The repeating unit represented by formula (AI) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group.

[0229] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0230] The repeating unit represented by formula (AI) is an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (Xa １ A repeating unit in which represents a hydrogen atom or a methyl group, and T represents a single bond, is preferred.

[0231] Specific examples of repeating units having an acid-degradable group are shown below, but are not limited to these. In the formula, Xa １ H, CH３ CF ３ , or CH ２ Rxa and Rxb represent OH groups, and each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0232]

[0233] The resin (C) may have repeating units having acid-degradable groups, specifically repeating units having acid-degradable groups containing unsaturated bonds. The repeating units having acid-degradable groups containing unsaturated bonds are preferably those represented by the formula (HB).

[0234]

[0235] In formula (HB), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. １ ~Ry ３ Each of these independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, Ry １ ~Ry ３ At least one of these represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ These two may combine to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.) structure.

[0236] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or -CH ２ -R １１ The group represented by R is an example. １１represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. For example, it includes an alkyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, and an alkoxy group having 5 or fewer carbon atoms which may be substituted by a halogen atom. An alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0237] As the divalent linking group of L, a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and an -O-Rt- group can be mentioned. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferred. As L, a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group is preferred. Rt may have substituents such as a halogen atom, a hydroxyl group, and an alkoxy group.

[0238] Ry １ ~Ry ３ As the alkyl group of, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group, etc., alkyl groups having 1 to 4 carbon atoms are preferred. Ry １ ~Ry ３ As the cycloalkyl group of Ry, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferred. Ry １ ~Ry ３ The cycloalkyl group of Ry may be a cycloalkyl group having 3 to 20 carbon atoms. Ry １ ~Ry ３ As the aryl group of Ry, an aryl group having 6 to 10 carbon atoms is preferred. For example, a phenyl group, a naphthyl group, and an anthryl group can be mentioned. Ry １ ~Ry ３ [[ID=2X]] As the alkenyl group of Ry, a vinyl group is preferred. Ry １ ~Ry ３As the alkynyl group, an ethynyl group is preferred. Ry １ ~Ry ３ As the cycloalkenyl group of Ry １ ~Ry ３ , a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred. Ry １ ~Ry ３ As the cycloalkyl group formed by bonding two of Ry １ ~Ry ３ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Ry １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of Ry ２ ~Ry ３ may be replaced, for example, by a heteroatom such as an oxygen atom, a carbonyl group, a -SO ２ - group and a -SO ３ - group, a vinylidene group, or a combination thereof, in one of the methylene groups constituting the ring. Further, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring in these cycloalkyl groups or cycloalkenyl groups may be replaced by a vinylene group. The repeating unit represented by the formula (HB) is, for example, a case where Ry １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group, which is preferred.

[0239] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0240] ​​​​​​​​​​The repeating units represented by formula (HB) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0241] The content of repeating units having an acid-degradable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (C). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (C). Specific examples of repeating units having an acid-degradable group containing an unsaturated bond include, for example, the repeating units described in

[0067] to

[0071] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0242] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (C). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (C).

[0243] The resin (C) may contain at least one repeating unit selected from the group consisting of Group A below, and / or at least one repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the repeating units (20) to (25) below. (20) A repeating unit having an acid group (21) A repeating unit having neither an acid-degradable group nor an acid group, but having a fluorine atom, a bromine atom, or an iodine atom (22) A repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (23) A repeating unit having a photoacid-generating group (24) A repeating unit represented by formula (V-1) or formula (V-2) (25) A repeating unit for reducing the mobility of the main chain Note that the repeating units represented by formulas (A) to (E), described later, correspond to (25) the repeating unit for reducing the mobility of the main chain. Group B: A group consisting of the repeating units (30) to (32) below. (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group

[0244] The resin (C) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When the resin (C) has acidic groups, the interaction between the resin (C) and the acid generated from the photoacid generator is improved. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0245] Resin (C) may have at least one repeating unit selected from the group consisting of A above. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (C) has at least one repeating unit selected from the group consisting of A above. Resin (C) may contain at least one of a fluorine atom and an iodine atom. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (C) contains at least one of a fluorine atom and an iodine atom. If resin (C) contains both a fluorine atom and an iodine atom, resin (C) may have one repeating unit containing both a fluorine atom and an iodine atom, or resin (C) may contain two types: a repeating unit having a fluorine atom and a repeating unit containing an iodine atom. Resin (C) may have a repeating unit having an aromatic group. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that resin (C) has a repeating unit having an aromatic group. Resin (C) may have at least one repeating unit selected from the group consisting of group B described above. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (C) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (C) does not contain either a fluorine atom or a silicon atom. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (C) does not have an aromatic group.

[0246] (Repeating units having acid groups) The resin (C) may have repeating units having acid groups. Preferred acid groups have a pKa of 13 or less. The acid dissociation constant of the above acid groups is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the resin (C) has acid groups with a pKa of 13 or less, the content of acid groups in the resin (C) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the content of acid groups is within the above range, development proceeds well, the pattern shape formed is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. The above hexafluoroisopropanol group may have one or more (preferably one to two) fluorine atoms substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As the acid group, the -C(CF) formed in this way may be used. ３ ) (OH)-CF ２ - is also preferable. In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom, -C(CF ３ ) (OH)-CF ２ A ring containing a - may be formed. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which a polar group is protected by a group that is eliminated by the action of the acid described above, and the repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group, which will be described later. The repeating unit having an acidic group may have a fluorine atom or an iodine atom. Specific examples of repeating units having an acidic group include, for example, the repeating units described in

[0088] to

[0089] and

[0103] to

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

[0247] As a repeating unit having an acidic group, the repeating unit represented by the following formula (b1-1) is preferred.

[0248]

[0249] In formula (b1-1), A ａ１ R represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. ２１ R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. ２１ If they have R, they may form a ring together. ２１ A hydrogen atom is preferred. 'a' represents an integer from 1 to 3. 'b' represents an integer from 0 to (5-a).

