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

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing an onium salt compound (I) that includes an organic anion and a cation having a specific structure, an onium salt compound (II) that includes an onium cation and an anion having a specific structure, an acid-decomposable resin, and a solvent; and a resist film, a pattern formation method, and an electronic device manufacturing method that use the actinic ray-sensitive or radiation-sensitive resin composition.

Description

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

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

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

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

[0004] For example, Patent Document 1 describes a resist composition containing an acid generator having a specific structure, a resin having an acid-unstable group, a quencher, and a solvent.

[0005] Japanese Patent Application Laid-Open No. 2023-88869

[0006] Recently, due to further miniaturization of the patterns to be formed and the like, the performance required for resist compositions has been increasing. In particular, further improvements in roughness performance and resolution are required. Also, a resist composition is required that has a small variation in sensitivity before and after storage (i.e., excellent stability over time) when stored for a certain period.

[0007] An object of the present invention is to provide a photoactive or radiation-sensitive resin composition excellent in roughness performance, resolution, and stability over time. Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above photoactive or radiation-sensitive resin composition.

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

[0009] [1] A photoactive or radiation-sensitive resin composition containing an onium salt compound (I) containing a cation represented by the following formula (a-1) and an organic anion, an onium salt compound (II) containing an anion represented by the following formula (b-1) and an onium cation, an acid-decomposable resin, and a solvent.

[0010]

[0011] In formula (a-1), X represents a sulfur atom or an iodine atom. R １ represents a monovalent organic group. When there are a plurality of R １ , the plurality of R １ may be the same or different. When there are a plurality of R １ , the plurality of R １ may be bonded. L １ represents a single bond or a divalent linking group. When there are a plurality of L １ , the plurality of L １ may be the same or different. Ar １ and Ar ２ each independently represent an aromatic group. When there are a plurality of Ar １ , the plurality of Ar １They may be the same or different. ２ If there are multiple Ar ２ They may be the same or different. At least one R １ and at least one Ar １ k and m may be combined. k and m each independently represent an integer of 1 or more. If m represents an integer of 2 or more, multiple ks may be the same value or different values. n represents an integer of 0 or more. If X represents a sulfur atom, the sum of m and n is 3. If X represents an iodine atom, the sum of m and n is 2.

[0012]

[0013] In formula (b-1), Ar ３ Y represents an aromatic group. １ represents a monovalent substituent. Y １ If there are multiple Y １ They may be the same or different. Y １ If there are multiple Y １ They may be combined. s represents an integer of 0 or more. t and u each independently represent an integer of 1 or more. [2] In the above formula (a-1) R １ However, the active photosensitive or radiation-sensitive resin composition according to [1], which represents an aromatic group. [3] Ar in the above formula (a-1) １ However, the photosensitive or radiation-sensitive resin composition according to [1] or [2], which represents a phenylene group. [4] -CO in formula (b-1) above ２ － Ar is joined ３ A photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein at least one -OH group is bonded to a ring member atom adjacent to a ring member atom. [5] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the anion represented by formula (b-1) is the anion represented by formula (b-2) below. In formula (b-2), Y １ represents a monovalent substituent. Y １ If there are multiple Y １ They may be the same or different. Y１ If there are multiple Y １ They may be combined. s represents an integer of 0 or more. t and u each independently represent an integer of 1 or more. [6] L in the above formula (a-1) １ [1] to [2] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [2], wherein the cation represented by formula (a-1) contains at least one fluorine atom. [3] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [2], wherein the organic anion of the onium salt compound (I) contains at least one iodine atom. [4] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [2], wherein the anion represented by formula (b-1) contains at least one fluorine atom selected from the group consisting of iodine atoms. [5] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [2], wherein the anion represented by formula (b-1) contains at least one fluorine atom selected from the group consisting of iodine atoms. [6] A resist film formed using the photosensitive or radiation-sensitive resin composition according to any one of [1] to [2].

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

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

[11] .

