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

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing a photoacid generator, a solvent, and a resin that has a repeating unit and in which a condensed ring is formed in the repeating unit by a reaction with an acid; an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition; a pattern; a pattern formation method; and a method for manufacturing an electronic device.

Description

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

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

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

[0004] Patent Document 1 describes a photosensitive or radiation-sensitive resin composition containing an onium salt compound (A) represented by a specific general formula (1) and a crosslinking agent (C).

[0005] Japanese Patent Application Publication No. 2018-189758

[0006] In recent years, the performance requirements for resist compositions have become increasingly stringent. In particular, there is a demand for improved resolution and LWR (Line Width Roughness) performance when forming fine patterns. Furthermore, there is a need for photosensitive or radiation-sensitive resin compositions that can improve the pattern shape when forming fine patterns.

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

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

[0009] [1] A photosensitive or radiation-sensitive resin composition comprising a resin having repeating units in which a condensed ring is formed within the repeating units by a reaction with an acid, a photoacid generator, and a solvent. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the repeating units are repeating units (A) having two or more aromatic rings linked by single bonds or divalent linking groups, and the condensed ring is formed from two of the two or more aromatic rings.

[0010] [3] The photosensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit (A) is a repeating unit represented by the following formula (1).

[0011]

[0012] In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２each independently represent an aromatic ring. R ｘ１ represents a hydrogen atom, or a substituent capable of forming a ring with Ar ２ through a reaction with an acid. R ｘ２ represents a hydrogen atom, or a substituent capable of forming a ring with Ar １ through a reaction with an acid. At least one of R ｘ１ and R ｘ２ is not a hydrogen atom.

[0013] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein in the formula (1), at least one of R ｘ１ and R ｘ２ is a group represented by the following formula (2) or a group represented by the following formula (3).

[0014]

[0015] In the formula (2), R ｂ１ represents a hydrogen atom or a group leaving by the action of an acid. In the formula (3), R ｂ２ represents a hydrogen atom or a group leaving by the action of an acid. R ｂ３ and R ｂ４ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * represents a bonding position.

[0016] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to [3] or [4], wherein in the formula (1), L ２ represents a single bond, or any one of -O-, -S-, -NR Ｌ１ -, and -CR Ｌ２ R Ｌ３ -, and R Ｌ１ to R Ｌ３ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [2] to [5], wherein the repeating unit (A) is a repeating unit represented by the following formula (4).

[0017]

[0018] In the formula (4), R ａ１ to R ａ３Each of these independently represents a hydrogen atom or a substituent. １ R represents a single bond or a divalent linking group. ｘ３ R represents a hydrogen atom, or a group represented by the following formula (2) or formula (3). ｘ４ R represents a group represented by the following formula (2) or the following formula (3). ｃ１ R represents a substituent. ｃ２ represents a substituent other than the group represented by formula (2) below or the group represented by formula (3) below. p represents an integer from 1 to 5. q represents an integer from 0 to (5-p). m represents an integer from 0 to 4. n represents an integer from 0 to (5-p-q). When p, q, m, and n are each 2 or greater, the structures of each substituent may be the same or different. R ｘ３ However, in the case of a hydrogen atom, q is 1 or greater, and there are q R ｘ４ At least one of these groups is bonded to the ortho position of the following group.

[0019]

[0020] R Ｘ３ , R ｃ１ , p, and m are as described above. When q is 0, R ｘ３ This represents a group represented by the following formula (2) or a group represented by the following formula (3).

[0021]

[0022] In formula (2), R ｂ１ R represents a group that is eliminated by the action of a hydrogen atom or an acid. In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

[0023] [7] The photosensitive or radiation-sensitive resin composition according to [6], wherein p + q in formula (4) is an integer of 2 or more. [8] The photosensitive or radiation-sensitive resin composition according to any one of [2] to [7], wherein the content of the repeating unit (A) is 50 mol% or more with respect to the total repeating units in the resin. [9] A photosensitive or radiation-sensitive film formed from the photosensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10] A pattern formed from the photosensitive or radiation-sensitive film according to [9].

[0024]

[11] A method for forming a pattern, comprising the steps of: forming an active photosensitive or radiation-sensitive film on a substrate with a composition according to any one of [1] to [8]; exposing the active photosensitive or radiation-sensitive film; and developing the exposed active photosensitive or radiation-sensitive film with a developer.

[12] The method for forming a pattern according to

[11] , wherein the repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, the condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is an alkaline developer.

[0025]

[0026] In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２ Each of these independently represents an aromatic ring. ｘ１ Ar is a reaction involving hydrogen atoms or acids. ２ R represents a substituent that can form a ring. ｘ２ Ar is a reaction involving hydrogen atoms or acids. １ R represents a substituent that can form a ring. ｘ１ , R ｘ２Of these, at least one is not a hydrogen atom. In formula (1) above, R ｘ１ , R ｘ２ Of these, at least one is a group represented by the following formula (2).

[0027]

[0028] In formula (2), R ｂ１ * represents a group that is eliminated by the action of a hydrogen atom or an acid. * represents the bond position.

[0029]

[13] The pattern forming method according to

[11] , wherein the repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, a condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is a developer containing an organic solvent.

[0030]

[0031] In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２ Each of these independently represents an aromatic ring. ｘ１ Ar is a reaction involving hydrogen atoms or acids. ２ R represents a substituent that can form a ring. ｘ２ Ar is a reaction involving hydrogen atoms or acids. １ R represents a substituent that can form a ring. ｘ１ , R ｘ２ Of these, at least one is not a hydrogen atom. In formula (1) above, R ｘ１ , R ｘ２ Of these, at least one is a group represented by the following formula (3).

[0032]

[0033] In formula (3), R ｂ２represents a hydrogen atom or a group that is eliminated by the action of an acid. R ｂ３ , R ｂ４ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * represents a binding position.

[0034]

[14] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of

[11] to

[13] .

[0035] According to the present invention, there can be provided an actinic ray-sensitive or radiation-sensitive resin composition excellent in resolution, LWR performance, and pattern shape. Further, according to the present invention, there can be provided an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[0036] Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0037] In the present specification, "actinic ray" or "radiation" means, for example, emission lines from a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, electron beams (EB: Electron Beam), and the like. In the present specification, "light" means actinic ray or radiation. In the present specification, unless otherwise specified, "exposure" includes not only exposure with emission lines from a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV, and the like, but also drawing with particle beams such as electron beams and ion beams. In the present specification, "to" is used to mean including the numerical values described before and after it as the lower limit and the upper limit.

[0038] In the present specification, (meth)acrylate represents at least one of acrylate and methacrylate. Further, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0039] 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).

[0040] 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.

[0041] (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 metactyl groups. Examples of substituents include acyl groups such as liloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; alkylsulfonyl groups; arylsulfonyl 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.

[0042] 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".

[0043] 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).

[0044] 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.

[0045] 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.

[0046] In this specification, "solids" refers to components that form photosensitive or radiation-sensitive films, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered a solid, even if its state is liquid.

[0047] <Photosensitive or Radiation-Sensitive Resin Composition> The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is a photosensitive or radiation-sensitive resin composition that contains a resin having repeating units in which condensed rings are formed within the repeating units by a reaction with an acid, a photoacid generator, and a solvent.

[0048] Although the mechanism by which the above-described effects are obtained by the composition of the present invention is not yet clear, the inventors have made the following hypothesis. However, the present invention is not limited in any way by the following hypothesis mechanism.

[0049] In general, in a resist composition (negative resist composition) containing a resin and a crosslinking agent, the exposed areas become rigid due to crosslinking of the resins themselves or through the crosslinking agent by the acid generated by exposure, and the solubility of the developer decreases. Therefore, a contrast can be created between the exposed and unexposed areas, but there was room for improvement in terms of the effects described above. The present inventors focused on creating a contrast between the exposed and unexposed areas within the repeating units of the resin, rather than through such crosslinking between resins. The composition of the present invention contains a resin having repeating units in which condensed rings are formed within the repeating units by a reaction with an acid, a photoacid generator, and a solvent. In the exposed areas, condensed rings are formed within the repeating units by a reaction with an acid generated by exposure. Thus, according to the composition of the present invention, in the exposed areas, the formation of condensed rings within the repeating units of the resin (so-called intramolecular cyclization) occurs, which rigidifies the exposed areas and reduces the solubility of the developer. Therefore, a contrast can be created between the exposed and unexposed areas. According to the composition of the present invention, compared to the negative-type resist composition using the crosslinking agent described above, crosslinking between resins does not occur, but intramolecular cyclization occurs within the repeating units of the resin. Therefore, the number of dissolving units in the unexposed areas becomes smaller, and it is thought that the contrast between the unexposed and exposed areas becomes more pronounced. Accordingly, it is thought that the above-mentioned effects can be obtained with the composition of the present invention.