[0250] When resin (C) contains repeating units having acidic groups, the content of repeating units having acidic groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (C). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (C).

[0251] (Repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom) Resin (C) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units that have an acid-degradable group> and <repeating units that have an acid group> described above. It is preferable that the <repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units that have at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group> and the <repeating units that have a photoacid generating group> described later.

[0252] As the unit X, a repeating unit represented by formula (HC) is preferred.

[0253]

[0254] L ５ R represents a single bond or an ester group. ９ R represents an alkyl group which may have a hydrogen atom, or a fluorine atom or an iodine atom. １０ This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof. Specific examples of repeating units having a fluorine atom or an iodine atom include, for example, the repeating units described in

[0116] to

[0117] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0255] The content of unit X is 0 mol% or more, may be 5 mol% or more, or may be 10 mol% or more, relative to the total repeating units in resin (C). Furthermore, the upper limit may be 50 mol% or less, 45 mol% or less, or 40 mol% or less, relative to the total repeating units in resin (C).

[0256] The total content of repeating units in resin (C) that contain at least one of a fluorine atom, a bromine atom, and an iodine atom may be 10 mol% or more, 20 mol% or more, 30 mol% or more, or 40 mol% or more, relative to the total repeating units of resin (C). There is no particular upper limit, and it is 100 mol% or less, relative to the total repeating units of resin (C). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.

[0257] (Repeating unit having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups) The resin (C) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0258] A lactone group only needs to have a lactone structure. A 5- to 7-membered ring lactone structure is preferred. Among these, a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo or spiro structure is more preferred. A sultone group only needs to have a sultone structure. A 5- to 7-membered ring sultone structure is preferred. Among these, a 5- to 7-membered ring sultone structure in which another ring structure is fused to form a bicyclo or spiro structure is more preferred. Examples of lactone groups include those 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). Examples of sultone groups include those obtained by removing one or more hydrogen atoms from the ring member atoms of a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3). Examples of carbonate groups include carbonate groups obtained by removing one or more hydrogen atoms from the ring member atoms of a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2). The lactone group, sultone group, and carbonate group may be directly bonded to the main chain of the resin (C). For example, the ring member atoms of the lactone group, sultone group, and carbonate group may constitute the main chain of the resin (C). The lactone group, sultone group, and carbonate group may have substituents.

[0259] 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. ＬExamples include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. If there are multiple e1s, they may be the same or different. If e1 is 2 or more, there may be multiple R Ｌ The Rs may be the same or different, and there may be multiple Rs. Ｌ They may join together to form a ring.

[0260]

[0261] As an example of the unit Y, a repeating unit represented by the following formula (AI-2) can be cited.

[0262]

[0263] 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 represented by Rb may have substituents. ０ The substituents that the alkyl group represented by Rb may have include a hydroxyl group and a halogen atom. ０ Examples of halogen atoms represented by Rb 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, a carboxyl 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 １is 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).

[0264] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0265] A cyclic carbonate ester group is preferred as the carbonate group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in

[0127] to

[0133] of International Publication No. 2022 / 024928. The above description is incorporated herein by reference.

[0266] If the resin (C) contains unit Y, the content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in the resin (C). Furthermore, the content of unit Y is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in the resin (C).

[0267] (Repeating units having photoacid generating groups) The resin (C) may have repeating units other than those described above, which have groups that generate acid upon irradiation with active light or radiation (also called "photoacid generating groups"). An example of a repeating unit having a photoacid generating group is the repeating unit represented by formula (4).

[0268]

[0269] 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. Specific examples of repeating units having photoacid-generating groups include, for example, the repeating units described in

[0094] to

[0105] of Japanese Patent Application 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 description is incorporated herein by reference.

[0270] 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.

[0271] When resin (C) contains repeating units having photoacid generating groups, the content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (C). Furthermore, the content of repeating units having photoacid generating groups is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (C).

[0272] (Repeating units represented by formula (V-1) or formula (V-2)) The resin (C) may have repeating units represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating units represented by the following formula (V-1) and formula (V-2) are different from the repeating units described above.

[0273]

[0274] In the formula, 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 This is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are given below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

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

[0275] (Repeating units to reduce the mobility of the main chain) The resin (C) is preferably given a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern breakdown during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or less, and more preferably 350°C or less. In this specification, the glass transition temperature (Tg) of polymers such as resin (C) 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.).

[0276] To increase the Tg of resin (C) (preferably to have a Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (C). Methods for reducing the mobility of the main chain of resin (C) include the following (a) to (e): (a) Introduction of bulky substituents to the main chain (b) Introduction of multiple substituents to the main chain (c) Introduction of substituents that induce interactions between resins (C) near the main chain (d) Formation of a main chain in a cyclic structure (e) Linking of a cyclic structure to the main chain The resin (C) may have repeating units in which the homopolymer Tg is 130°C or higher. The type of repeating unit in which the homopolymer Tg is 130°C or higher is not particularly limited, and any repeating unit in which the homopolymer Tg calculated by the Bicerano method is 130°C or higher is acceptable. Depending on the type of functional group in the repeating unit represented by formulas (A) to (E) described later, it may also correspond to a repeating unit in which the homopolymer Tg is 130°C or higher.

[0277] One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into the resin (C).

[0278]

[0279] Formula (A), R Ａ R represents a group containing a polycyclic structure. ｘ represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, which may or may not be fused. Specific examples of repeating units represented by formula (A) are those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0280] One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into the resin (C).

[0281]

[0282] In formula (B), R ｂ１ ~R ｂ４ Each of these independently represents a hydrogen atom or an organic group, R ｂ１ ~R ｂ４At least two of these represent organic groups. If at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of the other organic groups are not particularly limited. If none of the organic groups are groups in which a ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Specific examples of repeating units represented by formula (B) are those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0283] One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into the resin (C).