[0014] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that is excellent in roughness performance, resolution, and stability over time, a resist film formed from the photosensitive or radiation-sensitive resin composition, a pattern formation method using the photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0015] The present invention will now be described in detail. The following descriptions of the constituent elements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0016] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure with emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, and X-rays, but also drawing with particle beams such as electron beams and ion beams.

[0017] In this specification, "~" means that the numbers before and after it are included as the lower and upper limits. In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0018] 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).

[0019] 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.

[0020] (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; acetoxy groups, Examples include acyloxy groups such as propionyloxy and benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; and 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.

[0021] 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".

[0022] 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).

[0023] 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.

[0024] 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.

[0025] In this specification, "solids" means components contained in a photosensitive or radiation-sensitive resin composition that form a film (e.g., a resist film) formed using the photosensitive or radiation-sensitive resin composition, and does not include solvents. Furthermore, any component contained in a photosensitive or radiation-sensitive resin composition that forms a film (e.g., a resist film) formed using the photosensitive or radiation-sensitive resin composition shall be considered a solid, even if its properties are liquid.

[0026] [Photosensitive or Radiation-Sensitive Resin Composition] The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") contains an onium salt compound (I) comprising a cation represented by formula (a-1) and an organic anion, an onium salt compound (II) comprising an anion represented by formula (b-1) and an onium cation, an acid-degradable resin, and a solvent.

[0027] The mechanism by which the above effects are obtained by the composition of the present invention is not clear, but the inventors have made the following hypothesis. However, the present invention is not limited in any way by the following hypothesis mechanism. Onium salts containing a cation having an iodine atom can be used in resist compositions, for example, as a photoacid generator. In this case, although the effect of shot noise can be expected to be reduced because the iodine atom has a high absorption rate of EUV light, etc., the large volume of the iodine atom is thought to cause plasticization of the resist film, making it easier for the acid to diffuse and reducing the resolution. Furthermore, the roughness performance may also decrease. In the present invention, in addition to onium salt compound (I) containing a cation represented by formula (a-1) and an organic anion, which is an onium salt containing a cation having an iodine atom, onium salt compound (II) containing an anion represented by formula (b-1) and an onium cation can be used to suppress acid diffusion and improve resolution and roughness performance. Furthermore, the use of onium salt compound (II) improves the time-dependent stability of the resist composition. The anion represented by formula (b-1) in the onium salt compound (II) has -CO on the aromatic ring. ２ － It has -OH and -OH is -CO２ － Because it can interact with -CO ２ － Because the ability of the compound to attack cations is weakened, the long-term stability of the resist composition is expected to improve.

[0028] The composition of the present invention is typically a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. The composition of the present invention may be a resist composition for alkaline development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. Preferably, the composition of the present invention is a chemically amplified resist composition. A photosensitive or radiation-sensitive film can be formed using the composition of the present invention. A photosensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film.

[0029] The various components of the composition of the present invention will be described in detail below.

[0030] [Onium Salt Compound (I)] The composition of the present invention contains an onium salt compound (I) (also simply referred to as "onium salt compound (I)") comprising a cation represented by the following formula (a-1) and an organic anion.

[0031]

[0032] In formula (a-1), X represents a sulfur atom or an iodine atom. １ R represents a monovalent organic group. １ If multiple R １ They may be the same or different. １ If multiple R １ L may be combined. １ L represents a single bond or a divalent linking group. １ If there are multiple L １ They may be the same or different. １ and Ar ２ Each of these independently represents an aromatic group. Ar １ If there are multiple Ar１ They may be the same or different. ２ If there are multiple Ar ２ They may be the same or different. At least one R １ and at least one Ar １ k and m may be combined. k and m each independently represent an integer of 1 or more. If m represents an integer of 2 or more, multiple ks may be the same value or different values. n represents an integer of 0 or more. If X represents a sulfur atom, the sum of m and n is 3. If X represents an iodine atom, the sum of m and n is 2.