[0050] The composition of the present invention is preferably a resist composition, and may be 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 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.

[0051] [Resin] The composition of the present invention contains a resin (also referred to as "resin (P)") having repeating units, wherein a condensed ring is formed within the repeating units by a reaction with an acid. The acid is typically an acid generated from a photoacid generator contained in the composition of the present invention. Resin (P) is a resin in which a condensed ring is formed within the repeating units by a reaction with an acid (so-called intramolecular cyclization), and the condensed ring is not particularly limited.

[0052] The repeating unit described above is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, and it is preferable that the fused ring is formed from two of the two or more aromatic rings. The divalent linking group is not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, alkylene group (preferably 1 to 5 carbon atoms), alkenylene group (preferably 2 to 5 carbon atoms), arylene group (preferably 6 to 20 carbon atoms), -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ - and groups formed by combining two or more of these are examples. Ｌ１ ~R Ｌ３ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Ｌ１ ~R Ｌ３ These are, respectively, L as described below. ２ R in the divalent linking group represented by Ｌ１ ~R Ｌ３ The same applies, and the preferred range is also the same. Alkylene group, alkenylene group, arylene group, RＬ１ ~R Ｌ３ The alkyl group, aryl group, and heteroaryl group may have substituents. In one preferred embodiment, the repeating unit (A) is preferably a repeating unit having two or more aromatic rings linked by single bonds.

[0053] In two or more aromatic rings, the aromatic rings may be aromatic hydrocarbon rings or aromatic heterorings. The number of member carbon atoms in an aromatic hydrocarbon ring is not particularly limited, but for example, 6 to 20 is preferred, and 6 to 15 is more preferred. As aromatic hydrocarbon rings, benzene rings or naphthalene rings are preferred, and benzene rings are more preferred. The number of member atoms in an aromatic heteroring is preferably 4 to 20, and 5 to 10 is more preferred. As aromatic heterorings, it is preferable that they contain at least one of sulfur atoms, nitrogen atoms, and oxygen atoms. As aromatic heterorings are not particularly limited, but examples include five-membered aromatic heterorings such as pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, triazole rings, thiophene rings, and furan rings; six-membered aromatic heterorings such as pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, thiazine rings, and oxazine rings; and fused aromatic heterorings such as indole rings, quinoline rings, and isoquinoline rings. The two or more aromatic rings may each have substituents. The two or more aromatic rings may be identical or different.

[0054] It is preferable that the fused ring is formed from two of the two or more aromatic rings, and it is preferable that the "two of the two or more aromatic rings" are two aromatic rings linked by a single bond or a divalent linking group. It is preferable that at least one of the "two or more aromatic rings" has a substituent that can form a fused ring by an acid reaction.

[0055] The substituents that can form a fused ring in an acid reaction are not particularly limited, but examples include the group represented by formula (2) described below, the group represented by formula (3) described below, or the group represented by formula (5) below.

[0056]

[0057] In formula (5), * represents a bonding position.

[0058] In a preferred embodiment, "two of two or more aromatic rings" is two aromatic rings linked via a single bond or a divalent linking group, and when at least one of the above "two of two or more aromatic rings" has a substituent capable of forming a fused ring through an acid-catalyzed reaction, the substituent is preferably in the ortho position relative to the single bond or the divalent linking group.

[0059] In resin (P), a fused ring is formed in the above repeating unit through an acid-catalyzed reaction. An example of fused ring formation ((A) to (C)) is shown below.

[0060]

[0061]

[0062]

[0063] As described above, a fused ring is formed in the above repeating unit through an acid-catalyzed reaction.

[0064] The repeating unit (A) is preferably a repeating unit represented by the following formula (1).

[0065]

[0066] In formula (1), R ａ１ to R ａ３ each independently represent a hydrogen atom or a substituent. L １ , L ２ each independently represent a single bond or a divalent linking group. Ar １ , Ar ２ each independently represent an aromatic ring. R ｘ１ represents a hydrogen atom or a substituent capable of forming a ring with Ar ２ through an acid-catalyzed reaction. R ｘ２ represents a hydrogen atom or a substituent capable of forming a ring with Ar １ through an acid-catalyzed reaction. At least one of R ｘ１ and R ｘ２ is not a hydrogen atom.

[0067] R ａ１ to R ａ３ The substituent represented by is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group.

[0068] R ａ１ to R ａ３ The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a trifluoromethyl group. R ａ１ to R ａ３ Descriptions, specific examples, and preferred ranges of the alkyl groups contained in the alkoxy group and alkylthio group represented by are the same as those for the alkyl group represented by R ａ１ to R ａ３ above.

[0069] R ａ１ to R ａ３ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The cycloalkyl group may have a substituent. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, a sulfonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R ａ１ to R ａ３ Descriptions, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy group and cycloalkylthio group represented by are the same as those for the cycloalkyl group of Rａ１ ~R ａ３ This is the same as the cycloalkyl group represented by .

[0070] R ａ１ ~R ａ３ 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents. ａ１ ~R ａ３ The explanation, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by are as follows: ａ１ ~R ａ３ This is the same as the aryl group represented by .

[0071] R ａ１ ~R ａ３ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. ａ１ ~R ａ３ The heteroaryl group represented by preferably has 4 to 20 ring member atoms, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, and benzothiophenyl group. The heteroaryl group may have substituents.

[0072] L １ The divalent linking groups represented by are not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, alkylene group (preferably 1 to 5 carbon atoms), alkenylene group (preferably 2 to 5 carbon atoms), arylene group (preferably 6 to 20 carbon atoms), -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ - and groups formed by combining two or more of these are examples. Ｌ１ ~RＬ３ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Ｌ１ ~R Ｌ３ These are, respectively, L as described below. ２ R in the divalent linking group represented by Ｌ１ ~R Ｌ３ The same applies, and the preferred range is also the same. Alkylene group, alkenylene group, arylene group, R Ｌ１ ~R Ｌ３ The alkyl group, aryl group, and heteroaryl group may have substituents. The substituents are not particularly limited, but in one preferred embodiment, for example, R Ｘ１ It is also acceptable. L １ The divalent linking groups represented by are -O-, -CO-, -CO ２ - Preferably, it is an alkylene group, an arylene group, or a group formed by a combination of two or more of these. In one preferred embodiment, L １ It is preferable that this represents a single bond.

[0073] In formula (1), Ar １ The aromatic ring represented by includes an arylene group or a heteroarylene group. １ The arylene group represented by is not particularly limited, but for example, an arylene group having 6 to 20 carbon atoms is possible, and an arylene group having 6 to 15 carbon atoms is preferred. The arylene group is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferred. １ The heteroarylene group represented by is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. １ The number of ring member atoms of the heteroarylene group represented by is preferably 4 to 20, and more preferably 5 to 15. The aromatic ring is R of formula (1). Ｘ１In addition, it may have further substituents. The substituents are not particularly limited. In one preferred embodiment, the substituent is, for example, R Ｘ１ That's fine.

[0074] In formula (1), Ar ２ The aromatic ring represented by Ar can be an allerene group or a heteroarylene group. ２ The arylene group represented by is not particularly limited, but for example, an arylene group having 6 to 20 carbon atoms is possible, and an arylene group having 6 to 15 carbon atoms is preferred. The arylene group is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferred. ２ The heteroarylene group represented by is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. ２ The number of ring member atoms of the heteroarylene group represented by is preferably 4 to 20, and more preferably 5 to 15. The aromatic ring is R of formula (1). Ｘ２ In addition, it may have further substituents. The substituents are not particularly limited. In one preferred embodiment, the substituent is, for example, R Ｘ２ That's fine.

[0075] L ２ The divalent linking groups represented by are not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ - are some examples. R Ｌ１ ~R Ｌ３ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Ｌ１ ~R Ｌ３The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, trifluoromethyl group, and the like.

[0076] R Ｌ１ ~R Ｌ３ The aryl group represented 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents.