[0284]

[0285] In formula (C), R ｃ１ ~R ｃ４ Each of these independently represents a hydrogen atom or an organic group, R ｃ１ ~R ｃ４ At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. In particular, it is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of the resin (C). Specific examples of repeating units represented by formula (C) are those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0286] One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into the resin (C).

[0287]

[0288] In formula (D), "Cyclic" represents a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Specific examples of repeating units represented by formula (D) are those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0289] One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into the resin (C).

[0290]

[0291] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents. "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms in the cyclic group is not particularly limited. Specific examples of repeating units represented by formula (E) are those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0292] (Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (C) 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 the resin (C) include the repeating units described above in <Repeating units having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups>. The preferred content is also as described above in <Repeating units having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups>.

[0293] The resin (C) 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.

[0294] The resin (C) 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 (C) increases the resolution 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.

[0295] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) The resin (C) 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, or cyclohexyl (meth)acrylate.

[0296] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) The resin (C) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0297]

[0298] 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.

[0299] (Other Repeating Units) Furthermore, resin (C) may have other repeating units besides those described above. For example, resin (C) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0300] In addition to the repeating units described above, the resin (C) may have various repeating units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0301] As for the resin (C), in particular when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0302] Resin (C) can be synthesized according to conventional methods (e.g., radical polymerization). As polystyrene equivalent values ​​by the GPC method, the weight-average molecular weight (Mw) of resin (C) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Mw / Mn) of resin (C) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0303] The content of resin (C) in the composition of the present invention is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 99.9% 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. The composition of the present invention may contain one type of resin (C) or two or more types. If the composition of the present invention contains two or more types of resin (C), it is preferable that their total content is within the range of the above preferred content.

[0304] [Acid Diffusion Control Agent] The composition of the present invention may further contain an acid diffusion control agent (also called "compound (D)") different from compound (A). The acid diffusion control agent can act as a quencher to trap the acid generated from a photoacid generator such as compound (B) during exposure, and to suppress the reaction of the resin, whose polarity increases due to the action of the acid in the unexposed areas, caused by the excess generated acid. Compound (D) may be in the form of a low molecular weight compound or a high molecular weight compound. In addition, compound (D) may be in the form of a low molecular weight compound and a high molecular weight compound in combination. When compound (D) is in the form of a low molecular weight compound, the molecular weight of compound (D) is preferably 3000 or less, and more preferably 2000 or less. The lower limit of the molecular weight of compound (D) is not particularly limited, but for example it may be 100 or more. When compound (D) is in the form of a high molecular weight compound, compound (D) and resin (C) may be the same compound, or compound (D) may be a high molecular weight compound different from resin (C). Compound (D) is preferably in the form of a low molecular weight compound.

[0305] 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 an 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 the photoacid generator, and basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation. 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] of International Publication No. 2020 / 066824 and those described in 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) of acids that are relatively weak acids with respect to the acid generated from the photoacid generator include, for example, those described in paragraphs

[0305] to

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

[0306] 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.

[0307] When the composition of the present invention contains compound (D), the content of compound (D) is not particularly limited, but is preferably 0.01 to 30.0% by mass, more preferably 0.05 to 20.0% by mass, and even more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention. Compound (D) may be used alone or in combination of two or more types. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0308] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin different from resin (C) (also referred to as "hydrophobic resin (E)"). The hydrophobic resin (E) 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. Effects of adding the hydrophobic resin (E) include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.

[0309] Hydrophobic resin (E) is characterized by its uneven distribution on the film surface, and contains fluorine atoms, silicon atoms, and CH4 in the side chain portion of the resin. ３ It is preferable that the hydrophobic resin has 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 the hydrophobic resin (E) include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0310] When the composition of the present invention contains a hydrophobic resin (E), the content of the hydrophobic resin (E) is not particularly limited, but is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention. The hydrophobic resin (E) may be used alone or in combination of two or more types. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0311] [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.

[0312] Surfactants may be used individually or in combination of two or more types.

[0313] When the composition of the present invention contains a surfactant, the surfactant content is not particularly limited, but 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, relative to the total solid content of the composition of the present invention. The surfactant may be used alone 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.

[0314] [Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0315] Combining the solvent and resin described above 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 solvent described above has a good balance of solubility, boiling point and viscosity with the resin described above, 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.

[0316] 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.

[0317] The solvent content in the composition of the present invention is not particularly limited, but it is preferable to set it so that the solid content concentration in the composition of the present invention is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the applicability of the composition of the present invention.

[0318] [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).

[0319] The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developing solutions.

[0320] <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 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.

[0321] (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.

[0322] 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.

[0323] 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 undercoats (inorganic films, organic films, anti-reflective films) may be formed in the layer below the resist film.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] (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 being particularly preferred. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include an excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0328] 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. 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.

[0329] (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).

[0330] 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.

[0331] 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.

[0332] 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.

[0333] 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.

[0334] The following embodiments (OD1) and (OD2) are preferred embodiments of the organic developer: (OD1) An embodiment in which the organic developer is n-butyl acetate (OD2) An embodiment in which the organic developer is a mixed solvent of n-butyl acetate and a hydrocarbon having 11 or more carbon atoms The mixed solvent of (OD2) described above is also called the mixed solvent (OD2). The hydrocarbon having 11 or more carbon atoms in the mixed solvent (OD2) is preferably an alkane, more preferably an alkane having 11 to 15 carbon atoms, even more preferably an alkane having 11 to 13 carbon atoms, particularly preferably undecane or dodecane, and most preferably undecane. If structural isomers exist for the hydrocarbon having 11 or more carbon atoms, such as undecane or dodecane, the mixed solvent (OD2) may contain only one type of hydrocarbon having 11 or more carbon atoms, or two or more types. The content of hydrocarbons having 11 or more carbon atoms in the mixed solvent (OD2) (or the total amount if multiple types of hydrocarbons having 11 or more carbon atoms are included) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire mixed solvent (OD2).

