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

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing a compound including an organic anion and a cation having at least one group with a specific structure, and a resin; an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition; a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition; and a method for manufacturing an electronic device.

Description

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

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

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

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of active light or radiation are being developed.

[0004] Patent documents 1 and 2 describe resist compositions containing sulfonium salts having a specific structure.

[0005] Japanese Patent Publication No. 2023-169812 Japanese Patent Publication No. 2023-143838

[0006] Recently, the performance requirements for resist compositions have become increasingly stringent. In particular, further improvements are needed regarding line width roughness (LWR) when forming fine patterns. Furthermore, resist compositions are desired to exhibit no change in performance even after time has passed since exposure (for example, minimal influence on performance due to the time elapsed from exposure to post-exposure baking (PEB)), that is, excellent post-exposure time delay (PED) stability.

[0007] The present invention aims to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent LWR and PED stability. Furthermore, the present invention aims to provide a photosensitive or radiation-sensitive film formed from the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern-forming method using the above-mentioned photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

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

[0009] [1] A photosensitive or radiation-sensitive resin composition containing a compound (B) comprising an organic anion and a cation represented by the following formula (BC-1), and a resin.

[0010]

[0011] In formula (BC-1), Ar １ and Ar ２ Each of these independently represents an aromatic ring. １ and Ar ２ They may be joined together to form a ring. n represents an integer from 1 to 3. Ar １ If there are multiple Ar １ They may be the same or different from each other, and there may be multiple Ar １ They may bond to each other to form a ring. ２ If there are multiple Ar２ may be the same as or different from each other, and a plurality of Ar ２ may be bonded to each other to form a ring. R ｂ１ and R ｂ２ each independently represent a substituent. R ｂ１ and R ｂ２ may be bonded to each other to form a ring. k and m each independently represent an integer of 0 or more. When n represents 2 or 3, a plurality of k may be the same value or different values from each other. When n represents 1, a plurality of m may be the same value or different values from each other. When a plurality of R ｂ１ exist, the plurality of R ｂ１ may be the same as or different from each other, and a plurality of R ｂ１ may be bonded to each other to form a ring. When a plurality of R ｂ２ exist, the plurality of R ｂ２ may be the same as or different from each other, and a plurality of R ｂ２ may be bonded to each other to form a ring. Y ｂ１ represents a group represented by any one of the following formulas (Y-1) to (Y-4). When a plurality of Y ｂ１ exist, the plurality of Y ｂ１ may be the same as or different from each other. z represents an integer of 1 or more. When n represents 2 or 3, a plurality of z may be the same value or different values from each other.

[0012]

[0013] In formulas (Y-1) to (Y-4), * represents a bonding position. T １ and T ２ each independently represent a single bond or a divalent linking group. L １ is ＊１ -(C=O)O- ＊２ or -SO ２ -, and ＊１ represents the bonding position to an oxygen atom, ＊２ represents the bonding position to A １ . L ２ is ＊１ -(C=O)O- ＊２ or -SO ２ -. ＊１This indicates the bonding position with the oxygen atom. ＊２ is A ３ This indicates the connection position with A. １ Ha-CHR ｂ５ - or ＊３ -CR ｂ６ R ｂ７ C(=O)- ＊４ It represents. ＊３ is L １ This indicates the connection point with [the other element]. ＊４ Ar ３ Represents the connection position with R. ｂ５ and Ar ３ They may bond to each other to form a ring. ｂ６ or R ｂ７ and Ar ３ They may be joined to each other to form a ring. A ２ Ha-CR ｂ８ =CR ｂ９ - or -C≡C- represents R ｂ８ or R ｂ９ and Ar ４ They may be joined to each other to form a ring. ３ and Ar ４ Each of these independently represents an aromatic ring. A ３ Ha-CHR ｂ１０ - or ＊５ -CR ｂ１１ R ｂ１２ C(=O)- ＊６ It represents. ＊５ is L ２ This indicates the connection point with [the other element]. ＊６ Ar １ Represents the connection position with R. ｂ１０ and Ar １ They may bond to each other to form a ring. ｂ１１ or R ｂ１２ and Ar １ They may be joined to each other to form a ring. A ４ Ha-CR ｂ１３ =CR ｂ１４ - or -C≡C- represents R ｂ１３ or R ｂ１４ and Ar １ They may bond to each other to form a ring. ｂ３ and R ｂ４ Each of these independently represents a substituent. However, R ｂ３and R ｂ４ is not bonded to an adjacent oxygen atom and a tertiary carbon atom. R ｂ５ to R ｂ１４ each independently represent a hydrogen atom or a substituent. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin comprises a repeating unit having a phenolic hydroxyl group. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin comprises a repeating unit represented by the following formula (Ga1).

[0014]

[0015] In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ａ１ represents a single bond or a divalent linking group. X ａ１ represents -O- or -C(=O)O-. R ａ３ and L ａ１ may be bonded to each other to form a ring. G represents a group represented by the following formula (G-1) or (G-2).

[0016]

[0017] In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ５ and R ａ６ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ４ and R ａ５ may be bonded to each other to form a ring. R ａ４ and L in formula (Ga1) ａ１ may be bonded to each other to form a ring. * represents a bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. Rａ７ , R ａ８ and R ａ９ Two of them may bond to each other to form a ring. * indicates the bonding position. [4] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the above organic anion is an anion represented by the following formula (BA-1).

[0018]

[0019] In formula (BA-1), R Ｘ１ ' represents a substituent. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the above organic anion is at least one selected from the group consisting of anions represented by the following formula (BA-2) and anions represented by the following formula (BA-3).

[0020]

[0021] In formula (BA-2), R Ｘ２ represents a substituent. In formula (BA-3), L Ｘ１ These are single bonds, -(C=O)- or -SO ２ Represents -. R Ｘ３ and R Ｘ４ Each of these independently represents a substituent. Ｘ３ and R Ｘ４ They may be joined to each other to form a ring. [6] T in formula (Y-1) above １ and T in the above formula (Y-2) ２ A photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], in which Y represents a single bond. [7] Y in the above formula (BC-1) ｂ１ The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the R in formula (Y-1) is selected from the group consisting of the group represented by formula (Y-3). [8] ｂ５ and R in the above formula (Y-3) ｂ１０A photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein is a hydrogen atom. [9] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], further comprising a compound (C) different from the above compound (B) and the above resin, which generates acid upon irradiation with active light or radiation.

[10] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], further comprising an acid diffusion control agent (D) different from the above compound (B) and the above resin.

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

[10] .

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

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

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

[12] .

[0022] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition with excellent LWR and PED stability, a photosensitive or radiation-sensitive film formed from the above photosensitive or radiation-sensitive resin composition, a pattern forming method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

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

[0024] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "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.

[0025] In this specification, "~" means that the numbers before and after it are included as the lower and upper limits. In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0026] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene equivalent values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0027] In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both groups with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from, for example, the following substituent T.

[0028] (Substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, and methacryloyl Examples of substituents include acyl groups such as yl groups and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; nitro groups; and so on. Furthermore, if these substituents can have one or more substituents, groups having one or more substituents selected from the substituents listed above as further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.) are also included as examples of substituent T.

[0029] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -COO-, Y may also be -CO-O- or -O-CO-. The above compound may also be "X-CO-O-Z" or "X-O-CO-Z".

[0030] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the 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).

[0031] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated using, for example, the Density Functional Theory (DFT), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT, such as Gaussian 16.

[0032] In this specification, pKa refers to the value calculated using software package 1 based on a database of Hammett substituent constants and known literature values, as described above. However, if pKa cannot be calculated by this method, the value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above. However, if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0033] In this specification, "solids" means components contained in a photosensitive or radiation-sensitive resin composition that form a film (photosensitive or radiation-sensitive film) formed by the photosensitive or radiation-sensitive resin composition, and does not include solvents. Components contained in a photosensitive or radiation-sensitive resin composition that form a photosensitive or radiation-sensitive film shall be considered solids even if their properties are liquid.

[0034] [Photosensitive or Radiation-Sensitive Resin Composition] The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") contains a compound (B) comprising an organic anion and a cation represented by the following formula (BC-1), and a resin. The cation represented by the following formula (BC-1) is a sulfonium cation.

[0035]

[0036] In formula (BC-1), Ar １ and Ar ２ Each of these independently represents an aromatic ring. １ and Ar ２ They may be joined together to form a ring. n represents an integer from 1 to 3. Ar １ If there are multiple Ar １ They may be the same or different from each other, and there may be multiple Ar １ They may bond to each other to form a ring. ２ If there are multiple Ar ２ They may be the same or different from each other, and there may be multiple Ar ２ They may bond to each other to form a ring. ｂ１ and R ｂ２ Each of these independently represents a substituent. ｂ１ and R ｂ２ The elements may be joined together to form a ring. k and m each independently represent a non-negative integer. When n represents 2 or 3, the multiple k elements may be the same value or different values. When n represents 1, the multiple m elements may be the same value or different values. R ｂ１If multiple R ｂ１ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ１ They may bond to each other to form a ring. ｂ２ If multiple R ｂ２ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ２ They may be joined together to form a ring. ｂ１ Y represents a group that can be expressed by any of the following formulas (Y-1) to (Y-4). ｂ１ If there are multiple Y ｂ１ The values ​​of z may be the same or different. z represents an integer greater than or equal to 1. If n represents 2 or 3, the multiple z values ​​may be the same or different.

[0037]

[0038] In equations (Y-1) to (Y-4), * indicates the bonding position. １ and T ２ Each of these independently represents a single bond or a divalent linking group. １ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A １ This indicates the connection position with L. ２ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A ３ This indicates the connection position with A. １ Ha-CHR ｂ５ - or ＊３ -CR ｂ６ R ｂ７ C(=O)- ＊４ It represents. ＊３ is L １ This indicates the connection point with [the other element]. ＊４ Ar ３ Represents the connection position with R. ｂ５ and Ar ３ They may bond to each other to form a ring.ｂ６ or R ｂ７ and Ar ３ They may be joined to each other to form a ring. A ２ Ha-CR ｂ８ =CR ｂ９ - or -C≡C- represents R ｂ８ or R ｂ９ and Ar ４ They may be joined to each other to form a ring. ３ and Ar ４ Each of these independently represents an aromatic ring. A ３ Ha-CHR ｂ１０ - or ＊５ -CR ｂ１１ R ｂ１２ C(=O)- ＊６ It represents. ＊５ is L ２ This indicates the connection point with [the other element]. ＊６ Ar １ Represents the connection position with R. ｂ１０ and Ar １ They may bond to each other to form a ring. ｂ１１ or R ｂ１２ and Ar １ They may be joined to each other to form a ring. A ４ Ha-CR ｂ１３ =CR ｂ１４ - or -C≡C- represents R ｂ１３ or R ｂ１４ and Ar １ They may bond to each other to form a ring. ｂ３ and R ｂ４ Each of these independently represents a substituent. However, R ｂ３ and R ｂ４ It does not bond with adjacent oxygen atoms at tertiary carbon atoms. ｂ５ ~R ｂ１４ Each of these independently represents a hydrogen atom or a substituent.