[0033] The onium salt compound (I) preferably functions as a compound that generates acid upon irradiation with active light or radiation (photoacid generator). The onium salt compound (I) is preferably a compound that generates an acid with a pKa of less than 1 upon irradiation with active light or radiation, and more preferably a compound that generates an acid with a pKa of 0 or less. Furthermore, there is no particular lower limit to the pKa of the acid generated from the onium salt compound (I) upon irradiation with active light or radiation, but it may be, for example, -4 or higher. If the onium salt compound (I) further contains an anion of a weak acid, such as a carboxylic acid anion, in its structure, the onium salt compound (I) may also function as an acid diffusion control agent.

[0034] The onium salt compound (I) may be in the form of a low molecular weight compound or a high molecular weight compound. Furthermore, the onium salt compound (I) may be in the form of both a low molecular weight compound and a high molecular weight compound. When the onium salt compound (I) is in the form of a low molecular weight compound, its molecular weight is preferably 4000 or less, and more preferably 3000 or less. There is no particular lower limit to the molecular weight of the onium salt compound (I), but it is preferably 100 or more. When the onium salt compound (I) is in the form of a high molecular weight compound, the onium salt compound (I) and the acid-degradable resin may be the same compound, or the onium salt compound (I) may be a different high molecular weight compound from the acid-degradable resin. If the acid-degradable resin does not contain repeating units having photoacid-generating groups, the composition of the present invention preferably contains the onium salt compound (I) as a compound different from the acid-degradable resin. The onium salt compound (I) is preferably in the form of a low molecular weight compound.

[0035] In formula (a-1), X represents a sulfur atom or an iodine atom, and it is preferable that X represents a sulfur atom.

[0036] R in equation (a-1) １ R represents a monovalent organic group. １ The number of carbon atoms in the monovalent organic group represented by is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. １ Examples of monovalent organic groups represented by include aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, arylthio groups, arylcarbonyl groups, arylcarbonyloxy groups, aryloxycarbonyl groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, alkylthio groups, alkylcarbonyl groups, alkylcarbonyloxy groups, and alkoxycarbonyl groups.

[0037] R １ The aromatic hydrocarbon ring of the aryl group represented by may be monocyclic or polycyclic. The number of member atoms of the aromatic hydrocarbon ring of the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. １The aryl group represented is preferably a phenyl group, a naphthyl group, or an anthyl group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. The aryl group may have substituents.

[0038] R １ The descriptions, specific examples, and preferred ranges of aryl groups included in aryloxy groups, arylthio groups, arylcarbonyl groups, arylcarbonyloxy groups, and aryl groups represented by the aryloxycarbonyl group are as described above. １ This is the same as the case with the aryl group represented by .

[0039] R １ The aromatic heterocycle of the heteroaryl group represented by may be monocyclic or polycyclic. The aromatic heterocycle of the heteroaryl group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 9. １ Examples of heteroaryl groups represented by include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. The heteroaryl group may have substituents.

[0040] R １ The description, specific examples, and preferred range of the heteroaryl group contained in the heteroaryloxy group represented by R are as described above. １ This is the same as the case of the heteroaryl group represented by .

[0041] R １The alkyl group represented by may be linear or branched, and alkyl groups having 1 to 20 carbon atoms are preferred, with alkyl groups having 1 to 10 carbon atoms being more preferred. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. The alkyl group may have substituents.

[0042] R １ The descriptions, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group, alkylthio group, alkylcarbonyl group, alkylcarbonyloxy group, and alkoxycarbonyl group are as described above. １ This is the same as in the alkyl group represented by .

[0043] R １ The alkenyl group represented by may be linear or branched, and is preferably an alkenyl group having 2 to 20 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl groups and allyl groups. The alkenyl group may have substituents.

[0044] R １ The alkynyl group represented by may be linear or branched, and is preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl groups and propargyl groups. The alkynyl group may have substituents.