[0335] The content of n-butyl acetate in the mixed solvent (OD2) is preferably 65% ​​to 99% by mass, more preferably 70% to 95% by mass, and even more preferably 75% to 90% by mass, based on 100% by mass of the entire mixed solvent (OD2).

[0336] A particularly preferred embodiment of the mixed solvent (OD2) is one in which n-butyl acetate and undecane are contained, and the mass ratio of "n-butyl acetate / undecane" is "90 / 10".

[0337] The developer may contain other components in addition to the components described above. Examples of other components include surfactants, antioxidants, and basic compounds. The content of other components in the developer is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, even more preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass (i.e., no other components are present), based on 100% by mass of the entire developer.

[0338] (Other steps) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0339] 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.

[0340] 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.

[0341] 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).

[0342] 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.

[0343] The various materials used in the compositions and pattern forming methods of the present invention (for example, solvents, developers, rinse solutions, 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 billion) or less, particularly preferably 10 ppt (parts per billion) or less, and most preferably 1 ppt (parts per billion) or less. There is no particular lower limit, but 0 ppt (parts per billion) 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.

[0344] 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.

[0345] 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).

[0346] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the manufacturing equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred.

[0347] For organic treatment liquids such as rinsing liquids, a conductive compound may be added to prevent failures of chemical liquid pipes and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, and for example, methanol can be mentioned. The addition amount is not particularly limited, but in terms of maintaining preferable development characteristics or rinsing characteristics, 10% by mass or less is preferable, and 5% by mass or less is more preferable. The lower limit is not particularly restricted, and 0.01% by mass or more is preferable. As the chemical liquid pipe, for example, various pipes coated with SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to an antistatic treatment can be used. Similarly, regarding filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to an antistatic treatment can be used.

[0348] <Method for manufacturing an electronic device> The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method. A preferable embodiment of the electronic device of the present invention includes an embodiment mounted on electric and electronic devices (home appliances, OA (Office Automation), media-related devices, optical devices, communication devices, etc.).

[0349] <Compound> The present invention also relates to a compound represented by the following formula (1).

[0350]

[0351] In formula (1), Z ＋ represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-b). However, the molecular volume of A-H formed by adding a proton to A － is 310 Å ３ or more.

[0352]

[0353] In formula (1-b), X represents a halogen atom. L １L represents a divalent linking group. ２ Y represents a divalent hydrocarbon group which may contain heteroatoms. Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or hydrogen atom. ２ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of may be joined to form a ring. m and n each independently represent integers from 1 to 4, and the sum of m and n is 5 or less. If there are multiple X's, they may be the same or different. L １ If there are multiple L １ They may be the same or different. L ２ If there are multiple L ２ They may be the same or different. Y Ｎ１ If there are multiple Y Ｎ１ They may be the same or different. Y Ｎ２ If there are multiple Y Ｎ２ They may be the same or different. However, the monovalent anion represented by the above formula (1-b) satisfies at least one of the following (iii) and (iv). (iii) Y Ｎ１ and Y Ｎ２ The pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which the compound is bonded is 1 or greater. (iv) Y Ｎ１ and Y Ｎ２ At least one of these groups represents a group that is eliminated by the action of an acid, and the pKa of the conjugate acid formed when the group eliminated by the action of the acid is eliminated and a proton is added to the nitrogen atom to which a hydrogen atom is bonded is 1 or greater.

[0354] Z in equation (1) ＋ and A － The explanation, specific examples, and preferred ranges are the same as those described above. X, L in formula (1-b) １ The explanations, specific examples, and preferred ranges of m and n are given by X and L in formula (1-a) above, respectively. １ , is the same as in m and n. L in equation (1-b) ２ , Y Ｎ１ and Y Ｎ２The explanation, specific examples, and preferred ranges are given by L in formula (N-1) mentioned above. ２ , Y Ｎ１ and Y Ｎ２ It is the same as the one in [location].

[0355] The present invention also relates to a photosensitive or radiation-sensitive resin composition containing a compound (A) represented by the following formula (1), a photoacid generator (B) different from compound (A), and a resin (C).

[0356]

[0357] In formula (1), Z ＋ This represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-a). However, A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That's all.

[0358]

[0359] In formula (1-a), X represents a halogen atom. １ R represents a divalent linking group. Ｎ X represents a group containing at least one nitrogen atom, provided that the nitrogen atom is not bonded to a sulfonyl group. Furthermore, the nitrogen atom is not bonded to an aromatic ring to which a halogen atom is bonded. m and n each independently represent integers from 1 to 4, and the sum of m and n is 5 or less. If multiple X values ​​exist, they may be the same or different. L １ If there are multiple L １ They may be the same or different. Ｎ If multiple R Ｎ They may be the same or different.

[0360] Z in equation (1) ＋ and A － The explanation, specific examples, and preferred ranges are the same as those described above. X, R in equation (1-a) Ｎ , L １The descriptions, specific examples, and preferred ranges of m and n are the same as those described above. Furthermore, the descriptions, specific examples, and preferred ranges of components other than compound (A) contained in the photosensitive or radiation-sensitive resin composition are the same as those described above.

[0361] 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.

[0362] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0363] <Compound (A) and Comparative Compounds> Compounds A-1 to A-15 are used as Compound (A). Z-1 to Z-3 are used as comparative compounds. However, in Tables 3 and 7 below, Z-1 to Z-3 are listed in the "Compound (A)" column for convenience.