[0039] The mechanism by which the above effects are obtained by the composition of the present invention is not clear, but the inventors have made the following hypothesis. However, the present invention is not limited in any way by the following hypothesis mechanism. Compound (B) contains a cation having at least one group represented by any of the above formulas (Y-1) to (Y-4). The group represented by any of the above formulas (Y-1) to (Y-4) includes a highly polar and hydrophilic carbonate ester structure, a sulfone ester structure, a structure in which a double bond and an ester bond are linked, or a structure in which a triple bond and an ester bond are linked, and is thought to improve LWR because it has high compatibility with resins. Furthermore, compound (B) has high stability against acids, so it is thought to improve PED stability.

[0040] 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. A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0041] The various components of the composition of the present invention will be described in detail below.

[0042] [Compound (B)] The composition of the present invention contains compound (B) (also simply referred to as "compound (B)") which comprises an organic anion and a cation represented by the following formula (BC-1).

[0043]

[0044] In formula (BC-1), Ar １ and Ar ２ Each of these independently represents an aromatic ring. １ and Ar ２ They may be joined together to form a ring. n represents an integer from 1 to 3. Ar １ If there are multiple Ar １They may be the same or different from each other, and there may be multiple Ar １ They may bond to each other to form a ring. ２ If there are multiple Ar ２ They may be the same or different from each other, and there may be multiple Ar ２ They may bond to each other to form a ring. ｂ１ and R ｂ２ Each of these independently represents a substituent. ｂ１ and R ｂ２ The elements may be joined together to form a ring. k and m each independently represent a non-negative integer. When n represents 2 or 3, the multiple k elements may be the same value or different values. When n represents 1, the multiple m elements may be the same value or different values. R ｂ１ If multiple R ｂ１ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ１ They may bond to each other to form a ring. ｂ２ If multiple R ｂ２ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ２ They may be joined together to form a ring. ｂ１ Y represents a group that can be expressed by any of the following formulas (Y-1) to (Y-4). ｂ１ If there are multiple Y ｂ１ The values ​​of z may be the same or different. z represents an integer greater than or equal to 1. If n represents 2 or 3, the multiple z values ​​may be the same or different.

[0045]

[0046] In equations (Y-1) to (Y-4), * indicates the bonding position. １ and T ２ Each of these independently represents a single bond or a divalent linking group. １ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A １ This indicates the connection position with L.２ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A ３ This indicates the connection position with A. １ Ha-CHR ｂ５ - or ＊３ -CR ｂ６ R ｂ７ C(=O)- ＊４ It represents. ＊３ is L １ This indicates the connection point with [the other element]. ＊４ Ar ３ Represents the connection position with R. ｂ５ and Ar ３ They may bond to each other to form a ring. ｂ６ or R ｂ７ and Ar ３ They may be joined to each other to form a ring. A ２ Ha-CR ｂ８ =CR ｂ９ - or -C≡C- represents R ｂ８ or R ｂ９ and Ar ４ They may be joined to each other to form a ring. ３ and Ar ４ Each of these independently represents an aromatic ring. A ３ Ha-CHR ｂ１０ - or ＊５ -CR ｂ１１ R ｂ１２ C(=O)- ＊６ It represents. ＊５ is L ２ This indicates the connection point with [the other element]. ＊６ Ar １ Represents the connection position with R. ｂ１０ and Ar １ They may bond to each other to form a ring. ｂ１１ or R ｂ１２ and Ar １ They may be joined to each other to form a ring. A ４ Ha-CR ｂ１３ =CR ｂ１４ - or -C≡C- represents R ｂ１３ or R ｂ１４ and Ar １They may bond to each other to form a ring. ｂ３ and R ｂ４ Each of these independently represents a substituent. However, R ｂ３ and R ｂ４ It does not bond with adjacent oxygen atoms at tertiary carbon atoms. ｂ５ ~R ｂ１４ Each of these independently represents a hydrogen atom or a substituent.

[0047] Ar in equation (BC-1) １ and Ar ２ Each of these independently represents an aromatic ring. Below, Ar １ and Ar ２ I will explain, Ar １ and Ar ２ They may be the same or different. １ and Ar ２ The aromatic ring represented by Ar may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. １ and Ar ２ The aromatic carbocyclic ring represented by may be monocyclic or polycyclic. The number of carbon atoms in the aromatic carbocyclic ring 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 aromatic carbocyclic ring may have substituents. If the aromatic carbocyclic ring has two or more substituents, the substituents may bond together to form a non-aromatic ring. Examples of aromatic carbocyclic rings include benzene rings, naphthalene rings, anthracene rings, and the like. １ and Ar ２ The aromatic heterocycle represented by may be monocyclic or polycyclic. Preferably, the aromatic heterocycle contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle is preferably 5 to 20, and more preferably 5 to 15. The aromatic heterocycle may have substituents. If the aromatic heterocycle has two or more substituents, the substituents may bond to each other to form a non-aromatic ring. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, pyridine rings, indole rings, benzodiazole rings, carbazole rings, etc. １and Ar ２ It is preferable that this represents an aromatic carbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0048] Ar １ and Ar ２ They may be joined to each other to form a ring. １ and Ar ２ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR ｍ１ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these (hereinafter also referred to as "linking groups (U)"). ｍ１ R represents a hydrogen atom or substituent. ｍ１ The substituent represented by is not particularly limited, but examples include the substituent T mentioned above.

[0049] In formula (BC-1), n ​​represents an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

[0050] Ar １ If there are multiple Ar １ They may be the same or different from each other, and there may be multiple Ar １ They may be joined to each other to form a ring. １ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0051] Ar ２ If there are multiple Ar ２ They may be the same or different from each other, and there may be multiple Ar ２ They may be joined to each other to form a ring. ２When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0052] R in equation (BC-1) ｂ１ and R ｂ２ Each of these independently represents a substituent. Hereafter, R ｂ１ and R ｂ２ I will explain R ｂ１ and R ｂ２ They may be the same or different. ｂ１ and R ｂ２ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. ｂ１ and R ｂ２ The substituent represented by may be an organic group, and may be an organic group having 1 to 30 carbon atoms. ｂ１ and R ｂ２ The organic group represented is preferably an alkyl group, alkoxy group, alkylthio group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, heteroaryl group, aryloxy group, arylthio group, or acyl group. These groups may have one or more substituents.

[0053] R ｂ１ and R ｂ２ 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. Furthermore, the alkyl group may contain at least one selected from the group consisting of ether bonds (-O-) and thioether bonds (-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.

[0054] R ｂ１ and R ｂ２ The descriptions, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by the above are as follows: ｂ１ and R ｂ２ This is the same as in the alkyl group represented by .

[0055] R ｂ１ and R ｂ２ 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. Furthermore, the alkenyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0056] R ｂ１ and R ｂ２ 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. Furthermore, the alkynyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkynyl groups include the ethynyl group.

[0057] R ｂ１ and R ｂ２The cycloalkane ring of 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. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0058] R ｂ１ and R ｂ２ The descriptions, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy and cycloalkylthio groups represented by the above-mentioned R ｂ１ and R ｂ２ This is the same as in the cycloalkyl group represented by .

[0059] R ｂ１ and R ｂ２ The aromatic carbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group 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. Examples of aryl groups include phenyl, naphthyl, and anthryl groups.

[0060] R ｂ１ and R ｂ２ The descriptions, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by the above-mentioned R ｂ１ and R ｂ２ This is the same as the case with the aryl group represented by .

[0061] R ｂ１ and R ｂ２The aromatic heterocycle (aromatic heterocycle) of the heteroaryl group represented by may be monocyclic or polycyclic. The aromatic heterocycle of the heteroaryl group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 15. The heteroaryl group may have substituents. Examples of heteroaryl groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc.

[0062] R ｂ１ and R ｂ２ The acyl group represented by R Ｃ１ It is represented as -C (=O)-. Ｃ１ It is preferable that R represents an organic group. Ｃ１ The organic group represented is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. Ｃ１ The descriptions, specific examples, and preferred ranges of alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups represented by these groups are as described above in R ｂ１ and R ｂ２ This is the same as the case for alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups represented by .

[0063] R ｂ１ and R ｂ２ The organic group represented by may be a group formed by combining at least two selected from the group consisting of alkyl groups, alkoxy groups, alkylthio groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, arylthio groups, and acyl groups.

[0064] R ｂ１ and R ｂ２ They may bond to each other to form a ring. ｂ１ and R ｂ２When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0065] In equation (BC-1), k represents an integer greater than or equal to 0. For example, it may represent an integer from 0 to 8, an integer from 0 to 4, or an integer from 0 to 2. ｂ１ If multiple R ｂ１ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ１ Multiple R elements may be joined to each other to form a ring. ｂ１ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0066] In formula (BC-1), m represents an integer greater than or equal to 0, for example, an integer from 0 to 9, an integer from 0 to 5, or an integer from 0 to 2. ｂ２ If multiple R ｂ２ The Rs may be the same or different from each other, and there may be multiple Rs. ｂ２ Multiple R elements may be joined to each other to form a ring. ｂ２ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0067] Y in equation (BC-1) ｂ１ * represents a group represented by any of the above formulas (Y-1) to (Y-4). In formulas (Y-1) to (Y-4), * represents the bond position, and more specifically, Ar in formula (BC-1) １ This indicates the connection point with [the other element].

[0068] T in equation (Y-1) １ represents a single bond or a divalent linking group. １ Examples of divalent linking groups represented by include -O-, -CO-, -COO-, -S-, -SO-, and -SO ２ -, -NR ｍ１ -, -CONR ｍ１-, alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these. ｍ１ represents a hydrogen atom or substituent. Preferred alkylene groups include C1-C8 alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, and octylene. The alkylene group may have substituents. The cycloalkane ring of the cycloalkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3-20, more preferably 4-12, and even more preferably 5-10. The cycloalkylene group may have substituents. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Alternatively, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced by a vinylene group. The aromatic hydrocarbon ring of the arylene group may be monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon ring of the arylene group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Examples of arylene groups include phenylene, naphthylene, and anthreylene groups, with phenylene or naphthylene being preferred, and phenylene being more preferred. The arylene group may have substituents. The aromatic heterocycle of the heteroarylene group may be monocyclic or polycyclic. The aromatic heterocycle of the heteroarylene group preferably contains at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen as a ring member atom. The number of ring member atoms in the aromatic heterocycle of the heteroarylene group is preferably 5 to 20, more preferably 5 to 15. Examples of heteroarylene groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. The heteroarylene group may have substituents. ｍ１The substituent represented by is not particularly limited, but examples include the substituent T mentioned above. ｍ１ R preferably represents a hydrogen atom or an alkyl group. ｍ１ Examples of alkyl groups represented by include alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or fewer carbon atoms being preferred. １ It is preferable that this represents a single bond.