[0077] R Ｌ１ ~R Ｌ３ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｌ１ ~R Ｌ３ The number of ring member atoms of the heteroaryl group represented by is preferably 4 to 20, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, benzothiophenyl group, etc. The heteroaryl group may have substituents. As described above, alkyl groups, aryl groups, and heteroaryl groups may have substituents. The substituents are not particularly limited, but one preferred embodiment is, for example, R Ｘ１ It is also acceptable. L ２ The divalent linking groups represented are -O-, -S-, -CO-, -CO ２ -, -NR Ｌ１ - or -CR Ｌ２ R Ｌ３ - is preferred, -O-, -S-, -NR Ｌ１ - or -CR Ｌ２ R Ｌ３- is more preferable. In one preferred embodiment, L ２ These are single bonds, or -O-, -S-, -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ It is preferable to represent either - or .

[0078] R ｘ１ The reaction by acid represented by Ar ２ The substituents that can form a ring are not particularly limited, but examples include the group represented by formula (2) described below, the group represented by formula (3) described below, or the group represented by formula (5) above.

[0079] R ｘ２ The reaction by acid represented by Ar １ The substituents that can form a ring are not particularly limited, but examples include the group represented by formula (2) described below, the group represented by formula (3) described below, or the group represented by formula (5) above.

[0080] R ｘ１ , R ｘ２ At least one of them is not a hydrogen atom. ｘ１ Ar reacts with acid ２ R represents a substituent that can form a ring with it. ｘ２ Ar reacts with acid １ It is also a preferred embodiment to represent substituents that can form a ring.

[0081] In the above formula (1), R ｘ１ , R ｘ２ Preferably, at least one of these is a group represented by the following formula (2) or a group represented by the following formula (3).

[0082]

[0083] In formula (2), R ｂ１ R represents a group that is eliminated by the action of a hydrogen atom or an acid. In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

[0084] R ｂ１ , R ｂ２ The group that is removed by the action of the acid represented by is the same as the group that is removed by the action of the acid in a repeating unit having a group that decomposes by the action of the acid and increases in polarity, as described later, and the preferred range is also the same.

[0085] R ｂ３ , R ｂ４ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, trifluoromethyl group, and the like.

[0086] R ｂ３ , R ｂ４ The aryl group represented 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents.

[0087] R ｂ３ , R ｂ４ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. ｂ３ , R ｂ４ The heteroaryl group represented by preferably has 4 to 20 ring member atoms, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, and benzothiophenyl group. The heteroaryl group may have substituents.

[0088] The repeating unit (A) is preferably a repeating unit represented by the following formula (4).

[0089]

[0090] In formula (4), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ R represents a single bond or a divalent linking group. ｘ３ R represents a hydrogen atom, or a group represented by formula (2) or formula (3) above. ｘ４ R represents the group represented by formula (2) or the group represented by formula (3) above. ｃ１ R represents a substituent. ｃ２ represents a substituent other than the group represented by formula (2) or the group represented by formula (3) above. p represents an integer from 1 to 5. q represents an integer from 0 to (5-p). m represents an integer from 0 to 4. n represents an integer from 0 to (5-p-q). When p, q, m, and n are each 2 or greater, the structures of each substituent may be the same or different. R ｘ３ However, in the case of a hydrogen atom, q is 1 or greater, and there are q R ｘ４ At least one of these groups is bonded to the ortho position of the following group.

[0091]

[0092] R Ｘ３ , R ｃ１ , p, and m are as described above. When q is 0, R ｘ３ This represents the group represented by formula (2) or the group represented by formula (3) above.

[0093] R ａ１ ~R ａ３ The substituent represented by is R in formula (1) above. ａ１ ~R ａ３ The substituents represented by are the same, and the preferred range is also the same. １ The divalent linking group represented by is L in formula (1) above. １ This is similar to the divalent linking group represented by , and the preferred range is also the same.

[0094] R ｃ１The substituent represented by is not particularly limited, but examples include alkyl groups, alkoxy groups, alkylthio groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, and arylthio groups.

[0095] R ｃ１ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and trifluoromethyl groups. ｃ１ The explanation, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by are given in the above R. ｃ１ It is the same as the alkyl group represented by .

[0096] R ｃ１ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group may have substituents. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, and groups having heteroatoms such as ester bonds, or vinylidene groups. Furthermore, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by vinylene groups. ｃ１ The explanation, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy group and cycloalkylthio group represented by are given in the above R. ｃ１ This is the same as the cycloalkyl group represented by .

[0097] R ｃ１The 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents. ｃ１ The explanation, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by are as follows: ｃ１ This is the same as the aryl group represented by .

[0098] R ｃ１ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. ｃ１ The heteroaryl group represented by preferably has 4 to 20 ring member atoms, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, and benzothiophenyl group. The heteroaryl group may have substituents.

[0099] As mentioned above, each group, as an example of a substituent, may have further substituents. The further substituents are not particularly limited. Also, R ｃ１ The substituent represented by may be the substituent T mentioned above, or it may be the group represented by formula (2) or the group represented by formula (3).

[0100] R ｃ２ The substituent represented by is not particularly limited as long as it is a substituent other than the group represented by formula (2) or the group represented by formula (3) above, but examples include alkyl groups, alkoxy groups, alkylthio groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, and arylthio groups.

[0101] R ｃ２The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and trifluoromethyl groups. ｃ２ The explanation, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by are given in the above R. ｃ２ It is the same as the alkyl group represented by .

[0102] R ｃ２ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group may have substituents. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, and groups having heteroatoms such as ester bonds, or vinylidene groups. Furthermore, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by vinylene groups. ｃ２ The explanation, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy group and cycloalkylthio group represented by are given in the above R. ｃ２ This is the same as the cycloalkyl group represented by .

[0103] R ｃ２ 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents. ｃ２ The explanation, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by are as follows: ｃ２This is the same as the aryl group represented by .

[0104] R ｃ２ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. ｃ２ The heteroaryl group represented by preferably has 4 to 20 ring member atoms, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, and benzothiophenyl group. The heteroaryl group may have substituents.

[0105] As mentioned above, each group, as an example of a substituent, may have further substituents. The further substituents are not particularly limited.

[0106] p represents an integer from 1 to 5. Preferably, p represents an integer from 1 to 3. q represents an integer from 0 to (5-p). In a preferred embodiment, q is preferably an integer from 0 to 3, and more preferably an integer from 0 to 2. m represents an integer from 0 to 4. Preferably, m is preferably an integer from 0 to 2, and more preferably 0 or 1. n represents an integer from 0 to (5-p-q). In a preferred embodiment, n is preferably an integer from 0 to 3, and more preferably an integer from 0 to 2. In formula (4), p+q is preferably an integer of 2 or more. When p, q, m, and n are each 2 or more, the structures of each substituent may be the same or different.

[0107] R ｘ３ However, in the case of a hydrogen atom, q is 1 or greater, and there are q R ｘ４ At least one of these groups is bonded to the ortho position of the following group.

[0108]

[0109] R Ｘ３ , R ｃ１ p and m are as described above.

[0110] Specific examples of repeating units (A) are shown below, but the present invention is not limited to these. Me represents a methyl group.

[0111]

[0112]

[0113] The content of repeating units (A) is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units (A) is 100 mol% or less, relative to the total repeating units in the resin (P). In a preferred embodiment, the content of repeating units (A) is 80 to 100 mol%, relative to the total repeating units in the resin (P).

[0114] The resin (P) may contain one type of repeating unit (A) or two or more types. If the resin (P) contains two or more types of repeating units (A), it is preferable that their total content is within the range of the above-mentioned preferred content.

[0115] The repeating unit (A) may be the same as the repeating unit (UB) described later, or it may be a different repeating unit. It is preferable that the repeating unit (A) is a different repeating unit from the repeating unit (UB).

[0116] The resin (P) may or may not be an acid-degradable resin. In the pattern forming method using the composition of the present invention, when an alkaline developer is used as the developer, a negative-type pattern is suitably formed, and even when an organic developer is used as the developer, a negative-type pattern is suitably formed.

[0117] The resin (P) may have further repeating units.

[0118] (Repeating Unit (UA)) The resin (P) may have repeating units (UA). The repeating unit (UA) is a repeating unit having a group that decomposes upon the action of an acid and increases in polarity (also called an "acid-decomposable group"). Preferably, the acid-decomposable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-decomposable group has a structure in which the polar group is protected by a group that is left behind upon the action of an acid (leaving group). Typically, the resin (P) becomes more polar upon the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. Preferred polar groups include alkali-soluble groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups.