[0364]

[0365]

[0366] For each of the anions contained in A-1 to A-15 and Z-1 to Z-3, the molecular volume (Å) of the compound obtained by adding a proton to the anion is given. ３The values ​​are shown in Table 1 below. The molecular volume is the value calculated using the EF (Eigen Vector Following) method with the PM3 Hamiltonian implemented in MOPAC7 included with Winmostar v11.7.4, and is the value obtained during structural optimization. For the anions contained in A-1, A-5, A-7, A-8, A-10, A-12, A-14, and Z-1 to Z-3, the pKa of the conjugate acid formed by adding a proton to the nitrogen atom contained in the anion is shown in Table 1 below. Also, for the anions contained in A-2 to A-4, A-6, A-9, A-11, A-13, and A-15, the pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which a hydrogen atom is bonded after the group that is removed by the action of the acid contained in the anion is removed is shown in Table 1 below. The pKa of the conjugate acid is determined using "Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)".

[0367]

[0368] An example of the synthesis of compound (A) is shown below.

[0369] (Synthesis of A-1)

[0370]

[0371] In a three-necked flask, under a nitrogen atmosphere, 80.0 g of A-1-(I) (synthesized according to the method described in WO2024 / 185543) and 960 mL of acetonitrile were mixed. After cooling the reaction mixture to below 10°C, 89.0 g of isobutyl pentafluorobenzenesulfonate and 114.5 g of cesium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at room temperature (23°C) for 48 hours. The reaction mixture was filtered, and 400 mL of ethyl acetate and 200 mL of 10% aqueous ammonium chloride solution were added to the filtrate. The aqueous layer was removed using a separatory funnel. The resulting organic layer was washed three times with distilled water and then concentrated under reduced pressure. The mixture was purified by silica gel column chromatography using hexane / ethyl acetate as the eluent to obtain 14.4 g of A-1-(II). In a three-necked flask under a nitrogen atmosphere, 14.0 g of A-1-(II), 98 mL of acetonitrile, and 4.1 g of sodium iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and stirred at 50°C for 3 hours. After concentrating the reaction mixture under reduced pressure, 100 mL of methylene chloride and 80 mL of saturated saline solution were added, and the aqueous layer was removed using a separatory funnel. The resulting organic layer was concentrated under reduced pressure to obtain 11.4 g of A-1-(III). In a three-necked flask under a nitrogen atmosphere, 11.2 g of A-1-(III), 7.7 g of triphenylsulfonium bromide, 640 mL of methylene chloride, and 640 mL of distilled water were mixed and stirred at 25°C for 1 hour. After removing the aqueous layer using a separatory funnel, the organic layer was washed with distilled water. The washed organic layer was concentrated under reduced pressure to obtain 11.4 g of A-1. Identification of the obtained A-1 is as follows: １ H-NMR (nuclear magnetic resonance) and １９ This was performed using F-NMR. １ H-NMR (400 MHz, CDCl ３ )d = 1.23 (t, 3H), 1.30 (t, 3H), 1.72-1.95 (m, 4H), 2.30-2.39 (m, 1H), 2,58-2.66 (m, 2H), 2.73-2.86 (m, 2H) ), 2.94-3.00 (m, 1H), 3.73-3.77 (m, 1H), 4.12-4.25 (m, 4H), 4.27-4.34 (m, 1H), 7.68-7.83 (m, 15H) ppm １９ F-NMR (376.6 MHz, CDCl ３) d=-156.8, -139.8 ppm

[0372] (Composition of A-2)

[0373]

[0374] In a three-necked flask under a nitrogen atmosphere, 15.9 g of N-cyclohexylethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 mL of acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 30 mL of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and cooled to 5°C. A mixture of 24.9 g of di-tert-amyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 mL of acetonitrile was added dropwise, and the temperature was raised to 25°C and stirred for 4 hours. 250 mL of ethyl acetate and 150 mL of 0.5 mol / L HCl were added to the reaction mixture, and the aqueous layer was removed using a separatory funnel. The resulting organic layer was washed twice with 150 mL of distilled water. The washed organic layer was concentrated under reduced pressure to obtain 25.3 g of A-2-(I). In a three-necked flask, under a nitrogen atmosphere, 16.9 g of A-2-(I), 20.0 g of isobutyl pentafluorobenzenesulfonate, and 280 mL of acetonitrile were mixed and cooled to 5°C. 64.3 g of cesium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to 65°C and stirred for 2 hours. After cooling to 30°C, 600 mL of distilled water and 600 mL of ethyl acetate were added, and the aqueous layer was removed using a separatory funnel. The resulting organic layer was washed twice with 600 mL of distilled water and once with 600 mL of saturated brine. The washed organic layer was concentrated under reduced pressure and purified by silica gel column chromatography using hexane and ethyl acetate as the eluents to obtain 7.6 g of A-2-(II). In a three-necked flask, under a nitrogen atmosphere, 6.5 g of A-2-(II), 33 mL of acetonitrile, and 2.0 g of sodium iodide were mixed and stirred at 50°C for 3 hours. After cooling the reaction mixture to 5°C, 35 mL of diisopropyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and the mixture was stirred for 10 minutes. The precipitated solid was filtered to obtain 5.9 g of A-2-(III). In a three-necked flask under a nitrogen atmosphere, 4.5 g of A-2-(III), 3.2 g of triphenylsulfonium bromide, 45 mL of methylene chloride, and 45 mL of distilled water were mixed and stirred at 25°C for 1 hour. After removing the aqueous layer with a separatory funnel, the organic layer was washed with distilled water. The washed organic layer was concentrated under reduced pressure to obtain 7.0 g of A-2. Identification of the obtained A-2 is as follows: １ H-NMR (nuclear magnetic resonance) and １９ This was performed using F-NMR. １H-NMR (400 MHz, acetone-d6) d = 0.85-0.94 (br, 3H), 1.09-1.20 (m, 1H), 1.28-1.38 (br, 2H), 1.42 (br s, 6H), 1.51-1.64 (br, 3H), 1.69-1.82 (m, 6H), 3.53-3.57 (m, 2H), 3.64-3.90 (m, 1H), 4.30 (br s, 2H), 7.84-7.99 (m, 15H) ppm １９ F-NMR (376.6 MHz, acetone-d6) d=-160.0, -140.7 ppm

[0375] A-3 to A-15 can be synthesized according to the synthesis method of A-1 and A-2.