[0069] L in equation (Y-1) １ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A １ This indicates the connection position with L. １ teeth ＊１ -(C=O)O- ＊２ It is preferable to represent this.

[0070] A in equation (Y-1) １ Ha-CHR ｂ５ - or ＊３ -CR ｂ６ R ｂ７ C(=O)- ＊４ It represents. ＊３ is L １ This indicates the connection point with [the other element]. ＊４ Ar ３ Represents the bond position with R. ｂ５ R represents a hydrogen atom or substituent. ｂ５ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. ｂ５ The substituent represented by may be an organic group, and may be an organic group having 1 to 30 carbon atoms. ｂ５ The organic group represented is preferably an alkyl group, alkoxy group, alkylthio group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, heteroaryl group, aryloxy group, arylthio group, or acyl group. These groups may have one or more substituents.

[0071] R ｂ５ 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. Furthermore, the alkyl group may contain at least one selected from the group consisting of ether bonds (-O-) and thioether bonds (-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.

[0072] R ｂ５ The descriptions, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by the above are as follows: ｂ５ This is the same as in the alkyl group represented by .

[0073] R ｂ５ 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. Furthermore, the alkenyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0074] R ｂ５ 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. Furthermore, the alkynyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkynyl groups include the ethynyl group.

[0075] R ｂ５ The cycloalkane ring of 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. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0076] R ｂ５ The descriptions, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy and cycloalkylthio groups represented by the above-mentioned R ｂ５ This is the same as in the cycloalkyl group represented by .

[0077] R ｂ５ The aromatic carbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group 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. Examples of aryl groups include phenyl, naphthyl, and anthryl groups.

[0078] R ｂ５ The descriptions, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by the above-mentioned R ｂ５ This is the same as the case with the aryl group represented by .

[0079] R ｂ５The aromatic heterocycle (aromatic heterocycle) of the heteroaryl group represented by may be monocyclic or polycyclic. The aromatic heterocycle of the heteroaryl group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 15. The heteroaryl group may have substituents. Examples of heteroaryl groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc.

[0080] R ｂ５ The acyl group represented by R Ｃ１ It is represented as -C (=O)-. Ｃ１ It is preferable that R represents an organic group. Ｃ１ The organic group represented is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. Ｃ１ The descriptions, specific examples, and preferred ranges of alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups represented by these groups are as described above in R ｂ５ This is the same as the case for alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups represented by .

[0081] R ｂ５ The organic group represented by may be a group formed by combining at least two selected from the group consisting of alkyl groups, alkoxy groups, alkylthio groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, arylthio groups, and acyl groups.

[0082] R ｂ５ It is preferable that represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, or an aryl group, more preferably a hydrogen atom, a hydroxyl group, or an alkyl group, and even more preferably a hydrogen atom.

[0083] R ｂ５ and Ar ３They may bond to each other to form a ring. ｂ５ and Ar ３ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0084] R ｂ６ and R ｂ７ Each of these independently represents a hydrogen atom or a substituent. Hereinafter, R ｂ６ and R ｂ７ I will explain R ｂ６ and R ｂ７ They may be the same or different. ｂ６ and R ｂ７ The description, specific examples, and preferred range of substituents represented by R are as described above. ｂ５ This is the same as in the substituent represented by R. ｂ６ and R ｂ７ Each of these groups preferably independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, or an aryl group; more preferably a hydrogen atom, a hydroxyl group, or an alkyl group; and even more preferably a hydrogen atom.

[0085] R ｂ６ or R ｂ７ and Ar ３ They may bond to each other to form a ring. ｂ６ or R ｂ７ and Ar ３ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0086] A １ Ha-CHR ｂ５ It is preferable to represent it as -.

[0087] Ar in equation (Y-1) ３ Ar represents an aromatic ring. ３ The aromatic ring represented by Ar may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. ３The aromatic carbocyclic ring represented by may be monocyclic or polycyclic. The number of carbon atoms in the aromatic carbocyclic ring 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 aromatic carbocyclic ring may have substituents. If the aromatic carbocyclic ring has two or more substituents, the substituents may bond together to form a non-aromatic ring. Examples of aromatic carbocyclic rings include benzene rings, naphthalene rings, anthracene rings, and the like. ３ The aromatic heterocycle represented by may be monocyclic or polycyclic. Preferably, the aromatic heterocycle contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle is preferably 5 to 20, and more preferably 5 to 15. The aromatic heterocycle may have substituents. If the aromatic heterocycle has two or more substituents, the substituents may bond to each other to form a non-aromatic ring. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, pyridine rings, indole rings, benzodiazole rings, carbazole rings, etc. ３ It is preferable that this represents an aromatic carbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0088] T in equation (Y-2) ２ represents a single bond or a divalent linking group. ２ The explanation, specific examples, and preferred range of T in the aforementioned formula (Y-1) are given by １ It is the same as the one in [location / place].

[0089] A in equation (Y-2) ２ Ha-CR ｂ８ =CR ｂ９ - or -C≡C- represents R ｂ８ and R ｂ９ Each of these independently represents a hydrogen atom or a substituent. Hereinafter, R ｂ８ and R ｂ９ I will explain R ｂ８ and R ｂ９ They may be the same or different. ｂ８ and R ｂ９The description, specific examples, and preferred range of substituents represented by R are as described above. ｂ５ This is the same as in the substituent represented by R. ｂ８ and R ｂ９ Each of these groups preferably independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, or an aryl group; more preferably a hydrogen atom, a hydroxyl group, or an alkyl group; and even more preferably a hydrogen atom.

[0090] R ｂ８ or R ｂ９ and Ar ４ They may bond to each other to form a ring. ｂ８ or R ｂ９ and Ar ４ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0091] A ２ Ha-CR ｂ８ =CR ｂ９ It is preferable to represent it as -.

[0092] Ar in equation (Y-2) ４ Ar represents an aromatic ring. ４ The explanation, specific examples, and preferred range of Ar in formula (Y-1) mentioned above are provided. ３ It is the same as the one in [location / place].

[0093] L in equation (Y-3) ２ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A ３ This indicates the connection position with L. ２ teeth ＊１ -(C=O)O- ＊２ It is preferable to represent this.

[0094] A in equation (Y-3) ３ Ha-CHR ｂ１０ - or ＊５ -CR ｂ１１ R ｂ１２ C(=O)-＊６ It represents. ＊５ is L ２ This indicates the connection point with [the other element]. ＊６ Ar １ Represents the bond position with R. ｂ１０ R represents a hydrogen atom or substituent. ｂ１０ The explanation, specific examples, and preferred range are as described above in R ｂ５ It is the same as in R. ｂ１０ and Ar １ They may bond to each other to form a ring. ｂ１０ and Ar １ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0095] R ｂ１１ and R ｂ１２ Each of these independently represents a hydrogen atom or a substituent. Hereinafter, R ｂ１１ and R ｂ１２ I will explain R ｂ１１ and R ｂ１２ They may be the same or different. ｂ１１ and R ｂ１２ The explanation, specific examples, and preferred range are as described above in R ｂ６ and R ｂ７ It is the same as the one in R. ｂ１１ or R ｂ１２ and Ar １ They may bond to each other to form a ring. ｂ１１ or R ｂ１２ and Ar １ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0096] A ３ Ha-CHR ｂ１０ It is preferable to represent it as -.

[0097] R in equation (Y-3) ｂ３ represents a substituent. However, R ｂ３ It does not bond with adjacent oxygen atoms at tertiary carbon atoms. ｂ３The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. ｂ３ The substituent represented by may be an organic group, and may be an organic group having 1 to 30 carbon atoms. ｂ３ The organic group represented is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group. These groups may have one or more substituents.

[0098] R ｂ３ 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. Furthermore, the alkyl group may contain at least one selected from the group consisting of ether bonds (-O-) and thioether bonds (-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, pentyl 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.

[0099] R ｂ３ 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. Furthermore, the alkenyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0100] R ｂ３The 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. Furthermore, the alkynyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkynyl groups include the ethynyl group.

[0101] R ｂ３ The cycloalkane ring of 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, for example, one or more methylene groups constituting the cycloalkane ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group (e.g., tetrahydrofuran, tetrahydropyran, γ-butyrolactone). In addition, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, etc.

[0102] R ｂ３ The aromatic carbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group 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. Examples of aryl groups include phenyl, naphthyl, and anthryl groups.

[0103] R ｂ３ The organic group represented by may be a group formed by combining at least two groups selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and aryl groups mentioned above.

[0104] R ｂ３It is preferable that represents an alkyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group.

[0105] A in equation (Y-4) ４ Ha-CR ｂ１３ =CR ｂ１４ - or -C≡C- represents R ｂ１３ and R ｂ１４ Each of these independently represents a hydrogen atom or a substituent. Hereinafter, R ｂ１３ and R ｂ１４ I will explain R ｂ１３ and R ｂ１４ They may be the same or different. ｂ１３ and R ｂ１４ The explanation, specific examples, and preferred range are as described above in R ｂ８ and R ｂ９ It is the same as the one in R. ｂ１３ or R ｂ１４ and Ar １ They may bond to each other to form a ring. ｂ１３ or R ｂ１４ and Ar １ When these elements bond to each other, they may be bonded by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0106] A ４ Ha-CR ｂ１３ =CR ｂ１４ It is preferable to represent it as -.

[0107] R in equation (Y-4) ｂ４ represents a substituent. However, R ｂ４ It does not bond with adjacent oxygen atoms at tertiary carbon atoms. ｂ４ The explanation, specific examples, and preferred range of R in formula (Y-3) mentioned above are given by ｂ３ It is the same as the one in [location / place].

[0108] T in equation (Y-1) １ and T in equation (Y-2) ２ The embodiment in which a single bond is represented is a preferred embodiment of the present invention.

[0109] Y in equation (BC-1) ｂ１However, an embodiment having at least one selected from the group consisting of the group represented by formula (Y-1) and the group represented by formula (Y-3) is a preferred embodiment of the present invention.