[0119] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (Caution ３７ ) ( OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0120] In equations (Y1) and (Y2), Rx １ ~Rx ３Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). １ ~Rx ３ If all of them are alkyl groups (linear or branched), then Rx １ ~Rx ３ It is preferable that at least two of them are methyl groups. In particular, Rx １ ~Rx ３ Each preferably independently represents a linear or branched alkyl group, and Rx １ ~Rx ３ It is more preferable that each of these independently represents a linear alkyl group. １ ~Rx ３ These two may bond to each other to form a ring (which may be monocyclic or polycyclic). Rx １ ~Rx ３ Preferably, the alkyl group is a C1-C5 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group. １ ~Rx ３ The cycloalkyl group preferably has 3 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms. Rx １ ~Rx ３ The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Rx １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Rx ３ As for the aralkyl group, the above-mentioned Rx １ ~Rx ３A preferred group is one in which one hydrogen atom in the alkyl group is replaced with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), for example, a benzyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ A cycloalkyl group is preferred as the ring formed by the bonding of these two. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, 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, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group.

[0121] In formula (Y3), R ３６ ~R ３８ Each of these independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. ３６It is also preferable that R be a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with heteroatoms such as oxygen atoms and / or groups having heteroatoms such as 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.

[0122] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0123] Specific examples of repeating units (UA) include the structures described in

[0157] to

[0159] and

[0169] of Japanese Patent Application Publication No. 2022-135799.

[0124] (Repeating unit (UB)) The repeating unit (UB) is a repeating unit having a phenolic hydroxyl group. It is preferable that the repeating unit (UB) is a different repeating unit from the repeating unit (A) described above. It is preferable that the repeating unit (UB) is a repeating unit represented by the following formula (Pa3).

[0125]

[0126] In formula (Pa3), R １０１ , R １０２ and R １０３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０２ Ar Ａ It may also bond with to form a ring, in which case R １０２ L represents a single bond or an alkylene group. ＡAr represents a single bond or a divalent linking group. Ａ k represents an aromatic ring group. k represents an integer from 1 to 5.

[0127] R in equation (Pa3) １０１ , R １０２ and R １０３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０１ , R １０２ and R １０３ The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １０１ , R １０２ and R １０３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３ 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. １０１ , R １０２ and R １０３ Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine or iodine atoms being preferred. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred.

[0128] Ar in equation (Pa3) ＡThe symbol represents an aromatic ring group, and more specifically, an aromatic ring group with a (k+1) valency. When k is 1, preferred divalent aromatic ring groups include, for example, arylene groups having 6 to 18 carbon atoms, such as phenylene groups, torylene groups, naphthylene groups, and anthracenylene groups, or divalent aromatic ring groups containing heterocycles such as thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. The above aromatic ring groups may have substituents. Specific examples of (k+1) valency aromatic ring groups when k is an integer of 2 or more include groups obtained by removing (k-1) arbitrary hydrogen atoms from the above-mentioned specific examples of divalent aromatic ring groups. The (k+1) valency aromatic ring groups may further have substituents. The substituents that a (k+1) valent aromatic ring group may have are not particularly limited, but include, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl. Ａ It is preferable that represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.

[0129] L in equation (Pa3) Ａ L represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, but for example, -COO-, -CONR １０４ -, alkylene groups, or groups formed by combining two or more of these groups. The above R １０４ R represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene, are preferred. １０４Examples of alkyl groups that represent an alkyl group include alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or fewer carbon atoms being preferred.

[0130] The repeating unit represented by formula (Pa3) preferably has a hydroxystyrene structure. That is, Ar Ａ k preferably represents a benzene ring group. k preferably represents an integer from 1 to 3, and more preferably represents 1 or 2.

[0131] Specific examples of repeating units (UBs) are shown below, but the present invention is not limited to these. In the following structural formulas, a represents an integer from 1 to 3.

[0132]

[0133]

[0134]

[0135] The content of repeating units (UB) in the resin (P) is not particularly limited, but is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in the resin (P).

[0136] The resin (P) may contain one type of repeating unit (UB) or two or more types. If the resin (P) contains two or more types of repeating units (UB), it is preferable that their total content is within the range of the preferred content described above.

[0137] The resin (P) may contain other repeating units different from repeating unit (A), repeating unit (UA), and repeating unit (UB). For other repeating units, refer to paragraphs

[0112] to

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

[0138] As the resin (P), "P-1" to "P-10" described in the examples below are also preferred.

[0139] 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 50,000 or less, more preferably 1,000 to 50,000, even more preferably 3,000 to 50,000, and particularly preferably 5,000 to 30,000. 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.

[0140] In the composition of the present invention, the content of resin (P) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. Resin (P) may be used alone or two or more types may be used. When two or more types of resin (P) are used, it is preferable that their total content is within the above preferred content range.

[0141] [Compounds that generate acid upon irradiation with active light or radiation] The composition of the present invention contains a compound (photoacid generator) that generates acid upon irradiation with active light or radiation. The photoacid generator may be in the form of a low molecular weight compound, or it may be incorporated into a polymer. Alternatively, the low molecular weight compound form and the form incorporated into a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. When the photoacid generator is incorporated into a polymer, it may be incorporated into a resin (P), or it may be incorporated into a resin different from resin (P). The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid with a pKa of -2.0 or higher upon irradiation with active light or radiation, and even more preferably a compound that generates an acid with a pKa of -2.0 or higher and 1.0 or lower.

[0142] Examples of photoacid generators include, "M＋ X － Examples of photoacid generators include compounds represented by (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imide acid, and tris(alkylsulfonyl)methidic acid. As the photoacid generator, sulfonium salts or iodonium salts are preferred, and sulfonium salts are more preferred.

[0143] "M ＋ X － In the compound represented by ", M ＋ represents an organic cation. The organic cation is not particularly limited. The valency of the organic cation may be 1 or 2 or more. In particular, the organic cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0144]

[0145] 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.

[0146] 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.

[0147] 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.

[0148] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, with methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group being more preferred.

[0149] R ２０１ ~R ２０３ Preferred substituents on the aryl group, alkyl group, and cycloalkyl group include alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. The above substituents may also form an acid-degradable group in any combination. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a group that leaves upon the action of an acid. The polar group and leaving group are as described above.

[0150] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). ２０１ ~R ２０３ However, each of these independently represents a cation that does not have an aromatic ring. The term "aromatic ring" also includes aromatic rings containing heteroatoms. R ２０１ ~R ２０３ The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0151] R ２０１ ~R ２０３ Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). ２０１ ~R ２０３ R may be further substituted with halogen atoms, alkoxy groups (e.g., C1-C5), hydroxyl groups, cyano groups, or nitro groups. ２０１ ~R ２０３ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0152] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0153]

[0154] In formula (ZaI-3b), R １ｃ ~R ５ｃEach of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0155] 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.

[0156] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙExamples of groups formed by the bonding include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0157] 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.

[0158] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0159]

[0160] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. １３ R represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. １４R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. １４ If multiple instances exist, each independently represents one of the above groups, such as a hydroxyl group. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The above alkyl group, the above cycloalkyl group, and the above naphthyl group, and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0161] 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.

[0162] Next, we will explain equation (ZaII). In equation (ZaII), R ２０４ and R ２０５ Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. ２０４ and R ２０５ The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0163] 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.

[0164] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0165]

[0166]

[0167] "M ＋ X － In the compound represented by ", X －represents an organic anion. The organic anion is not particularly limited and can be a monovalent or divalent or more organic anion. The organic anion is preferably one with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0168] 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.

[0169] 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).

[0170] 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.

[0171] 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).

[0172] 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.

[0173] An example of a sulfonylimid anion is the saccharin anion.

[0174] 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.

[0175] 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.

[0176] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably having 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0177] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0178]

[0179] In formula (AN1), R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', and -NH. ２ ,-NR' ２ -NHR' or -NHCOR' are preferred. R' is a monovalent hydrocarbon group.

[0180] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. １ and R ２ Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0181] L represents a divalent linking group. If there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of divalent linking groups include alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining multiples thereof. Among these, examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ２ - or -COO-alkylene group- is more preferred.