[0376] <Compound (B)> Compound (B) (a photoacid generator different from compound (A)) is used, consisting of B-1 to B-18. Me represents a methyl group.

[0377]

[0378]

[0379]

[0380] <Resin (C)> C-1 to C-26 are used as resin (C) (resins whose polarity increases with the action of acid). The structural formulas and content (mol%) of each repeating unit contained in C-1 to C-26, the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of C-1 to C-26 are shown below. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to the total repeating units contained in each resin. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). In addition, the content of the repeating units is, １３ Measurement is performed using C-NMR (nuclear magnetic resonance).

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388] <Compound (D)> Compounds (D) (different acid diffusion control agents from compound (A)) are used, specifically D-1 to D-14.

[0389]

[0390]

[0391] <Hydrophobic Resins> E-1 to E-12 are used as hydrophobic resins. The structural formulas and content (mol%) of each repeating unit contained in E-1 to E-12, as well as the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of E-1 to E-12 are shown below. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to the total repeating units contained in each resin. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resins are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). In addition, the content of the repeating units is, １３ Measurement is performed using C-NMR.

[0392]

[0393]

[0394]

[0395] <Surfactant> F-1 is used as the surfactant. F-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0396] <Solvents> The solvents to be used are as follows: G-1: Propylene glycol monomethyl ether acetate (PGMEA) G-2: Propylene glycol monomethyl ether (PGME) G-3: γ-butyrolactone G-4: Ethyl lactate G-5: Cyclohexanone G-6: 2-heptanone

[0397] (ArF exposure) <Preparation and storage of resist compositions> Dissolve the components shown in Tables 2 and 3 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 0.03 μm to prepare the resist compositions (Re-1 to Re-42, Re-C1 to Re-C6). Solid content refers to all components other than the solvent. In the tables, the "mass%" column indicates the content (mass%) of each component relative to the total solid content in the resist composition. When two or more types of components are used, the types and their contents are separated by " / ". The order in which the types and contents separated by " / " are listed corresponds. When two or more types of solvents are used, the types and their mixing ratios (mass-based ratios when the total solvent is set to 100) are separated by " / ". The order in which the types and mixing ratios separated by " / " are listed corresponds. For convenience, when using only one solvent, "100" was written in the mixing ratio column. Each resulting resist composition was stored at 4°C for 6 months.

[0398]

[0399]

[0400] <Pattern Formation Method (1): ArF Exposure, Alkaline Development (Positive)> An organic anti-reflective film ARC29SR (manufactured by Brewer) is applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 95 nm. On top of the anti-reflective film, each resist composition shown in Table 4 below, after being stored at 4°C for 6 months, is applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 85 nm. An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20) is used to expose the wafer through a 6% halftone mask of a 1:1 line-and-space pattern with a line width of 60 nm. Ultrapure water is used as the immersion solution. The exposed resist film is baked at 95°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. Afterward, this is spin-dried to obtain a positive-type pattern.

[0401] <Performance Evaluation> [LWR over time] A pattern is formed using the exposure amount (optimal exposure amount) required to resolve a 1:1 line-and-space pattern with a line width of 60 nm. The above pattern is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi CG-4100)). The line width is observed at 50 arbitrary locations, and its standard deviation (σ) is determined. The measurement variability of the line width is evaluated using 3σ, and the value of 3σ is taken as the LWR (nm) over time. A smaller LWR value over time indicates better performance. A LWR of 4.4 (nm) or less is preferable. (Evaluation Criteria) A: LWR after time ≤ 3.3 B: 3.3 < LWR after time ≤ 3.5 C: 3.5 < LWR after time ≤ 3.8 D: 3.8 < LWR after time ≤ 4.1 E: 4.1 < LWR after time ≤ 4.4 F: 4.4 < LWR after time

[0402] [Evaluation of Pattern Shape After Time (Part 1)] The resist patterns of each example and comparative example obtained by pattern formation method (1) are evaluated according to the following procedure. The cross-sectional shape of the line patterns of each example and comparative example with an average line width of 60 nm is observed using a scanning electron microscope (SEM (Hitachi, Ltd. CG-4100)), and the pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern are measured. The pattern shape (rectangularity of the cross-section) after time is evaluated using the Lb / La value as an indicator according to the following criteria. A is the best and F is the worst. (Evaluation criteria) A: 1.00≦(Lb / La)≦1.01 B: 1.01<(Lb / La)≦1.02 C: 1.02<(Lb / La)≦1.03 D: 1.03<(Lb / La)≦1.04 E: 1.04<(Lb / La)≦1.05 F:1.05<(Lb / La)

[0403] The results shown in Table 4 below are obtained.

[0404]

[0405] <Pattern Formation Method (2): ArF Exposure, Organic Solvent Development (Negative)> An organic anti-reflective film ARC29SR (manufactured by Brewer) is applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 95 nm. On top of the anti-reflective film, each resist composition shown in Table 5 below, after being stored at 4°C for 6 months, is applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 85 nm. An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20) is used to expose the wafer through a 6% halftone mask of a 1:1 line-and-space pattern with a line width of 60 nm. Ultrapure water is used as the immersion solution. The exposed resist film is heated at 95°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative-type pattern.

[0406] <Performance Evaluation> [LWR over time] The LWR over time is evaluated using the same method as in the pattern formation method (1) described above.