[0110] Y in equation (BC-1) ｂ１ However, it has at least one selected from the group consisting of the group represented by formula (Y-1) and the group represented by formula (Y-3), and the R in formula (Y-1) ｂ５ and R in equation (Y-3) ｂ１０ A configuration in which represents a hydrogen atom is a preferred embodiment of the present invention.

[0111] In equation (BC-1), z represents an integer greater than or equal to 1, for example, an integer from 1 to 9, an integer from 1 to 5, or 1 or 2.

[0112] Specific examples of cations represented by formula (BC-1) are shown below, but are not limited to these. Me represents a methyl group.

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] Compound (B) may contain one type of cation represented by formula (BC-1), or two or more types.

[0124] Compound (B) may contain, in addition to the cation represented by formula (BC-1), cations other than the cation represented by formula (BC-1).

[0125] Compound (B) contains an organic anion (also called "organic anion (AX)"). The organic anion (AX) may be a monovalent organic anion or a divalent or more. The organic anion (AX) is preferably an anion with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0126] 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.

[0127] 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).

[0128] 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.

[0129] 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).

[0130] 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.

[0131] An example of a sulfonylimid anion is the saccharin anion.

[0132] 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.

[0133] 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.

[0134] The organic anion (AX) preferably has a group represented by any of the following formulas (an1) to (an7).

[0135]

[0136] In equations (an1) to (an7), * indicates the bonding position. In equations (an3) to (an7), R Ａ Each of these independently represents a substituent. The two R in formula (an3) Ａ They may be the same or different.

[0137] R Ａ The substituent represented by is not particularly limited, but may be an organic group, for example, an organic group having 1 to 20 carbon atoms, and an organic group having 1 to 10 carbon atoms is preferred. Ａ The organic group represented by may contain heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. Ａ The organic group represented by may have substituents. Ａ The description, specific examples, and preferred range of the organic group represented by the above R ｂ５ This is the same as the one in the organic group represented by .

[0138] R Ａ The substituent represented by is preferably an electron-withdrawing group. Preferred electron-withdrawing groups include, for example, halogen atoms (preferably fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms), cyano groups, nitro groups, dicyanomethyl groups, or groups represented by the following formula (1A).

[0139]

[0140] In formula (1A), Y １ and Y ３ Each is independently -O- or -NR ３ Represents -. R ３ Y represents a hydrogen atom or an alkyl group. ２ is -C(=O)- or -SO２ Represents -. R ４ R represents an alkyl group, cycloalkyl group, or aryl group. ３ and R ４ At least two elements selected from the group consisting of the following may be joined to form a ring. p and r each independently represent 0 or 1. q represents 1 or 2. * indicates a bond position.

[0141] Y in equation (1A) １ and Y ３ Each is independently -O- or -NR ３ Represents -. R ３ R represents a hydrogen atom or an alkyl group. ３ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be linear or branched. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, etc.

[0142] R in equation (1A) ４ R represents an alkyl group, a cycloalkyl group, or an aryl group, preferably an alkyl group or a cycloalkyl group. ４ The alkyl group represented by may be linear or branched, preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms. ４ Examples of alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl groups. The alkyl groups may further have substituents. ４ The cycloalkyl group represented by may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably having 4 to 15 carbon atoms, and even more preferably having 5 to 10 carbon atoms. ４Examples of cycloalkyl groups represented by include cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, adamantyl group, 1-ethyladamantyl group, norbornyl group, tetracyclodecanyl group, and tetracyclododecanyl group. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with heteroatoms such as oxygen atoms, groups having heteroatoms such as carbonyl groups and ester bonds, or vinylidene groups. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with vinylene groups. The above cycloalkyl groups may further have substituents. ４ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. The above aryl group may further have substituents.

[0143] Y in equation (1A) ２ is -C(=O)- or -SO ２ It represents -. In formula (1A), p and r each independently represent 0 or 1. In formula (1A), q represents 1 or 2, and preferably represents 1.

[0144] The group represented by formula (1A) is -O(C=O)R ４ , -(C=O) OR ４ , -O(SO ２ ) R ４ ,-(SO ２ ) OR ４ or - (SO ２ ) R ４ It is preferable that this be the case.

[0145] A preferred embodiment of the present invention is one in which the organic anion (AX) is represented by the following formula (BA-1).

[0146]

[0147] In formula (BA-1), R Ｘ１ represents a substituent.

[0148] R Ｘ１The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. Ｘ１ The substituent represented by may be an organic group, and may be an organic group having 1 to 30 carbon atoms. Ｘ１ The organic group represented is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. These groups may have one or more substituents.

[0149] R Ｘ１ 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. The substituents that the alkyl group may have are not particularly limited, for example, substituent T mentioned above. Examples of alkyl groups having substituents include alkyl fluorides. Furthermore, the alkyl group may contain at least one selected from the group consisting of ether bonds (-O-) and thioether bonds (-S-) in the chain. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups.

[0150] R Ｘ１ 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. Furthermore, the alkenyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0151] R Ｘ１The 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. Furthermore, the alkynyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkynyl groups include the ethynyl group.

[0152] R Ｘ１ The cycloalkane ring of 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. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0153] R Ｘ１ The aromatic carbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group 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. Examples of aryl groups include phenyl, naphthyl, and anthryl groups.

[0154] R Ｘ１The aromatic heterocycle (aromatic heterocycle) of the heteroaryl group represented by may be monocyclic or polycyclic. The aromatic heterocycle of the heteroaryl group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 15. The heteroaryl group may have substituents. Examples of heteroaryl groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc.

[0155] R Ｘ１ The organic group represented by may be a group formed by combining at least two selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups.

[0156] R Ｘ１ Preferably, represents an alkyl group, a cycloalkyl group, or an aryl group.

[0157] A preferred embodiment of the present invention is one in which the organic anion (AX) is selected from the group consisting of the anion represented by the following formula (BA-2) and the anion represented by the following formula (BA-3).

[0158]

[0159] In formula (BA-2), R Ｘ２ represents a substituent. In formula (BA-3), L Ｘ１ These are single bonds, -(C=O)- or -SO ２ Represents -. R Ｘ３ and R Ｘ４ Each of these independently represents a substituent. Ｘ３ and R Ｘ４ They may be joined together to form a ring.

[0160] R in equation (BA-2) Ｘ２ The explanation, specific examples, and preferred range of R in the aforementioned formula (BA-1) are given by Ｘ１ It is the same as in equation (BA-3).Ｘ３ and R Ｘ４ The explanation, specific examples, and preferred range of R in the aforementioned formula (BA-1) are given by Ｘ１ It is the same as in R. Ｘ３ and R Ｘ４ They can be the same or they can be different. Ｘ３ and R Ｘ４ They may bond to each other to form a ring. Ｘ３ and R Ｘ４ When they bond to each other, they may be bonded by a single bond or by a linking group. The above linking group is not particularly limited, but examples include the linking group (U) mentioned above. L in formula (BA-3) Ｘ１ It is preferable that this represents a single bond or -(C=O)-.

[0161] Compound (B) may contain one type of organic anion (AX), or two or more types.

[0162] Compound (B) may contain anions other than the organic anion (AX) in addition to the organic anion (AX).

[0163] The molecular weight of compound (B) is not particularly limited, but for example, it may be 100 or more, 150 or more, or 200 or more. Also, the molecular weight of compound (B) may be 3000 or less, 2500 or less, or 2000 or less.

[0164] Compound (B) is preferably a different compound from the resin described later.

[0165] Compound (B) can be synthesized by known methods.

[0166] The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% 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% by mass or less, more preferably 55% by mass or less, and even more preferably 50% 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 only 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.

[0167] [Resin] The composition of the present invention contains a resin (also referred to as "resin (P)").

[0168] (Repeating units having acid-degradable groups) It is preferable that the resin (P) contains repeating units having acid-degradable groups. When the resin (P) contains repeating units having acid-degradable groups, the resin (P) can function as an acid-degradable resin. An acid-degradable resin is a resin that decomposes due to the action of an acid. It is preferable that the resin (P) is a resin whose polarity changes when decomposed due to the action of an acid, and more preferably a resin whose polarity increases when decomposed due to the action of an acid. It is preferable that the resin (P) increases in polarity when decomposed due to the action of an acid, increases in solubility in alkaline developer, and decreases in solubility in organic solvents. It is preferable that the acid-degradable group is a group whose polarity increases when decomposed due to the action of an acid. It is preferable that the acid-degradable group is a group that generates a polar group when decomposed due to the action of an acid. It is preferable that the acid-degradable group has a structure in which the polar group is protected by a group that leaves due to the action of an acid (leaving group). Examples of the above polar groups include acidic 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. Preferably, the above polar groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups, with carboxyl groups being particularly preferred.

[0169] Examples of groups that are eliminated by the action of an acid include the groups represented by any of the following formulas: (Y1), (Y2), (Y3), and (Y4). Formula (Y1): -C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R３６ ) (Caution ３７ ) ( OR ３８ ) Formula (Y4): -C(Rn １ ) (Rn ２ ) (H)

[0170] In equations (Y1) and (Y2), Rx １ ~Rx ３ Each of these independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an aryl group. １ ~Rx ３ If all of them are alkyl groups, 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 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 A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The alkynyl group is preferably an ethynyl group or a propargyl group. 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.

[0171] 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) and the group represented by formula (Y2) are, 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.

[0172] 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.

[0173] 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, alkenyl groups, and alkynyl groups. ３６It is also preferable that it be a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl 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 this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. 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.

[0174] In formula (Y4), Rn １ Rn represents an alkenyl group, alkynyl group, aryl group, or heteroaryl group. ２ Rn represents a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group. １ and Rn ２ These elements may combine with each other to form a ring. Rn １ An aryl group is preferred. １ , and also, Rn ２ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group represented by may also preferably have a fluorine atom or an iodine atom as a substituent.

[0175] 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.

[0176] 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.

[0177] The repeating unit having an acid-degradable group is preferably a repeating unit represented by the following formula (Ga1). The resin (P) preferably contains a repeating unit represented by the following formula (Ga1).

[0178]

[0179] In formula (Ga1), R ａ１ , R ａ２ and R ａ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ X represents a single bond or a divalent linking group. ａ１ represents -O- or -C(=O)O-. ａ３ and L ａ１ These elements may bond with each other to form a ring. G represents a group represented by the following formula (G-1) or (G-2).

[0180]

[0181] In formula (G-1), R ａ４ R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ５ and R ａ６ Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ４ and R ａ５ These elements may combine with each other to form a ring. ａ４ and L in equation (Ga1) ａ１ These may bond to each other to form a ring. * indicates the bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９Each of these independently represents an alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group. ａ７ , R ａ８ and R ａ９ Two of these may be joined together to form a ring. * indicates the bonding position.