[0182] For L, a group represented by the following formula (AN1-1) is preferred. * ａ - (CR２ａ ２ ) Ｘ -Q- (CR ２ｂ ２ ) Ｙ - * ｂ (AN1-1)

[0183] In formula (AN1-1), * ａ R in equation (AN1) ３ This indicates the connection point with [the other element]. * ｂ -C(R) in equation (AN1) １ ) (Caution ２ ) - Represents the connection position with . X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3. R ２ａ and R ２ｂ Each of these independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ If there are multiple instances of each, then there are multiple instances of R ２ａ and R ２ｂ These can be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) １ ) (Caution ２ )- and CR that bind directly ２ｂ ２ In R ２ｂ is anything other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents the condition where X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) ２ａ and R ２ｂ If all of them are hydrogen atoms, then Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-*Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents. * Ａ R in equation (AN1) ３ This indicates the connection position on the side, * Ｂ This is -SO in equation (AN1). ３ － This indicates the connection point on the side.

[0184] In formula (AN1), R ３ represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0185] Among them, R ３Preferably, the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have substituents. Preferably, the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). The heteroatoms may be substituted for one or more carbon atoms forming the cyclic structure. Preferably, the organic group having a cyclic structure is a cyclic hydrocarbon group, a lactone ring group, and a sultone ring group. Among these, a cyclic hydrocarbon group is preferred. Preferably, the cyclic hydrocarbon group is a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.) and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone structure or sultone structure in any of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0186] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0187] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0188]

[0189] In equation (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0190] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and fluorine atom or CF ３ It is more preferable that both Xf atoms are fluorine atoms.

[0191] R ４ and R ５ Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If multiple instances exist, R ４ and R ５ These may be the same or different. ４ and R ５ The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. ４ and R ５ A hydrogen atom is preferred as the element.

[0192] L represents a divalent linking group. The definition of L is the same as the L in formula (AN1).

[0193] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0194] The aryl group may be monocyclic or polycyclic. Examples of the above aryl group include phenyl, naphthyl, phenanthryl, and anthryl groups. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic non-aromatic groups include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0195] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0196] Anions represented by formula (AN2) include SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W, or SO ３ － -CF ２ -CH(CF ３ )-OCO-(L) ｑ’ -W is preferred. Here, L, q, and W are the same as in formula (AN2). q' represents an integer from 0 to 10.

[0197] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0198]

[0199] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have substituents other than a sulfonic acid anion and a -(D-B) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0200] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations thereof.

[0201] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group).

[0202] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions include, for example, N － (SO ２ -R ｑ ) ２ This is an anion represented by R. Here, R ｑ R represents an alkyl group which may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. ｑ They may be joined to each other to form a ring. Two R ｑ The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0203] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0204]

[0205]

[0206] In formula (d1-1), R ５１represents a hydrocarbon group (e.g., an aryl group such as a phenyl group) which may have substituents (e.g., a hydroxyl group).

[0207] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). ２ｃ The hydrocarbon group in formula (d1-2) may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member carbon atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have substituents. The carbon atoms forming the norbornyl group may be carbonyl carbons. In formula (d1-2), "Z ２ｃ -SO ３ － It is preferable that the anion is different from the anion represented by the above formulas (AN1) to (AN3). For example, Z ２ｃ The group other than an aryl group is preferable. For example, Z ２ｃ In, -SO ３ － For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z ２ｃ is, -SO ３ － In relation to this, the atom at the α position and / or the atom at the β position are preferably ring member atoms in the cyclic group.

[0208] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0209] In formula (d1-4), R ５３ and R ５４ Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４They may be joined to each other to form a ring.

[0210] Organic anions may be used individually or in combination of two or more. Preferred examples of organic anions are shown below.

[0211]

[0212] The photoacid generator is preferably at least one selected from the group consisting of compounds (I) to (II).

[0213] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural site X: Anionic site A １ － and cation site M １ ＋ It consists of and is irradiated with active light or radiation, HA １ Structural site that forms the first acidic site represented by Structural site Y: Anionic site A ２ － and cation site M ２ ＋ It consists of and is irradiated with active light or radiation, HA ２ The structural site (I) that forms the second acidic site represented by satisfies the following condition I.

[0214] Condition I: In the above compound (I), the above cation site M in the above structural site X. １ ＋ and the cation portion M in the structural portion Y. ２ ＋ to H ＋ The compound PI obtained by replacing the above structural site X is the cation site M １ ＋ to H ＋ HA is obtained by replacing it with １ The acid dissociation constant a1 originates from the acidic site represented by the above structure site Y, and the cation site M in the above structural site Y. ２ ＋ to H ＋HA is obtained by replacing it with ２ It has an acid dissociation constant a2 derived from the acidic site represented by the above, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0215] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "HA １ and HA ２ This falls under the category of "compounds having the above characteristics". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, compound PI is "A １ － and HA ２ The pKa at which the compound becomes "a compound having " is the acid dissociation constant a1, and the above "A １ － and HA ２ Compounds having "A" １ － and A ２ － The pKa value at which the compound becomes "a compound having the above characteristics" is the acid dissociation constant a2.

[0216] If compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "two HA １ and one HA ２ This falls under the category of "compounds having one A". When the acid dissociation constant of compound PI is determined, compound PI is "a compound having one A １ － and one HA １ and one HA ２ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２The acid dissociation constant when the compound becomes "a compound having the two A's" corresponds to the above-mentioned acid dissociation constant a1. １ － and one HA ２ Compounds having "two A １ － and A ２ － The acid dissociation constant when a compound has the above-mentioned structure corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the above-mentioned cation site M in the above-mentioned structural site X. １ ＋ to H ＋ HA is obtained by replacing it with １ When a compound has multiple acid dissociation constants originating from the acidic site represented by , the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1. １ － and one HA １ and one HA ２ Let aa be the acid dissociation constant when a compound having " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２ When the acid dissociation constant for a compound having the above is denoted as ab, the relationship between aa and ab satisfies aa < ab.

[0217] The acid dissociation constants a1 and a2 are determined by the acid dissociation constant measurement method described above. The compound PI mentioned above corresponds to the acid generated when compound (I) is irradiated with active light or radiation. If compound (I) has two or more structural sites X, the structural sites X may be the same or different. Also, two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different. In compound (I), the above A １ － and A above ２ － , and the above M １ ＋and the above M ２ ＋ These may be the same or different, but A above １ － and A above ２ － It is preferable that they are all different.

[0218] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. There is no particular upper limit to the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2, but for example, it is 16 or less.

[0219] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0220] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0221] Anion part A １ － and anion part A ２ － This is a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion site A １ － Preferably, it is an acidic moiety that can form an acidic moiety with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion moiety A ２ － For example, Anion part A １ －It is preferable that the acidic site can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6) below, * represents the bond position. In formula (AA-2), R Ａ R represents a monovalent organic group. Ａ The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0222]

[0223]

[0224] Cation site M １ ＋ and cation site M ２ ＋ This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. ＋ Examples of organic cations represented by the following are given.

[0225] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acid

[0226] Definition of structural site X in compound (II), and A １ － and M １ ＋ The definition of is the definition of structural site X in compound (I) described above, and A １ － and M １ ＋ This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0227] In the above compound (II), the above cation moiety M in the above structural moiety X. １＋ to H ＋ In compound PII, which is obtained by replacing the above structural site X, the above cation site M １ ＋ to H ＋ HA is obtained by replacing it with １ The preferred range for the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in compound PI. Note that if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, then compound PII is "two HA １ This falls under the category of "a compound having one A". When the acid dissociation constant of this compound PII is determined, compound PII is "a compound having one A １ － and one HA １ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ Compounds having "two A １ － The acid dissociation constant when the compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0228] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. Compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. The two or more structural sites X may be the same or different. Two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different.

[0229] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, and is preferably a site containing a group that can electrostatically interact with a proton, or a functional group having electrons. Examples of groups that can electrostatically interact with a proton, or functional groups having electrons, include functional groups having a macrocyclic structure such as a cyclic polyether, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0230]

[0231] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0232] Examples of non-cationic sites that compound (I) and compound (II) may have are given below.

[0233]

[0234]

[0235] Specific examples of photoacid generators are shown below, but the present invention is not limited to these.

[0236]

[0237]

[0238]

[0239] As photoacid generators, "PA-1" to "PA-2" described in the examples below are also preferred.

[0240] The content of the photoacid generator is not particularly limited, but it is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the composition of the present invention. The content of the photoacid generator is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, relative to the total solid content of the composition of the present invention. One type of photoacid generator 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.