[0045] R １The cycloalkyl group represented by preferably has 3 to 20 carbon atoms, and more preferably 4 to 10 carbon atoms. 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. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with vinylene groups. The cycloalkyl group may have substituents.

[0046] R １ The description, specific examples, and preferred range of the cycloalkyl group contained in the cycloalkyloxy group represented by R are as described above. １ This is the same as in the cycloalkyl group represented by .

[0047] R １ It is preferable that this represents an aryl group or a heteroaryl group, and more preferably an aryl group.

[0048] R １ If multiple R １ They may be the same or different. １ If multiple R １ They may be joined together. Multiple R １ When bonding occurs, it may be a single bond or a bond via a linking group. The linking group is not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR ｍ１ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. ｍ１ R represents a hydrogen atom or substituent. ｍ１ The substituent represented by is not particularly limited, but an example is the substituent T mentioned above.

[0049] L in equation (a-1) １represents a single bond or a divalent linking group. L １ The divalent linking group represented by １ is not particularly limited. For example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR ｍ１ -, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these, etc. can be mentioned. R ｍ１ represents a hydrogen atom or a substituent. R ｍ１ The substituent represented by ｍ１ is not particularly limited. For example, the above-mentioned substituent T can be mentioned. L １ Preferably contains at least one selected from the group consisting of an oxygen atom and a sulfur atom. L １ is more preferably -O-, -S-, -CO-, -CO ２ -, -SO-, and -SO ２ - and contains at least one selected from the group consisting of these. L １ When there are a plurality of L １ they may be the same or different.

[0050] In formula (a-1), Ar １ represents an aromatic group, and preferably represents an arylene group or a heteroarylene group. Ar １ The aromatic hydrocarbon ring of the arylene group represented by １ may be a monocyclic ring or a polycyclic ring. The number of carbon atoms of the ring member atoms of the aromatic hydrocarbon ring of the arylene group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. Examples of the arylene group include a phenylene group, a naphthylene group, an anthrylene group, etc. A phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable. Ar １The aromatic heterocycle of the heteroarylene group represented by may be monocyclic or polycyclic. Preferably, the aromatic heterocycle of the heteroarylene group contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroarylene group is preferably 5 to 20, and more preferably 5 to 15. Examples of heteroarylene groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. １ Ar preferably represents an arylene group, and more preferably a phenylene group. １ The arylene group or heteroarylene group represented by Ar may have substituents. １ If there are multiple Ar １ They may be the same or different. At least one R １ and at least one Ar １ and may be combined.

[0051] Ar in equation (a-1) ２ Ar represents an aromatic group, preferably an aryl group or a heteroaryl group. ２ The aromatic hydrocarbon ring of the aryl group represented by Ar may be monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon ring of the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Examples of aryl groups include phenyl, naphthyl, and anthryl groups, with phenyl or naphthyl being preferred and phenyl being more preferred. ２The aromatic heterocycle of the heteroaryl group represented by Ar may be monocyclic or polycyclic. Preferably, the aromatic heterocycle of the heteroaryl group contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms of the aromatic heterocycle of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 15. Examples of heteroaryl groups include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. ２ Ar preferably represents an aryl group, and more preferably a phenyl group. ２ The aryl group or heteroaryl group represented by has k iodine atoms as substituents, but may have other substituents as well. ２ If there are multiple Ar ２ They may be the same or different.

[0052] In equation (a-1), k represents an integer greater than or equal to 1. For example, k may be an integer between 1 and 5, or an integer between 1 and 3.

[0053] In formula (a-1), m represents an integer of 1 or greater, and n represents an integer of 0 or greater. When X in formula (a-1) represents a sulfur atom, the sum of m and n is 3. When X represents an iodine atom, the sum of m and n is 2. It is preferable that m represents 1 or 2. It is preferable that n represents 0 or 1.