[0407] [Evaluation of Pattern Shape (Cross-sectional Rectangle) After Time (Part 2)] The resist patterns of each example and comparative example obtained by pattern formation method (2) are evaluated according to the following procedure. The values ​​of La and Lb are measured using the same procedure as shown in [Evaluation of Pattern Shape (Part 1)] above. The pattern shape (cross-sectional rectangularity) after time is evaluated according to the following criteria, using the La / Lb value as an indicator. A is the best and F is the worst. (Evaluation Criteria) A: 1.00 ≤ (La / Lb) ≤ 1.01 B: 1.01 < (La / Lb) ≤ 1.02 C: 1.02 < (La / Lb) ≤ 1.03 D: 1.03 < (La / Lb) ≤ 1.04 E: 1.04 < (La / Lb) ≤ 1.05 F: 1.05 < (La / Lb)

[0408] The results shown in Table 5 below are obtained.

[0409]

[0410] (EUV exposure) <Preparation and storage of resist compositions> The resist compositions (Re-43 to Re-74, Re-C7 to Re-C8) are prepared by mixing each component shown in Tables 6 and 7 so that the solid content concentration is 2.0% by mass, and filtering the resulting mixture in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm. Solid content refers to all components other than the solvent. In the tables, the "mass%" column indicates the content (mass%) of each component relative to the total solid content in the resist composition. When two or more types of components are used, the type and content are shown separated by " / ". The order in which the types and content separated by " / " are listed corresponds. When two or more types of solvents are used, the type and mixing ratio (mass-based ratio when the total solvent is 100) are shown separated by " / ". The order in which the types and mixing ratios separated by " / " are listed corresponds. For convenience, when using only one solvent, "100" was written in the mixing ratio column. Each resulting resist composition was stored at 4°C for 6 months.

[0411]

[0412]

[0413] <Pattern Formation Method (3): EUV Exposure, Alkali Development (Positive)> A base layer formation composition AL412 (manufactured by Brewer Science) is applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer with a thickness of 20 nm. On top of the base layer, each resist composition shown in Table 8 below, after being stored at 4°C for 6 months, is applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Pattern irradiation is performed on the silicon wafer with the resist film using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). As the reticle, a mask with a line size of 25 nm and a line:space ratio of 1:1 is used. The resist film after exposure is baked at 90°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it is spin-dried to obtain a positive-type pattern.

[0414] <Performance Evaluation> [LWR over time] A pattern is formed using the exposure amount (optimal exposure amount) required to resolve a 1:1 line-and-space pattern with a line width of 25 nm. The above pattern is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi Ltd. S-9380II)). The line width is observed at 50 locations, and its standard deviation (σ) is determined. The measurement variability of the line width is evaluated using 3σ, and the value of 3σ is taken as the LWR (nm) over time. A smaller LWR value over time indicates better performance. A LWR of 4.4 (nm) or less is preferable. (Evaluation Criteria) A: LWR after time ≤ 3.3 B: 3.3 < LWR after time ≤ 3.5 C: 3.5 < LWR after time ≤ 3.8 D: 3.8 < LWR after time ≤ 4.1 E: 4.1 < LWR after time ≤ 4.4 F: 4.4 < LWR after time

[0415] [Evaluation of Pattern Shape After Time (Part 3)] The resist patterns of each example and comparative example obtained by pattern formation method (3) are evaluated according to the following procedure. The cross-sectional shape of the line patterns of each example and comparative example with an average line width of 25 nm is observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), and the pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern are measured. The pattern shape (rectangularity of the cross-section) after time is evaluated using the Lb / La value as an indicator according to the following criteria. A is the best and F is the worst. (Evaluation criteria) A: 1.00≦(Lb / La)≦1.01 B: 1.01<(Lb / La)≦1.02 C: 1.02<(Lb / La)≦1.03 D: 1.03<(Lb / La)≦1.04 E: 1.04<(Lb / La)≦1.05 F:1.05<(Lb / La)

[0416] The results shown in Table 8 below are obtained.

[0417]

[0418] <Pattern Formation Method (4): EUV Exposure, Organic Solvent Development (Negative)> A base layer formation composition AL412 (manufactured by Brewer Science) is applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer with a thickness of 20 nm. On top of the base layer, each resist composition shown in Table 9 below, after being stored at 4°C for 6 months, is applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Pattern irradiation is performed on the silicon wafer having the obtained resist film using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). As the reticle, a mask with a line size of 25 nm and a line:space ratio of 1:1 is used. The resist film after exposure is baked at 90°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative-type pattern.

[0419] <Performance Evaluation> [LWR over time] The LWR over time is evaluated using the same method as in the pattern formation method (3) described above.

[0420] [Evaluation of Pattern Shape After Time (Part 4)] The resist patterns of each example and comparative example obtained by pattern formation method (4) are evaluated according to the following procedure. The values ​​of La and Lb are measured using the same procedure as shown in [Evaluation of Pattern Shape After Time (Part 3)] above. The pattern shape (rectangular cross-section) after time is evaluated according to the following criteria, using the La / Lb value as an indicator. A is the best and F is the worst. (Evaluation Criteria) A: 1.00 ≤ (La / Lb) ≤ 1.01 B: 1.01 < (La / Lb) ≤ 1.02 C: 1.02 < (La / Lb) ≤ 1.03 D: 1.03 < (La / Lb) ≤ 1.04 E: 1.04 < (La / Lb) ≤ 1.05 F: 1.05 < (La / Lb)

[0421] The results shown in Table 9 below are obtained.

[0422]

[0423] From the above, it can be seen that the resist composition of the embodiment of the present invention is excellent in terms of LWR after time and pattern shape after time.

[0424] The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits excellent LWR and pattern shape over time. Furthermore, the present invention provides a resist film formed using the above photosensitive or radiation-sensitive resin composition, a pattern formation method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Moreover, the present invention provides compounds that can be used in the above photosensitive or radiation-sensitive resin composition.

[0425] 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. 2024-206246, filed on 27 November 2024, the contents of which are incorporated herein by reference.