[0241] [Acid Diffusion Control Agent] The composition of the present invention may further contain an acid diffusion control agent. The acid diffusion control agent traps the acid generated from the photoacid generator, etc., during exposure and acts as a quencher to suppress the reaction of the acid-degradable resin in the unexposed area by the excess generated acid. The type of acid diffusion control agent is not particularly limited and examples include basic compounds (DA), low molecular weight compounds (DB) having a nitrogen atom and a group that is eliminated by the action of acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (DC) include onium salt compounds (DD) of acids that are relatively weak acids with respect to the acid generated from the photoacid generator, and basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation. 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.

[0242] In one preferred embodiment, a specific example of a basic compound (DA) is, for example, a compound represented by the following formula (X).

[0243]

[0244] In formula (X), W represents a non-aromatic heterocycle containing a nitrogen atom. Ｂ represents a hydrogen atom or an alkyl group. q represents an integer from 1 to 5.

[0245] W represents a non-aromatic heterocycle having a nitrogen atom. The number of member atoms of the non-aromatic heterocycle is preferably 4 to 20, and more preferably 5 to 10. The non-aromatic heterocycle may be monocyclic or polycyclic. In addition to the nitrogen atom in formula (X), the non-aromatic heterocycle may further contain at least one of a sulfur atom, a nitrogen atom, and an oxygen atom. Examples of non-aromatic heterocycles include piperidine rings, piperazine rings, morpholine rings, and thiomorphone rings.

[0246] R Ｂ The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 5 is more preferred. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc. Q preferably represents an integer from 1 to 4.

[0247] Specific examples of onium salt compounds (DDs) that are relatively weak acids with respect to photoacid generators include, for example, those described in paragraphs

[0305] to

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

[0248] In one preferred embodiment, the acid diffusion control agent is, for example, "E ＋ G －Examples of compounds represented by '' (onium salts) include compounds that change into organic acids upon exposure. Examples of the above organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), phenols, carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids, with carboxylic acids or phenols being preferred, and carboxylic acids being more preferred. As the acid diffusion control agent, onium salts are preferred, sulfonium salts or iodonium salts are preferred, and sulfonium salts are more preferred.

[0249] "E ＋ G － In the compound represented by ", E ＋ represents an organic cation. Preferably, the organic cation is a cation represented by formula (ZbI) (hereinafter also referred to as "cation (ZbI)") or a cation represented by formula (ZbII) (hereinafter also referred to as "cation (ZbII)").

[0250]

[0251] In equation (ZbI), R ３０１ , R ３０２ , and R ３０３ Each of these independently represents an organic group. ３０１ , R ３０２ , and R ３０３ The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. ３０１ ~R ３０３ 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. ３０１ ~R ３０３ 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.

[0252] R ３０１, R ３０２ , and R ３０３ The organic group is preferably an alkyl group, cycloalkyl group, aryl group, or heteroaryl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. As cycloalkyl groups, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are preferred. The aryl group 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 a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms. Examples of heteroaryl groups include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues.

[0253] In formula (ZbII), R ３０４ and R ３０５ Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. ３０４ and R ３０５ The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. ３０４ and R ３０５ 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. ３０４ and R３０５ The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0254] R ３０４ and R ３０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ３０４ and R ３０５ 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. ３０４ and R ３０５ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0255] "E ＋ G － In the compound represented by ", G － G represents an anion. － It is preferably a carboxylate anion or a phenoxide anion, and more preferably a carboxylate anion.

[0256] The acid diffusion control agent is more preferably a compound containing a sulfonium cation.

[0257] The acid diffusion control agent preferably contains a carboxylic acid anion or a phenoxide anion as an anion, and more preferably a carboxylic acid anion. Examples of carboxylic acid anions include aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions. The aliphatic moiety in the aliphatic carboxylic acid anion 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 a fluorine atom; it may also be a perfluoroalkyl group). The aryl group in the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, and a naphthyl group. The aryl group in the phenoxide anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, and a naphthyl group. The alkyl groups, cycloalkyl groups, and aryl groups mentioned 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). As the aralkyl group in the aralkyl carboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0258] The acid diffusion control agent preferably contains an anion represented by the following formula (xa1) or (xa2).

[0259]

[0260] In equations (xa1) and (xa2), Ar ａ１ E represents an aromatic ring. ａ１ represents a substituent. q represents an integer from 0 to 7. If q is 2 or greater, multiple E ａ１ They may be the same or different from each other. If q is 2 or more, there may be multiple E ａ１ They may be joined together to form a ring.

[0261] Ar ａ１ The aromatic ring represented by may be either an aromatic hydrocarbon ring or an aromatic heteroring. The number of member carbon atoms in an aromatic hydrocarbon ring is preferably 6 to 20, and more preferably 6 to 15. As the aromatic hydrocarbon ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The number of member atoms in an aromatic heteroring is preferably 4 to 20, and more preferably 5 to 10. As the aromatic heteroring, it is preferable that it contains at least one of a sulfur atom, a nitrogen atom, and an oxygen atom. Examples of aromatic heterorings include five-membered aromatic heterorings such as pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, triazole rings, thiophene rings, and furan rings; six-membered aromatic heterorings such as pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, thiazine rings, and oxazine rings; and fused aromatic heterorings such as indole rings, quinoline rings, and isoquinoline rings.

[0262] E ａ１ The substituent represented by is not particularly limited, but examples include the substituent T mentioned above, and hydroxyl groups, carboxyl groups, alkyl groups, alkoxy groups, and halogen atoms are preferred.

[0263] q represents an integer from 0 to 7, preferably from 0 to 5, and more preferably from 0 to 3.

[0264] In addition to the above, known compounds disclosed in, for example, 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 also be suitably used as acid diffusion control agents. As acid diffusion control agents, "Q-1" to "Q-4" described in the examples below are also preferred.

[0265] The content of the acid diffusion control agent in the composition of the present invention is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the acid diffusion control agent in the composition of the present invention is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, and even more preferably 20.0% by mass or less, based on the total solid content of the composition of the present invention. Only one type of acid diffusion control agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0266] [Hydrophobic Resin (Resin (T))] The composition of the present invention may further contain a hydrophobic resin (also called "Resin (T)") 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.

[0267] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 atoms in the side chain portion of the resin. ３ It is preferable that the hydrophobic resin has one or more of the substructures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

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

[0268] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition of the present invention. 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.

[0269] [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.

[0270] 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.

[0271] [Solvent] The composition of the present invention contains a solvent. Preferably, the solvent contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0272] Combining the solvent and resin described above is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The solvent described above has a good balance of solubility, boiling point and viscosity with the resin described above, and can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0273] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0274] Bio-derived solvents can also be used as solvents. Examples of bio-derived solvents include those described in Japanese Patent Publication No. 2002-363135, U.S. Patent Application Publication No. 2015 / 0004664A1, International Publication No. 2025 / 106697, etc., as well as commercially available products such as the PURASOLV® ELECT series (see https: / / www.corbion.com / solutions / biochemical-specialties / electronics and https: / / www.corbion.com / - / media / Corbion / Files / PLA-PDFs-7-of-24 / brch-electronics-purasolv-eng-0421_940879.ashx). The bio-derived solvents described above can be purified using methods such as distillation and filtration as appropriate to achieve the purity required in the technical field of the present invention.

[0275] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably so that it is 1 to 20% by mass. This further improves the applicability of the composition of the present invention.

[0276] [Other Additives] The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, a crosslinking agent, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0277] The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developing solutions.

[0278] <Photosensitive or Radiation-Sensitive Film, Pattern, Pattern Forming Method> The present invention also relates to a photosensitive or radiation-sensitive film formed by the composition of the present invention. Preferably, the photosensitive or radiation-sensitive film of the present invention is a resist film. The present invention also relates to a pattern formed by the photosensitive or radiation-sensitive film of the present invention. Preferably, the pattern of the present invention is a pattern obtained by the pattern forming method of the present invention described below. The present invention also relates to a pattern forming method. Preferably, the pattern forming method of the present invention comprises the steps of: forming a photosensitive or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention; exposing the photosensitive or radiation-sensitive film; and developing the exposed photosensitive or radiation-sensitive film using a developer. The procedure for a pattern forming method using the composition of the present invention is not particularly limited, but it is preferable to have the following steps: Step 1: A step of forming a resist film on a substrate using the composition of the present invention. Step 2: A step of exposing the resist film. Step 3: A step of developing the exposed resist film using a developer. The procedure for each of the above steps will be described in detail below.