[0054] The cation represented by formula (a-1) preferably contains at least one fluorine atom. １ Ar １ and Ar ２ Preferably, at least one selected from the group consisting of has at least one fluorine atom.

[0055] It is preferable that the cation represented by formula (a-1) is the cation represented by the following formula (a-2).

[0056]

[0057] In formula (a-2), X represents a sulfur atom or an iodine atom. １ R represents a monovalent organic group. １ If multiple R １ They may be the same or different. １ If multiple R １ They may be joined together. ２ and R ３ Each of these independently represents a substituent. ２ If multiple R ２ They may be the same or different. ３ If multiple R ３ They may be the same or different. L １ L represents a single bond or a divalent linking group. １ If there are multiple L １ They may be the same or different. At least one R １ And, R ２ It may be bonded to a substituted benzene ring. k and m each independently represent an integer of 1 or more. If m represents an integer of 2 or more, multiple k values ​​may be the same or different. n represents an integer of 0 or more. p and q each independently represent an integer between 0 and 4, inclusive. If m represents an integer of 2 or more, multiple p values ​​may be the same or different. If m represents an integer of 2 or more, multiple q values ​​may be the same or different. If X represents a sulfur atom, the sum of m and n is 3. If X represents an iodine atom, the sum of m and n is 2.

[0058] X, R in equation (a-2) １ , L １ The explanations, specific examples, and preferred ranges of X, R in formula (a-1) above are given by X, R １ , L １ , is the same as in k, m and n. R in equation (a-2) ２ and R ３The substituent represented by is not particularly limited, and for example, the substituent T is a alkyl group, a hydroxyl group, a bromine atom, or a fluorine atom, and is more preferably a fluorine atom. In formula (a-2), p and q each independently represent an integer between 0 and 4, and may represent an integer between 0 and 3, or an integer between 0 and 2.

[0059] The onium salt compound (I) contains an organic anion. The organic anion is not particularly limited and may be monovalent or divalent or more. The organic anion is preferably one with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0060] 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.

[0061] 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).

[0062] 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.

[0063] 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).

[0064] 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.

[0065] An example of a sulfonylimid anion is the saccharin anion.

[0066] 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.

[0067] 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.

[0068] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0069]

[0070] 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.

[0071] 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 R２ Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0072] L represents a divalent linking group. 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.

[0073] For L, a group represented by the following formula (AN1-1) is preferred. * ａ - (CR ２ａ ２ ) Ｘ -Q- (CR ２ｂ ２ ) Ｙ - * ｂ (AN1-1)

[0074] 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 ２ｂThese may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) １ ) (Caution ２ )- and CR that bind directly ２ｂ ２ In R ２ｂ is anything other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents the condition where X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) ２ａ and R ２ｂ If all of them are hydrogen atoms, then Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents. * Ａ R in equation (AN1) ３ This indicates the connection position on the side, * Ｂ This is -SO in equation (AN1). ３ － This indicates the connection point on the side.

[0075] In formula (AN1), R ３represents 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.).

[0076] Among them, R ３ Preferably, the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have substituents. Preferably, the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). The heteroatoms may be substituted for one or more carbon atoms forming the cyclic structure. Preferably, the organic group having a cyclic structure is a cyclic hydrocarbon group, a lactone ring group, and a sultone ring group. Among these, a cyclic hydrocarbon group is preferred. Preferably, the cyclic hydrocarbon group is a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.) and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone structure or sultone structure in any of the structures represented by formulas (LC1-1) to (LC1-22) and (SL1-1) to (SL1-3), as described later.

[0077] 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.

[0078] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0079]

[0080] 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.

[0081] 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.

[0082] 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.

[0083] L represents a divalent linking group. The description, specific examples, and preferred range of L are the same as those for L in formula (AN1) described above. If there are multiple Ls, they may be the same or different.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0089]

[0090] 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.

[0091] 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.

[0092] 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).