[0182] R in equation (Ga1) ａ１ , R ａ２ and R ａ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Hereinafter, R ａ１ , R ａ２ and R ａ３ I will explain R ａ１ , R ａ２ and R ａ３ They may be the same or they may be different.

[0183] R ａ１ , R ａ２ and R ａ３ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited; 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. The alkyl group may also contain an ether bond (-O-) or 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.

[0184] R ａ１ , R ａ２ and R ａ３The cycloalkane ring of 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. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0185] R ａ１ , R ａ２ and R ａ３ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or an iodine atom.

[0186] R ａ１ , R ａ２ and R ａ３ The description, specific examples, and preferred range of alkyl groups included in the alkoxycarbonyl group represented by R are as described above. ａ１ , R ａ２ and R ａ３ This is the same as in the alkyl group represented by .

[0187] R ａ１ , R ａ２ and R ａ３ Each of these elements preferably independently represents a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

[0188] L in equation (Ga1) ａ１ L represents a single bond or a divalent linking group. ａ１ The divalent linking group represented by is not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR ａ１０ -, -CONRａ１０ -, arylene groups, heteroarylene groups, alkylene groups, cycloalkylene groups, and groups formed by combining two or more of these. ａ１０ R represents a hydrogen atom or substituent. ａ１０ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. ａ１０ Preferably, represents a hydrogen atom or an alkyl group.

[0189] L ａ１ Arylene group and L represented by ａ１ When the divalent linking group represented by contains an arylene group, the aromatic hydrocarbon ring of the arylene group may be monocyclic or polycyclic. The number of carbon atoms in the ring member atoms of the aromatic hydrocarbon ring of the arylene group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Examples of arylene groups include phenylene groups, naphthylene groups, and anthrylene groups, with phenylene or naphthylene groups being preferred, and phenylene groups being more preferred. The arylene group may have substituents.

[0190] L ａ１ A heteroarylene group and L represented by ａ１ When the divalent linking group represented by contains a heteroarylene group, the aromatic heterocycle of the heteroarylene group may be monocyclic or polycyclic. Preferably, the aromatic heterocycle of the heteroarylene group contains at least one member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of member atoms of the aromatic heterocycle of the heteroarylene group is preferably 5 to 20, and more preferably 5 to 15. Examples of heteroarylene groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. The heteroarylene group may have substituents.

[0191] L ａ１ The alkylene group and L represented by ａ１When the divalent linking group represented by contains an alkylene group, the alkylene group may be linear or branched. The number of carbon atoms in the alkylene 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 alkylene group may have substituents. The alkylene group may also contain an ether bond (-O-) or a thioether bond (-S-) in the chain. Examples of alkylene groups include methylene, ethylene, propylene, butylene, hexylene, and octylene groups.

[0192] L ａ１ A cycloalkylene group and L represented by ａ１ When the divalent linking group represented by contains a cycloalkylene group, the cycloalkane ring of the cycloalkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene 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 cycloalkylene group may have substituents. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a vinylene group. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, norbornylene, tetracyclodecanylene, tetracyclododecanylene, adamantylene, and the like.

[0193] R ａ１０ The description, specific examples, and preferred range of alkyl groups represented by R are as described above. ａ１ , R ａ２ and R ａ３ This is the same as in the alkyl group represented by .

[0194] L ａ１ It is preferable that represents a divalent linking group containing an arylene group, and more preferably that it represents an arylene group.

[0195] R ａ３ and L in equation (Ga1) ａ１These elements may combine with each other to form a ring. ａ３ and L in equation (Ga1) ａ１ When bonding occurs, it may be a single bond or a bond via a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0196] X in equation (Ga1) ａ１ represents -O- or -C(=O)O-.

[0197] In formula (Ga1), G represents the group represented by formula (G-1) or (G-2).

[0198] R in equation (G-1) ａ４ The symbol represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, or alkenyl group.

[0199] R ａ４ 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. Furthermore, the alkyl group may contain at least one selected from the group consisting of ether bonds (-O-) and thioether bonds (-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.

[0200] R ａ４ 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. Furthermore, the alkenyl group may contain at least one selected from the group consisting of ether bonds and thioether bonds in the chain. Examples of alkenyl groups include vinyl groups and allyl groups.

[0201] R ａ４ The cycloalkane ring of 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. For example, one or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a vinylene group. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like.

[0202] R ａ４ The aromatic carbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group 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. Examples of aryl groups include phenyl, naphthyl, and anthryl groups.

[0203] R ａ４ The aromatic heterocycle (aromatic heterocycle) of the heteroaryl group represented by may be monocyclic or polycyclic. The aromatic heterocycle of the heteroaryl group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 15. The heteroaryl group may have substituents. Examples of heteroaryl groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc.

[0204] R ａ４ The aralkyl group represented by the above-mentioned R ａ４A preferred group is one in which one hydrogen atom in the alkyl group represented by is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), for example, a benzyl group, a phenethyl group, etc.

[0205] R ａ４ Preferably, represents a hydrogen atom, an alkyl group, or a cycloalkyl group.

[0206] R in equation (G-1) ａ５ and R ａ６ Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. Hereinafter, R ａ５ and R ａ６ I will explain R ａ５ and R ａ６ They may be the same or different. ａ５ and R ａ６ The descriptions, specific examples, and preferred ranges for alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, and alkenyl groups represented by the aforementioned R ａ４ This is the same as the alkyl, cycloalkyl, aryl, heteroaryl, aralkyl, and alkenyl groups represented by R. ａ５ and R ａ６ Preferably, each of these independently represents an alkyl group or a cycloalkyl group.

[0207] R ａ４ and R ａ５ These elements may combine with each other to form a ring. ａ４ and R ａ５ When bonding occurs, it may be a single bond or a bond via a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0208] R ａ４ and L ａ１ These elements may combine with each other to form a ring. ａ４ and L ａ１ When bonding occurs, it may be a single bond or a bond via a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0209] R in equation (G-2) ａ７ , R ａ８ and R ａ９ Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. Hereinafter, R ａ７ , R ａ８ and R ａ９ I will explain R ａ７ , R ａ８ and R ａ９ They may be the same or different. ａ７ , R ａ８ and R ａ９ The descriptions, specific examples, and preferred ranges for alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, and alkenyl groups represented by the aforementioned R ａ４ This is the same as the alkyl, cycloalkyl, aryl, heteroaryl, aralkyl, and alkenyl groups represented by R. ａ７ , R ａ８ and R ａ９ Preferably, each of these independently represents an alkyl group or a cycloalkyl group.

[0210] R ａ７ , R ａ８ and R ａ９ Two of them may combine to form a ring. ａ７ , R ａ８ and R ａ９ When two of them bond, they may bond by a single bond or by a linking group. The linking group is not particularly limited, but examples include the aforementioned linking group (U).

[0211] For specific examples of repeating units having acid-degradable groups, see, for example, the descriptions in

[0029] to

[0071] of International Publication No. 2022 / 024928, which are incorporated herein by reference. Specific examples of repeating units having acid-degradable groups include M-8 to M-14 described in the examples below.

[0212] When the resin (P) contains repeating units having acid-degradable groups, the content of these repeating units is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units having acid-degradable groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to the total repeating units in the resin (P). When the resin (P) contains repeating units having acid-degradable groups, there may be one type of repeating unit having acid-degradable groups or two or more types. When the resin (P) contains two or more types of repeating units having acid-degradable groups, it is preferable that their total content is within the range of the above preferred content.

[0213] (Repeating units having phenolic hydroxyl groups) The resin (P) preferably contains repeating units having phenolic hydroxyl groups. The repeating units having phenolic hydroxyl groups are preferably different from the repeating units having acid-degradable groups described above. The repeating units having phenolic hydroxyl groups are preferably repeating units represented by the following formula (Pa1).

[0214]

[0215] In formula (Pa1), R １１ , R １２ and R １３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １２ Ar １ It may also combine with to form a ring. １１ This is a single bond, -COO- or -CONR １４ Represents -. R １４ L represents a hydrogen atom or substituent. １１ Ar represents a single bond or an alkylene group. １ represents an aromatic ring. k represents an integer from 1 to 5.

[0216] R in equation (Pa1) １１ , R １２ and R １３Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Hereinafter, R １１ , R １２ and R １３ I will explain R １１ , R １２ and R １３ They may be the same or different. １１ , R １２ and R １３ The explanation, specific examples, and preferred range of R in the aforementioned formula (Ga1) are given below. ａ１ , R ａ２ and R ａ３ It is the same as the one in [location / place].

[0217] X in equation (Pa1) １１ This is a single bond, -COO- or -CONR １４ Represents -. R １４ R represents a hydrogen atom or substituent. １４ The substituents represented by are not particularly limited, and examples include the substituent T mentioned above. １４ R preferably represents a hydrogen atom or an alkyl group. １４ The description, specific examples, and preferred range of alkyl groups represented by R are as described above. ａ１ , R ａ２ and R ａ３ This is the same as in the alkyl group represented by X. １１ It is preferable that this represents a single bond or -COO-.

[0218] L in equation (Pa1) １１ L represents a single bond or an alkylene group. １１ The alkylene group represented by may be linear or branched. The number of carbon atoms in the alkylene 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 alkylene group may have substituents. The alkylene group may also contain an ether bond (-O-) or a thioether bond (-S-) in the chain. Examples of alkylene groups include methylene, ethylene, propylene, butylene, hexylene, and octylene.

[0219] Ar in equation (Pa1) １ Ar represents an aromatic ring. １ The aromatic ring represented by Ar may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. １ The aromatic carbocyclic ring represented by may be monocyclic or polycyclic. The number of carbon atoms in the aromatic carbocyclic ring 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. Examples of aromatic carbocyclic rings include benzene rings, naphthalene rings, anthracene rings, and the like. １ The aromatic heterocycle represented by may be monocyclic or polycyclic. Preferably, the aromatic heterocycle contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle is preferably 5 to 20, and more preferably 5 to 15. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, pyridine rings, indole rings, benzodiazole rings, carbazole rings, and the like. １ Ar preferably represents an aromatic carbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring. １ The aromatic ring represented by has a hydroxyl group, but may also have substituents other than hydroxyl groups. １ If the aromatic ring represented by has two or more substituents, the substituents may bond together to form a non-aromatic ring.

[0220] In formula (Pa1), k represents an integer from 1 to 5, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0221] Specific examples of repeating units having phenolic hydroxyl groups include, but are not limited to, M-1 to M-5 described in the examples below.