[0279] (Step 1: Resist film formation step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0280] One method for forming a resist film on a substrate using the composition of the present invention is to coat the substrate with the composition of the present invention. It is preferable to filter the composition of the present invention before coating, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0281] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After applying the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed in the layer below the resist film.

[0282] As for drying methods, for example, a method of drying by heating can be used. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0283] 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.

[0284] Furthermore, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods. For example, a topcoat can be formed based on paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be contained in the composition of the present invention. It is also preferable that the topcoat contains a compound that includes at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0285] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film. The method of exposure is to irradiate the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, with wavelengths of 250 nm or less being preferred, more preferably 220 nm or less, and far ultraviolet light with wavelengths of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams are particularly preferred.

[0286] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, and may also be done using a hot plate or the like. This process is also called post-exposure baking.

[0287] (Step 3: Development Step) Step 3 is the process of developing the exposed resist film using a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0288] Examples of development methods include immersing the substrate in a tank filled with developer for a certain period of time (dip method), puddling the developer onto the substrate surface using surface tension and letting it stand for a certain period of time (paddle method), spraying the developer onto the substrate surface (spray method), and continuously dispensing the developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). In addition, after the development process, a step of stopping the development while replacing the solvent with another solvent may be performed. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0289] 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.

[0290] 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.

[0291] Bio-derived solvents can also be used as organic solvents in organic developing solutions. Examples of bio-derived solvents include those described in U.S. Patent Application Publication 2025 / 0068079A1, Proceedings of SPIE, 12957, 1295719 (2024), etc. The above-mentioned bio-derived solvents can be purified using methods such as distillation and filtration as appropriate to achieve the purity required in the technical field of the present invention.

[0292] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0293] (Other steps) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0294] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may also be added to the rinsing solution.

[0295] The rinsing solution used in the rinsing step after the development process using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Bio-derived solvents can also be used as the rinsing solution. Examples of bio-derived solvents include the bio-derived solvents presented above as organic solvents in the organic developer.

[0296] The rinsing process is not particularly limited and includes methods such as continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), and spraying rinsing solution onto the substrate surface (spray method). The pattern formation method may also include a heating process (post bake) after the rinsing process. This process removes developer and rinsing solution remaining between and inside the patterns due to baking. This process also has the effect of softening the resist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0297] In a preferred embodiment, the pattern forming method of the present invention is a pattern forming method wherein the repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, a condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is an alkaline developer.

[0298]

[0299] In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２ Each of these independently represents an aromatic ring. ｘ１ Ar is a reaction involving hydrogen atoms or acids. ２ R represents a substituent that can form a ring. ｘ２ Ar is a reaction involving hydrogen atoms or acids. １ R represents a substituent that can form a ring. ｘ１ , R ｘ２ Of these, at least one is not a hydrogen atom. In formula (1) above, Rｘ１ , R ｘ２ Of these, at least one is a group represented by the following formula (2).

[0300]

[0301] In formula (2), R ｂ１ * represents a group that is eliminated by the action of a hydrogen atom or an acid. * represents the bond position.

[0302] Each group in formulas (1) and (2) above is equivalent to each group in formulas (1) and (2) in the resin (P) of the composition of the present invention.

[0303] In a preferred embodiment, the pattern forming method of the present invention is a pattern forming method wherein the repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, a condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is a developer containing an organic solvent.

[0304]

[0305] In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２ Each of these independently represents an aromatic ring. ｘ１ Ar is a reaction involving hydrogen atoms or acids. ２ R represents a substituent that can form a ring. ｘ２ Ar is a reaction involving hydrogen atoms or acids. １ R represents a substituent that can form a ring. ｘ１ , R ｘ２ Of these, at least one is not a hydrogen atom. In formula (1) above, R ｘ１ , R ｘ２ Of these, at least one is a group represented by the following formula (3).

[0306]

[0307] In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

[0308] Each group in formulas (1) and (3) above is equivalent to each group in formulas (1) and (3) in the resin (P) of the composition of the present invention.

[0309] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate. The method of processing the substrate (or the underlying film and substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask is preferred. For dry etching, oxygen plasma etching is preferred.

[0310] The various materials used in the compositions and pattern forming methods of the present invention (for example, solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0311] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

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

[0312] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as constituent materials for various materials, filtering the constituent materials of various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon (registered trademark).

[0313] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the manufacturing equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0314] To prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge in organic treatment solutions such as rinsing solutions, a conductive compound may be added. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. As for chemical piping, for example, various pipes coated with SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that have been treated with an antistatic agent can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that have been treated with an antistatic agent can be used.

[0315] <Method for Manufacturing Electronic Devices> This specification relates to a method for manufacturing electronic devices, including the pattern formation method described above, and to electronic devices manufactured by this method. Preferred embodiments of the electronic devices described herein include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0316] 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.

[0317] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0318] <Resin> P-1 to P-10 are used as resin (P). In addition, RP-1 to RP-2 are used as resins that are not resin (P). However, in the table below, for convenience, RP-1 to RP-2 may also be listed in the resin (P) column. The structures of P-1 to P-10 and RP-1 to RP-2 (structure of the repeating units possessed by each resin and their content) are shown below. The content of each repeating unit is indicated by a subscript to the right of the parentheses of each repeating unit. The content of each repeating unit (content ratio to the total repeating units in the resin) is expressed as a molar ratio (mol%). The composition ratio (mol% ratio), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in each resin are also shown. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the 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).

[0319]

[0320]

[0321] <Photoacid Generator> The structure of the photoacid generator used is shown below. Me represents a methyl group.

[0322]

[0323] <Acid Diffusion Control Agent> The structure of the acid diffusion control agent used is shown below. Me represents a methyl group.

[0324]

[0325] <Surfactants> The surfactants used are as follows: W-1: Megafac R08 (manufactured by DIC Corporation)

[0326] <Solvents> The solvents to be used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane) S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) S-3: Ethyl lactate S-4: γ-butyrolactone

[0327] <Preparation of Resist Composition> The components shown in Table 1 are dissolved in the solvents shown in each table, and solutions are prepared at the solid content concentrations shown in each table. These solutions are then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare the resist composition. The resulting resist composition is used in the examples and comparative examples. In the table, the "mass%" column indicates the content (mass ratio) of each component relative to the total solid content in the resist composition. Solid content refers to all components other than the solvent. If multiple types of resin (P), photoacid generators, and acid diffusion control agents are used, the table is divided into multiple rows. In resist compositions using surfactants, the surfactant content is set to 0.1 mass%. The "mass ratio" of the solvent is the content of each solvent listed in the "type" column relative to the total amount of solvents listed in the "type" column. If two or more types of solvents are used, each type and mass ratio are separated by " / ". The types and mass ratios are listed in order from left to right.

[0328]

[0329] [Examples 1-1 to 1-16, Comparative Examples 1-1 to 1-2] <Pattern Formation Method (1): EB Exposure, Organic Solvent Development (EB-Negative)> The resist composition 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. The wafer coated with the resist film obtained above is subjected to pattern irradiation using an electron beam lithography system (Hitachi Ltd. HL750, acceleration voltage 50 keV). At this time, drawing is performed so that a 1:1 line and space pattern is formed. After electron beam lithography, the wafer is heated on a hot plate at 110°C for 60 seconds (this heating is also called "post-exposure heating"), then developed with butyl acetate for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a line width of 50 nm and a 1:1 line-and-space pattern.

[0330] <Performance Evaluation> [LWR Performance] Sensitivity (Eop) is defined as the exposure amount (electron beam irradiation amount) required to resolve a 1:1 line-and-space pattern with a line width of 50 nm using a length-measuring scanning electron microscope (Hitachi S-9380II). A line-and-space pattern with a line width of 50 nm (1:1) that resolves at the exposure amount that shows the above sensitivity (Eop) is observed from above using a length-measuring scanning electron microscope (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 smaller the LWR value, the better the LWR performance.

[0331] [Resolution] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi S-9380II). The exposure amount (electron beam irradiation amount) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm is defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure amount that shows the above sensitivity (Eop) is defined as the resolution (nm). The smaller this value, the higher the resolution.

[0332] [Pattern Shape] The cross-sectional shape of a 1:1 line-and-space pattern with a line width of 50 nm at the exposure dose that shows the sensitivity described above is observed using a scanning electron microscope (Hitachi, Ltd. S-4300). In the cross-sectional shape of the line pattern, those with a ratio of [line width at the top (surface) of the line pattern / line width at the middle (half the height of the line pattern)] of less than 0.9 are classified as "T-top", and those with a ratio of 0.9 or more are classified as "rectangle", and are evaluated accordingly.