[0093] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions include, for example, N － (SO ２ -R ｑ ) ２ This is an anion represented by R. Here, R ｑ R represents an alkyl group which may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. ｑ They may be joined to each other to form a ring. Two R ｑ The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0094] The organic anion of the onium salt compound (I) may be a divalent or higher anion. For example, the organic anion may have two or more groups represented by any of the following formulas (AA-1) to (AA-3) and (BB-1) to (BB-6). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents the bond position. In formula (AA-2), R ＡR 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.

[0095]

[0096]

[0097] Specific examples of organic anions with two or more valent values ​​are shown below, but the examples are not limited to these.

[0098]

[0099]

[0100] Furthermore, the organic anion may have a nonionic site capable of neutralizing the acid. The nonionic site capable of neutralizing the acid is not particularly limited, and is preferably, for example, 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.

[0101]

[0102] 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.

[0103] The organic anion of the onium salt compound (I) preferably contains at least one iodine atom.

[0104] Specific examples of onium salt compounds (I) include (I)-1 to (I)-24 described in the examples below, but the present invention is not limited to these.

[0105] The content of onium salt compound (I) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, the content of onium salt compound (I) is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total solid content of the composition of the present invention. The composition of the present invention may contain one type of onium salt compound (I) or two or more types. If the composition of the present invention contains two or more types of onium salt compound (I), it is preferable that their total content is within the range of the above preferred content.

[0106] The onium salt compound (I) can be synthesized by referring to known methods (for example, the method described in Japanese Patent Application Publication No. 2020-15713).

[0107] [Onium Salt Compound (II)] The composition of the present invention contains an onium salt compound (II) (also simply referred to as "onium salt compound (II)") comprising an anion represented by the following formula (b-1) and an onium cation.

[0108]

[0109] In formula (b-1), Ar ３ Y represents an aromatic group. １ represents a monovalent substituent. Y １ If there are multiple Y １ They may be the same or different. Y １ If there are multiple Y １ They may be combined. s represents a non-negative integer. t and u each independently represent a non-negative integer of 1 or more.

[0110] The onium salt compound (II) preferably functions as an acid diffusion control agent. The acid diffusion control agent can act as a quencher that traps excess acid generated from the photoacid generator upon irradiation with active light or radiation (also called "exposure"), and suppresses the reaction of the acid-degradable resin in the unexposed areas due to the excess acid. The onium salt compound (II) preferably generates a weaker acid (a compound with a higher pKa) than the acid generated from the onium salt compound (I) upon irradiation with active light or radiation. The pKa of the compound generated from the onium salt compound (II) upon irradiation with active light or radiation may be 1 to 10 or 1.5 to 6. Furthermore, if the onium salt compound (II) has strong acid anions such as sulfonate anions or sulfonimide anions in its structure, the onium salt compound (II) may also function as a photoacid generator.

[0111] The onium salt compound (II) may be in the form of a low molecular weight compound or a high molecular weight compound. Furthermore, the onium salt compound (II) may be in the form of both a low molecular weight compound and a high molecular weight compound. When the onium salt compound (II) is in the form of a low molecular weight compound, its molecular weight is preferably 3000 or less, and more preferably 2000 or less. There is no particular lower limit to the molecular weight of the onium salt compound (II), but it is preferably 100 or more. When the onium salt compound (II) is in the form of a high molecular weight compound, the onium salt compound (II) and the acid-degradable resin may be the same compound, or the onium salt compound (II) may be a different high molecular weight compound from the acid-degradable resin. The onium salt compound (II) is preferably in the form of a low molecular weight compound.