[0222] When the resin (P) contains repeating units having phenolic hydroxyl groups, the content of repeating units having phenolic hydroxyl groups is not particularly limited, but it is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units having phenolic hydroxyl groups is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less, relative to the total repeating units in the resin (P). When the resin (P) contains repeating units having phenolic hydroxyl groups, there may be one type of repeating unit having phenolic hydroxyl groups or two or more types. When the resin (P) contains two or more types of repeating units having phenolic hydroxyl groups, it is preferable that their total content is within the range of the above preferred content.

[0223] (Repeating units having lactone groups, sultone groups, or carbonate groups) The resin (P) may contain repeating units having lactone groups, sultone groups, or carbonate groups (hereinafter also referred to as "unit Y"). It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0224] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferred. The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in International Publication No. 2022 / 024928

[0127] to

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

[0225] Resin (P) preferably has a repeating unit having a lactone group, a sultone group or a carbonate group formed by removing one or more hydrogen atoms from a ring atom of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any one of the following formulas (SL1-1) to (SL1-3) or a cyclic carbonate structure represented by any one of the following formulas (CC1-1) to (CC1-2), and the lactone group, sultone group or carbonate group may be directly bonded to the main chain. For example, a ring atom of the lactone group, sultone group or carbonate group may constitute the main chain of Resin (P). The lactone group, sultone group and carbonate group may have a substituent.

[0226] R in the following structural formula Ｌ represents a substituent. When multiple R Ｌ are present, the multiple R Ｌ may be the same or different. Examples of R Ｌ include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1 are present, the multiple e1 may be the same or different. When e1 is 2 or more, the multiple R Ｌ may be the same or different, and two or more R Ｌ may be bonded to each other to form a ring.

[0227]

[0228] Examples of the repeating unit having a lactone group, a sultone group or a carbonate group include a repeating unit represented by the following formula (AI-2).

[0229]

[0230] In formula (AI-2), Rb ０ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by Rb ０ may have a substituent. Rb ０Examples of the substituent which may be possessed by the alkyl group represented by include a hydroxyl group and a halogen atom. Rb ０ Examples of the halogen atom represented by Rb include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group combining these. Among these, Ab is a single bond or -Ab １ -CO ２ - A linking group represented by is preferable. Ab １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group is preferable. V represents a group formed by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22), a group formed by removing one hydrogen atom from a ring member atom of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3), or a group formed by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any one of formulas (CC1-1) to (CC1-2).

[0231] When the resin (P) contains the unit Y, the content of the unit Y may be 1 mol% or more, or 10 mol% or more, based on all repeating units in the resin (P). Further, the content of the unit Y may be 80 mol% or less, or 70 mol% or less, based on all repeating units in the resin (P). It is also preferable that the resin (P) does not contain the unit Y.

[0232] (Repeating unit having a photoacid generating group) The resin (P) may contain a repeating unit having a group that generates an acid upon irradiation with an actinic ray or radiation (also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0233]

[0234] In formula (4), R ４１L 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 group that decomposes upon irradiation with active light or radiation, generating an acidic group.

[0235] L ４１ represents a single bond or a divalent linking group, preferably a single bond or an ester bond (-COO-).

[0236] L ４２ These are alkylene groups, cycloalkylene groups, arylene groups, -O-, -CO-, -S-, -SO-, -SO ２ It is preferable that the linking group consists of at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, cycloalkyl group, or aryl group). The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred. The cycloalkylene group may be a monocyclic or polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but 3 to 20 is preferred, and 5 to 15 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. The alkylene group, cycloalkylene group and arylene group may have substituents, and the substituent T mentioned above is an example of a substituent.

[0237] R ４０ Preferably, the group is represented by the following formula (S4-1).

[0238]

[0239] In equation (S4-1), Q － represents an acid residue, M ＋ * represents a cation. * represents L ４１ This indicates the bonding position. An acid residue is a group formed when a proton dissociates from an acid. Q － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ －), or sulfonamide group (N － -SO ２ R Ｎ１ It is represented by R Ｎ１ represents an organic group, and examples include organic groups having 1 to 10 carbon atoms, with alkyl groups, fluoroalkyl groups, or aryl groups being preferred. A sulfonate anion group is more preferred. ＋ The description, specific examples, and preferred range of the cation represented by are the same as those for the cation that compound (C) may contain, as described later.

[0240] Specific examples of repeating units having photoacid generating groups include, for example, the repeating units described in

[0094] to

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

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

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

[0241] If the resin (P) contains repeating units having photoacid-generating groups, the content of repeating units having photoacid-generating groups may be 0.1 mol% or more, 0.5 mol% or more, or 1 mol% or more, relative to the total repeating units in the resin (P). Alternatively, the content of repeating units having photoacid-generating groups may be 40 mol% or less, 30 mol% or less, or 20 mol% or less, relative to the total repeating units in the resin (P). It is also preferable that the resin (P) does not contain repeating units having photoacid-generating groups.

[0242] (Repeating units represented by formula (V-1) or formula (V-2)) The resin (P) may have repeating units represented by the following formula (V-1) or formula (V-2). It is also preferable that the repeating units represented by formula (V-1) and formula (V-2) are different from the repeating units described above.

[0243]

[0244] In equations (V-1) and (V-2), R ６ and R ７Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ n represents an integer between 0 and 6. ４ X represents an integer between 0 and 4. ４ is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

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

[0245] (Repeating units to reduce the mobility of the main chain) The resin (P) may have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg may be greater than 90°C, greater than 100°C, greater than 110°C, or greater than 125°C. The Tg may be 400°C or less, or 350°C or less, in order to have a good dissolution rate in the developer. In this specification, the glass transition temperature (Tg) of a polymer such as resin (P) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer 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.).

[0246] For repeating units that reduce the mobility of the main chain, refer to paragraphs

[0144] to

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

[0247] (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 (P) 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 (P) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0248] The resin (P) 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.

[0249] The resin (P) 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 (P) improves resolution, particularly in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

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

[0250] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) The resin (P) may have repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0251] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) The resin (P) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0252]

[0253] 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.

[0254] (Other Repeating Units) Furthermore, the resin (P) may have other repeating units besides those described above. For example, the resin (P) 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. Examples of such repeating units include those described in

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

[0255] Regarding resin (P), further reference can be made to the contents of International Publication No. 2022 / 024928,

[0112] to

[0118] and

[0171] to

[0172] .

[0256] The resin (P) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight (Mw) of the resin (P), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Pd, Mw / Mn) of the resin (P) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. A lower degree of dispersion results in better resolution and resist shape, smoother sidewalls of the resist pattern, and superior roughness.

[0257] The content of resin (P) in the composition of the present invention is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the content of resin (P) is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% 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 only one type of resin (P) or two or more types. If the composition of the present invention contains two or more types of resin (P), it is preferable that their total content is within the range of the above preferred content.

[0258] The composition of the present invention preferably contains a compound (photoacid generator) that generates acid upon irradiation with active light or radiation. The photoacid generator is preferably a compound that generates acid with a pKa of less than 0 upon irradiation with active light or radiation. The pKa of the acid generated from the photoacid generator upon irradiation with active light or radiation may be -0.1 or less, or -0.2 or less. Furthermore, the pKa of the acid generated from the photoacid generator upon irradiation with active light or radiation may be -3.0 or more, or -2.0 or more. The type of photoacid generator is not particularly limited. For example, compound (B) described above may function as a photoacid generator. The resin (P) described above may also function as a photoacid generator. The composition of the present invention may further contain a compound (C) (also simply referred to as "compound (C)") which is a compound different from compound (B) and resin (P) and generates acid upon irradiation with active light or radiation. If the resin (P) does not contain the repeating units having the aforementioned photoacid generating group, it is preferable that the composition of the present invention contains a compound different from the resin (P) that functions as a photoacid generating agent. If the resin (P) does contain the repeating units having the photoacid generating group, the composition of the present invention may or may not contain a separate photoacid generating agent.

[0259] [Compound (C)] Compound (C) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. In addition, in the present invention, compound (C) in the form of a low molecular weight compound and compound (C) incorporated as part of a polymer may be used in combination. When compound (C) is in the form of a low molecular weight compound, the molecular weight of compound (C) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0260] The type of compound (C) is not particularly limited, but it may be a compound containing a cation and an organic anion, for example. Compound (C) is preferably a compound that generates an organic acid upon exposure. Examples of organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imide acid, and tris(alkylsulfonyl)methidic acid.

[0261] Compound (C) may contain a monovalent cation or a divalent or higher cation. The cation is preferably a sulfonium cation or an iodonium cation. It is even more preferable that the cation is 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)").

[0262]

[0263] 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.

[0264] 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.

[0265] 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.

[0266] As the aryl group contained in the arylsulfonium cation, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different from each other. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation 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, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0267] R ２０１ to R ２０３ As the substituent that may be contained in the aryl group, alkyl group, or cycloalkyl group of, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group is preferred. The above substituents may further have a substituent if possible. It is also preferred that the above substituents form an acid-decomposable group by any combination.

[0268] Next, the cation (Za I-2) will be described. The cation (Za I-2) is R in formula (Za I) ２０１ to R ２０３ is each independently a cation representing an organic group having no aromatic ring. The term "aromatic ring" also includes aromatic rings containing a hetero atom. R ２０１ to 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.

[0269] 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.

[0270] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0271]

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0277]

[0278] 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.

[0279] 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.

[0280] 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).

[0281] 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.

[0282] The following are specific examples of cations, but they are not limited to these.

[0283]

[0284]

[0285] The description, specific examples, and preferred range of organic anions that compound (C) may contain are the same as those described above for organic anion (AX).

[0286] When the composition of the present invention contains compound (C), the content of compound (C) is not particularly limited, but may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the content of compound (C) may be 50% by mass or less, 40% by mass or less, or 30% by mass or less, relative to the total solid content of the composition of the present invention. When the composition of the present invention contains compound (C), the composition of the present invention may contain only one type of compound (C), or two or more types. When the composition of the present invention contains two or more types of compound (C), it is preferable that their total content is within the range of the above preferred content.

[0287] The composition of the present invention may contain an acid diffusion control agent. The acid diffusion control agent can act as a quencher that traps the acid generated during exposure, for example from a photoacid generator, and suppresses the reaction of the acid-degradable resin in the unexposed area due to the excess generated acid. The type of acid diffusion control agent is not particularly limited. For example, compound (B) described above may function as an acid diffusion control agent. The resin (P) described above may also function as an acid diffusion control agent. Furthermore, the composition of the present invention may also contain an acid diffusion control agent (D) (also referred to as "compound (D)") that is different from compound (B) and resin (P).

[0288] [Compound (D)] Examples of compound (D) 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] and paragraph

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

[0156] to

[0163] of International Publication No. 2020 / 066824. Specific examples of onium salt compounds (DDs) 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.

[0289] 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.