[0333] Table 2 below shows the resist compositions used in each example and comparative example, and the evaluation results for each example and comparative example.

[0334]

[0335] [Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-2] <Pattern Formation Method (2): EB Exposure, Alkaline Development (EB-Negative)> The process is the same as in Pattern Formation Method (1) up to electron beam lithography. After exposure, the wafer is heated on a hot plate at 110°C for 60 seconds (this heating is also called "post-exposure heating"), then immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. After that, the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a line width of 50 nm and a 1:1 line and space pattern.

[0336] <Performance Evaluation> LWR performance, resolution, and pattern shape are evaluated in the same manner as in the pattern formation method (1) described above.

[0337] Table 3 below shows the resist compositions used in each example and comparative example, and the evaluation results for each example and comparative example.

[0338]

[0339] [Examples 3-1 to 3-16, Comparative Examples 3-1 to 3-2] <Pattern Formation Method (3): EUV Exposure, Organic Solvent Development (EUV-Negative)> The resist composition 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. The wafer coated with the resist film obtained above is subjected to pattern exposure using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) with an exposure mask (line / space = 1 / 1). After exposure, the wafer is heated on a hot plate at 110°C for 60 seconds (this heating is also called "post-exposure heating"), then immersed in butyl acetate for 60 seconds, and then rinsed with water for 30 seconds. After that, the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a line width of 50 nm and a 1:1 line-and-space pattern.

[0340] <Performance Evaluation> [LWR Performance] Sensitivity (Eop) is defined as the exposure amount (EUV irradiation amount) required to resolve a 1:1 line-and-space pattern with a line width of 50 nm using a length-measuring scanning electron microscope (Hitachi S-9380II). A line-and-space pattern with a line width of 50 nm (1:1) that resolves at the exposure amount that shows the above sensitivity (Eop) is observed from above using a length-measuring scanning electron microscope (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 smaller the LWR value, the better the LWR performance.

[0341] [Resolution] The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi S-9380II). The exposure dose (EUV irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm is defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure dose that shows the above sensitivity (Eop) is defined as the resolution (nm). The smaller this value, the higher the resolution.

[0342] [Pattern Shape] The cross-sectional shape of a 1:1 line-and-space pattern with a line width of 50 nm at the exposure dose that shows the sensitivity described above is observed using a scanning electron microscope (Hitachi, Ltd. S-4300). In the cross-sectional shape of the line pattern, those with a ratio of [line width at the top (surface) of the line pattern / line width at the middle (half the height of the line pattern)] of less than 0.9 are classified as "T-top", and those with a ratio of 0.9 or more are classified as "rectangle", and are evaluated accordingly.

[0343] Table 4 below shows the resist compositions used in each example and comparative example, and the evaluation results for each example and comparative example.

[0344]

[0345] The results in Tables 2-4 show that the resist compositions used in the examples exhibit excellent resolution, LWR performance, and pattern shape.

[0346] The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution, LWR performance, and pattern shape. Furthermore, the present invention provides a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition.

[0347] 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. 2025-057032 filed on 28 March 2025, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiation-sensitive resin composition comprising a resin having repeating units in which condensed rings are formed within the repeating units by a reaction with an acid, a photoacid generator, and a solvent.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, and the condensed ring is formed from two of the two or more aromatic rings.

3. The actinic-ray-sensitive or radiation-ray-sensitive resin composition according to claim 2, wherein the repeating unit (A) is a repeating unit represented by the following formula (1). In formula (1), R ａ１ to R ａ３ each independently represent a hydrogen atom or a substituent. L １ , L ２ each independently represent a single bond or a divalent linking group. Ar １ , Ar ２ each independently represent an aromatic ring. R ｘ１ represents a hydrogen atom or a substituent capable of forming a ring with Ar ２ through an acid-catalyzed reaction. R ｘ２ represents a hydrogen atom or a substituent capable of forming a ring with Ar １ through an acid-catalyzed reaction. Among R ｘ１ and R ｘ２ , at least one of them is not a hydrogen atom.

4. In formula (1) above, R ｘ１ , R ｘ２ The photosensitive or radiation-sensitive resin composition according to claim 3, wherein at least one of the groups is a group represented by the following formula (2) or a group represented by the following formula (3). In formula (2), R ｂ１ R represents a group that is eliminated by the action of a hydrogen atom or an acid. In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

5. In formula (1) above, L ２ is a single bond, or -O-, -S-, -NR Ｌ１ -, -CR Ｌ２ R Ｌ３ - A photosensitive or radiation-sensitive resin composition according to claim 3, representing any of the following: Ｌ１ ~R Ｌ３ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

6. The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit (A) is a repeating unit represented by the following formula (4). In formula (4), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ R represents a single bond or a divalent linking group. ｘ３ R represents a hydrogen atom, or a group represented by the following formula (2) or formula (3). ｘ４ R represents a group represented by the following formula (2) or the following formula (3). ｃ１ R represents a substituent. ｃ２ represents a substituent other than the group represented by formula (2) below or the group represented by formula (3) below. p represents an integer from 1 to 5. q represents an integer from 0 to (5-p). m represents an integer from 0 to 4. n represents an integer from 0 to (5-p-q). When p, q, m, and n are each 2 or greater, the structures of each substituent may be the same or different. R ｘ３ However, in the case of a hydrogen atom, q is 1 or greater, and there are q R ｘ４ At least one of these groups is bonded to the ortho position of the following group. R Ｘ３ , R ｃ１ , p, and m are as described above. When q is 0, R ｘ３ This represents a group represented by the following formula (2) or a group represented by the following formula (3). In formula (2), R ｂ１ R represents a group that is eliminated by the action of a hydrogen atom or an acid. In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

7. The photosensitive or radiation-sensitive resin composition according to claim 6, wherein p + q in formula (4) is an integer of 2 or more.

8. The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the content of the repeating unit (A) is 50 mol% or more relative to the total repeating units in the resin.

9. A photosensitive or radiation-sensitive film formed from the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 8.

10. A pattern formed by a photosensitive or radiation-sensitive film as described in claim 9.

11. A pattern forming method comprising the steps of: forming a photosensitive or radiation-sensitive film on a substrate using the composition described in any one of claims 1 to 8; exposing the photosensitive or radiation-sensitive film; and developing the exposed photosensitive or radiation-sensitive film using a developer.

12. The repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by a single bond or a divalent linking group, the condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is an alkaline developer. The pattern forming method according to claim 11. In formula (1), R ａ１ to R ａ３ each independently represent a hydrogen atom or a substituent. L １ and L ２ each independently represent a single bond or a divalent linking group. Ar １ and Ar ２ each independently represent an aromatic ring. R ｘ１ represents a hydrogen atom or a substituent capable of forming a ring with Ar ２ through an acid-catalyzed reaction. R ｘ２ represents a hydrogen atom or a substituent capable of forming a ring with Ar １ through an acid-catalyzed reaction. At least one of R ｘ１ and R ｘ２ is not a hydrogen atom. In formula (1), at least one of R ｘ１ and R ｘ２ is a group represented by the following formula (2). In formula (2), R ｂ１ represents a hydrogen atom or a group that is eliminated by the action of an acid. * represents a bonding position.

13. The pattern forming method according to claim 11, wherein the repeating unit in the resin in the composition is a repeating unit (A) having two or more aromatic rings linked by single bonds or divalent linking groups, the condensed ring is formed from two of the two or more aromatic rings, the repeating unit (A) is a repeating unit represented by the following formula (1), and the developer is a developer containing an organic solvent. In formula (1), R ａ１ ~R ａ３ Each of these independently represents a hydrogen atom or a substituent. １ , L ２ Each of these independently represents a single bond or a divalent linking group. １ Ar ２ Each of these independently represents an aromatic ring. ｘ１ Ar is a reaction involving hydrogen atoms or acids. ２ R represents a substituent that can form a ring. ｘ２ Ar is a reaction involving hydrogen atoms or acids. １ R represents a substituent that can form a ring. ｘ１ , R ｘ２ Of these, at least one is not a hydrogen atom. In formula (1) above, R ｘ１ , R ｘ２ Of these, at least one is a group represented by the following formula (3). In formula (3), R ｂ２ R represents a group that is eliminated by the action of a hydrogen atom or an acid. ｂ３ , R ｂ４ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * indicates a bond position.

14. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 11.

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