[0112] Ar in equation (b-1) ３ Ar represents an aromatic group. ３ The aromatic group represented by Ar is not particularly limited. ３ The aromatic group represented by Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. ３The aromatic hydrocarbon group represented by may be monocyclic or polycyclic. The number of ring member atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Examples of aromatic hydrocarbon groups include groups having a benzene ring, a naphthalene ring, an anthracene ring, etc., with groups having a benzene ring or a naphthalene ring being preferred, and groups having a benzene ring being more preferred. ３ The aromatic heterocyclic group represented by may be monocyclic or polycyclic. The aromatic heterocyclic group preferably contains at least one ring member atom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The number of ring member atoms in the aromatic heterocyclic group is preferably 5 to 15. ３ Examples of aromatic heterocyclic groups represented by Ar include groups having a furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, indole ring, benzodiazole ring, carbazole ring, etc. ３ It is preferable that this represents an aromatic hydrocarbon group, and more preferably a group having a benzene ring.

[0113] Y in equation (b-1) １ represents a monovalent substituent. Y １ The monovalent substituent represented by is not particularly limited, and examples include the substituent T mentioned above, with a preferred monovalent organic group, halogen atom, or nitro group.

[0114] Y １ The number of carbon atoms in the monovalent organic group represented by is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. １ The monovalent organic group represented by is not particularly limited, but examples include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, alkylthio groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, arylthio groups, arylcarbonyl groups, arylcarbonyloxy groups, and aryloxycarbonyl groups.

[0115] Y１ The alkyl group represented by may be linear or branched, and alkyl groups having 1 to 20 carbon atoms are preferred, with alkyl groups having 1 to 10 carbon atoms being more preferred. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. The alkyl group may have substituents.

[0116] Y １ The descriptions, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group, alkylthio group, alkylcarbonyl group, alkylcarbonyloxy group, and alkoxycarbonyl group are as described above in Y. １ This is the same as in the alkyl group represented by .

[0117] Y １ The alkenyl group represented by may be linear or branched, and is preferably an alkenyl group having 2 to 20 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl groups and allyl groups. The alkenyl group may have substituents.

[0118] Y １ The alkynyl group represented by may be linear or branched, and is preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl groups and propargyl groups. The alkynyl group may have substituents.

[0119] Y １The cycloalkyl group represented by preferably has 3 to 20 carbon atoms, and more preferably 4 to 10 carbon atoms. 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. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with vinylene groups. The cycloalkyl group may have substituents.

[0120] Y １ The description, specific examples, and preferred range of the cycloalkyl group contained in the cycloalkyloxy group represented by Y are as described above. １ This is the same as in the cycloalkyl group represented by .

[0121] Y １ The aryl group represented is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents.

[0122] Y １ The descriptions, specific examples, and preferred ranges of aryl groups included in aryloxy groups, arylthio groups, arylcarbonyl groups, arylcarbonyloxy groups, and aryl groups represented by the aryloxycarbonyl group are as described above in Y. １ This is the same as the case with the aryl group represented by .

[0123] Y １ The heteroaryl group represented by is preferably an aromatic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms as a ring member. The number of ring member atoms of the heteroaryl group is preferably 3 to 20, and more preferably 4 to 10. The number of carbon atoms of the heteroaryl group is preferably 1 to 19, and more preferably 3 to 9. The heteroaryl group may have substituents.

[0124] Y １ The description, specific examples, and preferred range of the heteroaryl group contained in the heteroaryloxy group represented by Y are as described above. １ This is the same as the case of the heteroaryl group represented by .

[0125] Y １ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0126] Y １ If there are multiple Y １ They may be the same or different. Y １ If there are multiple Y １ They may be joined together. Multiple Y １ When bonding occurs, it may be a single bond or a bond via a linking group. The linking group is not particularly limited, but for example, -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, -NR ｍ１ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. ｍ１ R represents a hydrogen atom or substituent. ｍ１ The substituent represented by is not particularly limited, but an example is the substituent T mentioned above.

[0127] In equation (b-1), t represents an integer greater than or equal to 1. For example, t may represent an integer from 1 to 3, or it may represent 1 or 2, or it may represent 1.

[0128] In equation (b-1), u represents an integer greater than or equal to 1. For example, u may represent an integer from 1 to 3, or it may represent 1 or 2, or it may represent 1.