[0290] Examples of compound (DC) include compounds containing a cation and an organic anion. Compound (DC) may also be a compound that generates an organic acid that is relatively weak to the acid generated from the photoacid generator upon exposure. The description, specific examples, and preferred range of cations that compound (DC) may contain are the same as those described above for compound (C).

[0291] The description, specific examples, and preferred ranges of organic anions that compound (DC) may contain are the same as those described above for organic anions (AX). The pKa of the acid generated from compound (DC) upon irradiation with active light or radiation is preferably greater than the pKa of the acid generated from the photoacid generator, preferably 0.5 or more greater than the pKa of the acid generated from the photoacid generator, and may be 1 or more greater than the pKa of the acid generated from the photoacid generator. The pKa of the acid generated from compound (DC) upon irradiation with active light or radiation is preferably 0 or greater, may be 1 or greater, and may be 2 or greater.

[0292] The molecular weight of compound (D) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0293] If the composition of the present invention contains compound (D), the content of compound (D) is not particularly limited, but may be 0.01 to 50% by mass, 0.1 to 40% by mass, or 1 to 30% by mass, relative to the total solid content of the composition of the present invention. If the composition of the present invention contains compound (D), there may be only one type of compound (D) or two or more types. If the composition of the present invention contains two or more types of compound (D), it is preferable that their total content is within the range of the above preferred content. It is also preferable that the composition of the present invention does not contain compound (D).

[0294] [Hydrophobic Resin] The composition of the present invention may contain a hydrophobic resin different from resin (P). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances.

[0295] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 contained in the side chain portion of the resin. ３ It is preferable that the substructure has one or more of these substructures, and more preferably two or more. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306, which are incorporated herein by reference.

[0296] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and even more preferably 0.1 to 5.0% by mass, based on the total solid content of the composition of the present invention. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0297] [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.

[0298] When the composition of the present invention contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0299] [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). 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. Bio-derived solvents can also be used as solvents. Examples of bio-derived solvents include those described in Japanese Patent Publication No. 2002-363135, U.S. Patent Application Publication No. 2015 / 0004664A1, and International Publication No. 2025 / 106697, as well as commercially available products such as the PURASOLV® ELECT series (see https: / / www.corbion.com / solutions / biochemical-specialties / electronics and https: / / www.corbion.com / - / media / Corbion / Files / PLA-PDFs-7-of-24 / brch-electronics-purasolv-eng-0421_940879.ashx). The bio-derived solvents described above can be purified using methods such as distillation and filtration as appropriate to achieve the purity required in the technical field of the present invention. The solvent content in the composition of the present invention is not particularly limited, but it is preferably set so that the solid content concentration of the composition of the present invention is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. 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 with respect to the total amount of the solvent.

[0300] [Other Additives] The composition of the present invention may further contain other additives such as resin (P) and resins other than hydrophobic resins, dissolution inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in developer (for example, phenol compounds with a molecular weight of 1000 or less, alicyclic or aliphatic compounds containing a carboxyl group). The above-mentioned "dissolution inhibitor" refers to a compound with a molecular weight of 3000 or less that decomposes due to the action of acid and reduces its solubility in organic developer.

[0301] If the composition of the present invention contains other additives, the content of the other additives is not particularly limited, but may be 20% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the total solid content of the composition of the present invention. Only one type of other additive may be used, or two or more types may be used. If two or more types are used, their total content may be within the range of the preferred content described above.

[0302] Furthermore, the composition of the present invention may contain water as an impurity. When water is present as an impurity, a smaller amount of water is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total composition of the present invention. Furthermore, the composition of the present invention may contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are present as impurities, a smaller amount of residual monomers is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total solid content of the composition of the present invention.

[0303] [Photosensitive or Radiation-Sensitive Film, Pattern Forming Method] The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive or radiation-sensitive film of the present invention is preferably a resist film. The present invention also relates to a pattern forming method. The pattern forming method of the present invention preferably includes the steps of: forming a photosensitive or radiation-sensitive film on a substrate using the composition of the present invention; exposing the photosensitive or radiation-sensitive film; and developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern. The pattern forming method of the present invention more preferably includes the steps of: forming a resist film on a substrate using the composition of the present invention (1); exposing the resist film (2); and developing the exposed resist film using a developer to form a pattern (3). Each of the above steps will be described in detail below.

[0304] [Step (1)] Step (1) is a step of forming a resist film on a substrate using the composition of the present invention. Details of the composition of the present invention used in step (1) are as described above.

[0305] 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 (also referred to as the "resist composition"). If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but if it is a polymer, it is preferably made of polyolefins such as polyethylene (PE) and polypropylene (PP) (including high density and ultra-high molecular weight); polyamides such as nylon 6 and nylon 66; polyimide (PI); polyamideimide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimide, polyesters, polysulfones, cellulose, polyfluorocarbons and their derivatives. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0306] The resist composition may be filtered using one filter or a combination of two or more filters. If two or more filters are used, they may be the same filter or different filters. The resist composition may also be circulated and filtered repeatedly using the same filter.

[0307] The resist composition can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) 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 preferred rotation speed when spin coating using a spinner is 1000 to 3000 rpm (rotations per minute). After applying the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films, etc.) may be formed in the layer below the resist film.

[0308] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in at least one of a normal exposure machine and a developer machine, and may also be carried out using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0309] 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.

[0310] A topcoat may be formed on the upper layer of the resist film using a topcoat composition. 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 resist composition.

[0311] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). Methods of exposure include irradiating the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0312] It is preferable to bake (heat) the image after exposure but before developing. This step is also called post-exposure baking. Baking promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. The baking temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The baking time is not particularly limited, but 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 at least one of a normal exposure machine and a developer, and may also be done using a hot plate or the like.

[0313] [Step (3)] Step (3) is a step in which the resist film exposed in step (2) is developed using a developer to form a pattern. By performing step (3), a resist pattern (also simply called a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (hereinafter also called an organic developer). 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 on the substrate surface using surface tension and letting it stand for a certain period of time to develop (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). The development time is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C. In step (3), a step of stopping the development process while substituting with another solvent may be performed.

[0314] 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.

[0315] 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. Bio-derived solvents can also be used as the organic solvent in the organic developer. Examples of bio-derived solvents include those described in U.S. Patent Application Publication 2025 / 0068079A1, Proceedings of SPIE, 12957, 1295719 (2024), etc. The bio-derived solvents described above can be purified by appropriate methods such as distillation and filtration to achieve the purity required in the technical field of the present invention.

[0316] The above organic solvents may be mixed in multiple quantities, or mixed with solvents other than the above organic solvents or with water. The water content of the organic 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 organic developer.

[0317] The organic developer preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having 9 to 12 carbon atoms. The hydrocarbon having 9 to 12 carbon atoms contained in the organic developer may be just one type or two or more types. The hydrocarbon having 9 to 12 carbon atoms is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes and cycloalkanes, more preferably an alkane, even more preferably at least one selected from the group consisting of nonanes, decanes, undecanes and dodecanes, particularly preferably at least one selected from the group consisting of undecanes and dodecanes, and most preferably undecanes. The hydrocarbon having 9 to 12 carbon atoms may also contain structural isomers.

[0318] The butyl acetate content in the organic developer 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 organic developer. The hydrocarbon content (total amount if multiple hydrocarbons with 9 to 12 carbon atoms are included) in the organic developer is preferably 1% to 35% by mass, more preferably 5% to 30% by mass, and even more preferably 10% to 25% by mass, based on 100% by mass of the entire organic developer.

[0319] The mass ratio of butyl acetate to hydrocarbons having 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having 9 to 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, even more preferably 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0320] Organic developers may contain other components in addition to butyl acetate and hydrocarbons having 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having 9 to 12 carbon atoms, surfactants, antioxidants, and basic compounds.

[0321] [Rinsing Step] After step (3), rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Bio-derived solvents can also be used as the rinsing solution. Examples of bio-derived solvents include the bio-derived solvents presented as organic solvents in the organic developer above.

[0322] The rinsing method is not particularly limited and includes, for example, a method in which rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (rotary coating method), a method in which the substrate is immersed in a tank filled with rinsing liquid for a certain period of time (dip method), and a method in which rinsing liquid is sprayed onto the surface of the substrate (spray method).

[0323] Furthermore, the pattern formation method of the present invention may include a heating step (Post Bake) after step (3). This step removes any developer and rinse solution remaining between and inside the patterns. This step also has the effect of mellowing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250°C (preferably 90 to 200°C) for, for example, 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0324] 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 preferred method is to form 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. Dry etching is not particularly limited, but oxygen plasma etching is preferred.

[0325] In the pattern forming method of the present invention, the developer, resist composition, and other various materials (e.g., solvent, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) used are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 ppt or more. 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.

[0326] 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, performing filter filtration on 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®. Details of filtration using filters are described in paragraph

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

[0327] 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 equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0328] [Method for Manufacturing Electronic Devices] This specification relates to a method for manufacturing electronic devices, including the pattern forming method of the present invention described above, and to electronic devices manufactured by this manufacturing method. Preferred embodiments of the electronic devices of this specification include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0329] 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.

[0330] <Components of the resist composition> The components of the resist composition used in the examples and comparative examples are shown below.

[0331] [Resin (P)] Resins (P) used are P-1 to P-12. P-1 to P-12 contain the repeating units shown in Table 1 below in the amounts shown in the table. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of P-1 to P-12 are also listed in the table. 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). The content of the repeating units is, １３ Measurement is performed using C-NMR (nuclear magnetic resonance).

[0332]

[0333] The structural formula of the repeating unit is shown below. Me represents a methyl group.

[0334]

[0335] [Compound (B)] Compound (B) is a compound containing a cation and an organic anion in a 1:1 (molar ratio), as shown in Tables 2-3 below. The structural formulas of cations C-1 to C-22, CX-1 and CX-2, and organic anions A-1 to A-6 are shown below. Me represents a methyl group. C-1 to C-22 are cations represented by formula (BC-1). CX-1 and CX-2 are not cations represented by formula (BC-1). However, in the table below, compounds containing CX-1 and CX-2 as cations may also be listed in the Compound (B) column for convenience.

[0336]

[0337]

[0338]

[0339]

[0340] [Compound (C)] Compounds (C) are RC-1 to RC-2. The structures of RC-1 to RC-2 are shown below. RC-1 to RC-2 can function as photoacid generators. RC-1 generates an acid with a pKa of -0.63 upon irradiation with active light or radiation. RC-2 generates an acid with a pKa of -3.29 upon irradiation with active light or radiation.

[0341]

[0342] [Compound (D)] Compounds D-1 to D-2 are used as compound (D). The structures of D-1 to D-2 are shown below. D-1 to D-2 can function as acid diffusion control agents. D-1 generates an acid with a pKa of 3.01 upon irradiation with active light or radiation.