Claims

A photosensitive or radiation-sensitive resin composition comprising a compound (A) represented by the following formula (1), a photoacid generator (B) different from compound (A), and a resin (C). In formula (1), Z ＋ This represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-a). However, A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That's all. In formula (1-a), X represents a halogen atom. L １ This represents a divalent linking group. R Ｎ This represents a group containing at least one nitrogen atom. 　 m and n each represent an integer between 1 and 4, and the sum of m and n is 5 or less. If there are multiple instances of X, these instances of X may be the same or different. L １ If there are multiple L １ They may be the same or different. R Ｎ When there are a plurality of R's Ｎ they may be the same or different. However, the monovalent anion represented by formula (1-a) satisfies at least one of the following conditions (i) and (ii). (i) The R Ｎ The pKa of the conjugate acid, which is formed by adding a proton to at least one nitrogen atom contained in the compound, is 1 or greater. (ii) The above R Ｎ A group that is removed by the action of an acid is bonded to at least one nitrogen atom contained in the acid, and the pKa of the conjugate acid formed when the group that is removed by the action of the acid is removed and a proton is added to the nitrogen atom to which a hydrogen atom is bonded is 1 or more. The aforementioned R Ｎ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein is represented by the following formula (N-1). In formula (N-1), L ２ This represents a divalent hydrocarbon group which may contain a heteroatom. Y Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or a hydrogen atom. L ２ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of these elements may be joined together to form a ring. * is L １ This indicates the connection point with [the other element]. The aforementioned R Ｎ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein is represented by the following formula (N-2). In formula (N-2), L ２ This represents a divalent hydrocarbon group which may contain a heteroatom. Y Ｎ１ This represents a monovalent organic group or hydrogen atom. R １ , R ２ and R ３ Each of these independently represents a monovalent hydrocarbon group. L ２ and Y Ｎ１ They may combine to form a ring. * is L １ This indicates the connection point with [the other element]. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the benzene ring in formula (1-a) is not bonded to a group represented by the following formula (W-1). In formula (W-1), R ４ This represents a monovalent organic group. * １ The symbol () represents the bond position with the benzene ring in formula (1-a). 　 Y in the above formula (N-1) Ｎ１ and Y Ｎ２ The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the composition does not contain at least one selected from the group consisting of fluorine atoms and aromatic carbon rings. 　 -L in the above formula (1-a) １ -R Ｎ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the group represented by does not contain an aromatic ring. 　 -L in the above formula (1-a) １ -R Ｎ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the group represented by is the group represented by the following formula (Q-1). In formula (Q-1), L １１ is -O-, -S-, or -SO ２ It represents -. R １１ and R １２ Each of these independently represents a hydrogen atom or a substituent. １１ If multiple R １１ They may be the same or different. １２ If multiple R １２ They may be the same or different. L １２ is -O-, -CO-, * ２ -COO-* ３ , * ２ -OCO-* ３ -S-, -SO-, or -SO ２ It represents -. L １３ This represents a divalent hydrocarbon group. Y Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or a hydrogen atom. L １３ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of these elements may be joined together to form a ring. 　 k1 represents an integer greater than or equal to 1. k2 represents either 0 or 1. * １ The symbol () represents the bond position with the benzene ring in formula (1-a). * ２ CR １１ R １２ This indicates the bonding position with the carbon atoms inside. * ３ is L １３ This indicates the connection point with [the other element]. A － The molecular volume of A-H, formed by adding a proton to A, is 325 Å. ３ The above describes the photosensitive or radiation-sensitive resin composition according to claim 1. 　 The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (C) has a structure in which polar groups are protected by groups that are removed by the action of an acid, and the groups that are removed by the action of an acid are represented by the following formula (Y10) or (Y20). Formula (Y10): -C(Rx) １０ (Rx) ２０ (Rx) ３０ ) Formula (Y20): -C(=O)OC(Rx １０ )(Rx ２０ )(Rx ３０ ) In equations (Y10) and (Y20), Rx １０ ~Rx ３０ Each of these independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, Rx １０ ~Rx ３０ Two of them are joined together to form a monoring. 　 A resist film formed using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 9. 　 A method for forming a pattern, comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 9; exposing the resist film; and developing the exposed resist film using a developer. 　 A method for manufacturing an electronic device, comprising the pattern forming method described in claim 11. 　 A compound represented by the following formula (1). In formula (1), Z ＋ This represents a monovalent cation. A － represents a monovalent anion represented by the following formula (1-b). However, A － The molecular volume of A-H, formed by adding a proton to A, is 310 Å. ３ That's all. In formula (1-b), X represents a halogen atom. L １ This represents a divalent linking group. L ２ This represents a divalent hydrocarbon group which may contain a heteroatom. Y Ｎ１ and Y Ｎ２ Each of these independently represents a monovalent organic group or a hydrogen atom. L ２ , Y Ｎ１ and Y Ｎ２ At least two elements selected from the group consisting of these elements may be joined together to form a ring. 　 m and n each represent an integer between 1 and 4, and the sum of m and n is 5 or less. If there are multiple instances of X, these instances of X may be the same or different. L １ If there are multiple L １ They may be the same or different. L ２ If there are multiple Ls ２ they may be the same or different. Y Ｎ１ If there are multiple Y Ｎ１ They may be the same or different. Y Ｎ２ If there are multiple Y Ｎ２ They may be the same or different. However, the monovalent anion represented by formula (1-b) satisfies at least one of the following conditions (iii) and (iv). (iii) Y Ｎ１ and Y Ｎ２ The pKa of the conjugate acid, formed by adding a proton to the nitrogen atom to which the compound is bonded, is 1 or greater. (iv) Y Ｎ１ and Y Ｎ２ At least one of which represents a group that is eliminated by the action of an acid, and the pKa of the conjugate acid formed by adding a proton to the nitrogen atom to which a hydrogen atom is bonded after the group eliminated by the action of the acid is eliminated is 1 or more.

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