[0343]

[0344] [Hydrophobic Resin] T-1 is used as the hydrophobic resin. The structural formula of T-1, the content (mol%) of each repeating unit, the weight-average molecular weight (Mw), and the degree of dispersion (Mw / Mn) are shown below. The content of each repeating unit is the molar ratio of each repeating unit to the total number of repeating units.

[0345]

[0346] [Solvent] The following solvents S-1 to S-4 are used: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: γ-butyrolactone

[0347] [Preparation of Resist Compositions] Dissolve the components (solids) shown in Tables 2 and 3 below in the solvents shown in the tables and mix so that the solids concentration is 3.0% by mass. Filter the resulting mixture through a polyethylene filter with a pore size of 0.03 μm to prepare the resist compositions (R-1 to R-50, XR-1 to XR-3). Solids refer to all components other than the solvent. The obtained resist compositions are used in the examples and comparative examples. In the tables, the "Content" column shows the content (unit mass%) of each component relative to the total solids in the resist composition. If two or more types of each component are used, the types and their contents are shown separated by " / ". The order in which the types and contents separated by " / " are listed corresponds. However, if two types of cations of compound (B) are used, the content of the compound containing each cation and the organic anion in a 1:1 (molar ratio) is shown separated by " / ". For example, resist composition R-46 contains 10.0% by mass of a compound (B) containing C-3 and A-4 in a 1:1 molar ratio, and 12.4% by mass of a compound (B) containing C-9 and A-4 in a 1:1 molar ratio. When two types of organic anions are used in compound (B), the content of the compound containing the cation and each organic anion in a 1:1 molar ratio is indicated separated by a " / ". For example, resist composition R-45 contains 22.2% by mass of a compound (B) containing C-1 and A-1 in a 1:1 molar ratio, and 12.0% by mass of a compound (B) containing C-1 and A-4 in a 1:1 molar ratio. For solvents, the type of compound used and the mixing ratio (ratio based on mass, with the total solvent being 100) are indicated separated by a " / ". The order in which the types and mixing ratios separated by " / " are listed corresponds to the order in which they are listed.

[0348]

[0349]

[0350] [Examples 1-1 to 1-50, Comparative Examples X1-1 to X1-3] <Pattern Formation Method (1): EB Exposure, Alkali Development (Positive)> The resist composition shown in Table 4 below is applied to a 6-inch Si wafer that has been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by changing the Si wafer to a chromium substrate. Pattern irradiation is performed on the wafer having the resist film obtained above using an electron beam lithography system (Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, drawing is performed so that a 1:1 line and space pattern is formed. After electron beam lithography, post-exposure heating (also called "PEB treatment") is performed by heating on a hot plate at 100°C for 60 seconds. Next, as a developing process, the wafer is immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, then rinsed with water for 30 seconds and dried. After that, the wafer is rotated at 4000 rpm for 30 seconds, and then baked at 95°C for 60 seconds to dry.

[0351] <Performance Evaluation> [LWR Performance] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi S-9380II). The exposure amount when resolving a 1:1 line-and-space resist pattern with a line width of 50 nm is defined as the sensitivity (Eop). A line-and-space pattern with a line width of 50 nm (1:1) that is resolved with the exposure amount that shows the above sensitivity (Eop) is observed from above using a length-measuring scanning electron microscope (SEM (Hitachi S-9380II)). The line width of the pattern is observed at an arbitrary point, and its standard deviation (σ) is determined. The measurement variability of the line width is evaluated using 3σ, and the value of 3σ is defined as LWR (nm). The value of LWR (nm) is evaluated according to the following criteria. The smaller the value of LWR (nm), the better the LWR. [Judgment criteria] A: 3.4 nm or less B: 3.5 to 4.4 nm C: 4.5 nm or more

[0352] [PED Stability] For a 1:1 line-and-space pattern with a line width of 50 nm and a space width of 50 nm, the line width (L0h) (unit: nm) is measured when PEB processing is performed immediately after exposure, and when PEB processing is performed 1 hour after exposure, and the line width (L1h) (unit: nm) is measured. PEB processing is performed by heating at 100°C for 60 seconds. The line width change rate is calculated using the following formula and is used as an indicator of PED stability. "│L1h-L0h│" is the absolute value of "L1h-L0h". Line width change rate (%) = 100 × (│L1h-L0h│) / 50 The line width change rate is evaluated according to the following criteria. A smaller line width change rate indicates better PED stability. [Judgment Criteria] A: Line width change rate is less than 2% B: Line width change rate is 2% or more and less than 5% C: Line width change rate is 5% or more

[0353] The results shown in Table 4 below are obtained.

[0354]

[0355] [Examples 2-1 to 2-50, Comparative Examples X2-1 to X2-3] <Pattern Formation Method (2): EUV Exposure, Alkali Development (Positive)> The same steps as in Pattern Formation Method (1) above are performed, except that an EUV exposure apparatus (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) is used instead of an electron beam lithography apparatus, using the resist composition shown in Table 5 below. LWR and PED stability are evaluated using the same method as described above. The results shown in Table 5 below are obtained.

[0356]

[0357] As shown in Tables 4 and 5 above, the resist compositions of the examples exhibit excellent LWR and PED stability.

[0358] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition with excellent LWR and PED stability, a photosensitive or radiation-sensitive film formed from the above photosensitive or radiation-sensitive resin composition, a pattern forming method using the above photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0359] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2025-051619 filed on 26 March 2025, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin, and a compound (B) containing an organic anion and a cation represented by the following formula (BC-1). In formula (BC-1), Ar １ and Ar ２ each independently represent an aromatic ring. Ar １ and Ar ２ may be bonded to each other to form a ring. n represents an integer of 1 to 3. Ar １ when a plurality of Ar １ are present, the plurality of Ar １ may be the same as or different from each other, and a plurality of Ar ２ when a plurality of Ar ２ are present, the plurality of Ar ２ may be the same as or different from each other, and a plurality of Ar ｂ１ and R ｂ２ each independently represent a substituent. R ｂ１ and R ｂ２ may be bonded to each other to form a ring. k and m each independently represent an integer of 0 or more. When n represents 2 or 3, the plurality of k may be the same or different. When n represents 1, the plurality of m may be the same or different. R ｂ１ when a plurality of R ｂ１ are present, the plurality of R ｂ１ may be the same as or different from each other, and a plurality of R ｂ２ when a plurality of R ｂ２ are present, the plurality of R ｂ２ may be the same as or different from each other, and a plurality of R ｂ１ represents a group represented by any one of the following formulas (Y-1) to (Y-4). Y ｂ１ when a plurality of Y ｂ１ are present, the plurality of Y may be the same as or different from each other. z represents an integer of 1 or more. When n represents 2 or 3, the plurality of z may be the same or different. In formulas (Y-1) to (Y-4), * represents a bonding position. T １ and T ２ Each of these independently represents a single bond or a divalent linking group. １ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A １ This indicates the connection position with L. ２ teeth ＊１ -(C=O)O- ＊２ or -SO ２ It represents -. ＊１ This indicates the bonding position with the oxygen atom. ＊２ is A ３ This indicates the connection position with A. １ Ha-CHR ｂ５ - or ＊３ -CR ｂ６ R ｂ７ C(=O)- ＊４ It represents. ＊３ is L １ This indicates the connection point with [the other element]. ＊４ Ar ３ Represents the connection position with R. ｂ５ and Ar ３ They may bond to each other to form a ring. ｂ６ or R ｂ７ and Ar ３ They may be joined to each other to form a ring. A ２ Ha-CR ｂ８ =CR ｂ９ - or -C≡C- represents R ｂ８ or R ｂ９ and Ar ４ They may be joined to each other to form a ring. ３ and Ar ４ Each of these independently represents an aromatic ring. A ３ Ha-CHR ｂ１０ - or ＊５ -CR ｂ１１ R ｂ１２ C(=O)- ＊６ It represents. ＊５ is L ２ This indicates the connection point with [the other element]. ＊６ Ar １ Represents the connection position with R. ｂ１０ and Ar １ They may bond to each other to form a ring. ｂ１１ or R ｂ１２ and Ar １ They may be joined to each other to form a ring. A ４ Ha-CR ｂ１３ =CR ｂ１４ - or -C≡C- represents R ｂ１３ or R ｂ１４ and Ar １ They may bond to each other to form a ring. ｂ３ and R ｂ４ Each of these independently represents a substituent. However, R ｂ３ and R ｂ４ It does not bond with adjacent oxygen atoms at tertiary carbon atoms. ｂ５ ~R ｂ１４ Each of these independently represents a hydrogen atom or a substituent.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin comprises repeating units having phenolic hydroxyl groups.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin comprises a repeating unit represented by the following formula (Ga1). In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ａ１ represents a single bond or a divalent linking group. X ａ１ represents -O- or -C(=O)O-. R ａ３ and L ａ１ may be bonded to each other to form a ring. G represents a group represented by the following formula (G-1) or (G-2). In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ５ and R ａ６ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. R ａ４ and R ａ５ may be bonded to each other to form a ring. R ａ４ and L in formula (Ga1) ａ１ may be bonded to each other to form a ring. * represents a bonding site. In formula (G-2), R ａ７ , R ａ８ and R ａ９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group or an alkenyl group. Two of R ａ７ , R ａ８ and R ａ９ may be bonded to each other to form a ring. * represents a bonding site.

4. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the organic anion is an anion represented by the following formula (BA-1). In formula (BA-1), R Ｘ１ represents a substituent.

5. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the organic anion is at least one selected from the group consisting of anions represented by the following formula (BA-2) and anions represented by the following formula (BA-3). In formula (BA-2), R Ｘ２ represents a substituent. In formula (BA-3), L Ｘ１ These are single bonds, -(C=O)- or -SO ２ Represents -. R Ｘ３ and R Ｘ４ Each of these independently represents a substituent. Ｘ３ and R Ｘ４ They may be joined together to form a ring.

6. T in the above formula (Y-1) １ and T in formula (Y-2) ２ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein represents a single bond.

7. Y in the above formula (BC-1) ｂ１ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein it has at least one selected from the group consisting of the group represented by formula (Y-1) and the group represented by formula (Y-3).

8. R in the above formula (Y-1) ｂ５ and R in formula (Y-3) ｂ１０ The photosensitive or radiation-sensitive resin composition according to claim 7, wherein represents a hydrogen atom.

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

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

11. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.

12. A pattern forming method comprising the steps of: forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10; exposing the active photosensitive or radiation-sensitive film; and developing the exposed active photosensitive or radiation-sensitive film using a developer to form a pattern.

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

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