[0129] In equation (b-1), s represents an integer greater than or equal to 0. For example, s may represent an integer from 0 to 4, an integer from 0 to 3, or an integer from 0 to 2.

[0130] It is preferable that the anion represented by formula (b-1) contains at least one selected from the group consisting of fluorine atoms and iodine atoms.

[0131] -CO in equation (b-1) ２ － Ar is joined ３ It is preferable that at least one -OH group is bonded to a ring member atom adjacent to a ring member atom.

[0132] The anion represented by formula (b-1) is preferably the anion represented by the following formula (b-2).

[0133]

[0134] In formula (b-2), Y １ represents a monovalent substituent. Y １ If there are multiple Y １ They may be the same or different. Y １ If there are multiple Y １ They may be combined. s represents a non-negative integer. t and u each independently represent a non-negative integer of 1 or more.

[0135] Y in equation (b-2) １ The explanations, specific examples, and preferred ranges of s, t, and u are given in the aforementioned formula (b-1) Y １ This is the same as in s, t, and u.

[0136] The onium salt compound (II) contains an onium cation. The onium cation is not particularly limited and may be monovalent or divalent or more. The onium cation is preferably a sulfonium cation or an iodonium cation. The onium cation is preferably a cation represented by the following formula (ZaI) (also called "cation (ZaI)") or a cation represented by the following formula (ZaII) (also called "cation (ZaII)").

[0137]

[0138] 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 ２０３The number of carbon atoms of the organic group as is preferably 1 to 30, more preferably 1 to 20. R ２０１ ~R ２０３ Two of them may be bonded 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. R ２０１ ~R ２０３ Examples of the group formed by bonding two of R ２ ~R ２ include an alkylene group (e.g., a butylene group and a pentylene group), and -CH ２ -CH ２ [[ID=I6]]-O-CH ２０１ -CH ２０３ -

[0139] Preferred embodiments of the organic cation in the formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the cation (ZaI-3b), and the cation (ZaI-4b), which will be described later.

[0140] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R ２０１ ~R ２０３ is an aryl group. All of R ２０１ ~R ２０３ may be aryl groups, or a part of R ２０１ ~R ２０３ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. One of R ２０１ ~R ２０３ is an aryl group, and the remaining two of R ２０１ ~R ２０３ may be bonded 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. Examples of the group formed by bonding two of R ２ ~R ２ include an alkylene group 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., a butylene group, a pentylene group, and -CH ２ -CH２ Examples include (-). Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0141] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation may have as necessary 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, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0142] R ２０１ ~R ２０３ Preferred substituents that the aryl group, alkyl group, and cycloalkyl group of may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above substituents may further have substituents when possible. It is also preferable that the above substituents form an acid-decomposable group in any combination.

[0143] 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.

[0144] R ２０１ ~R ２０３ Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, norbornyl group). ２０１ ~R ２０３ R may be further substituted with halogen atoms, alkoxy groups (e.g., C1-C5), hydroxyl groups, cyano groups, or nitro groups. ２０１ ~R ２０３ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0145] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0146]

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0152]

[0153] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. １３ R represents a group containing a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. １４R represents a hydroxyl group, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. １４ If multiple instances exist, each independently represents one of the above groups, such as a hydroxyl group. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0154] 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.

[0155] 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).

[0156] 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.

[0157] The following are specific examples of onium cations, but are not limited to these.

[0158]

[0159]

[0160] The onium cation of the onium salt compound (II) may be the cation represented by the formula (a-1) described above.

[0161] Specific examples of onium salt compounds (II) include (II)-1 to (II)-24 described in the examples below, but the present invention is not limited to these.

[0162] The content of onium salt compound (II) is not particularly limited, but is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and even more preferably 1 to 35% by mass, relative to the total solid content of the composition of the present invention. The composition of the present invention may contain one type of onium salt compound (II) or two or more types. If the composition of the present invention contains two or more types of onium salt compound (II), it is preferable that their total content is within the range of the above preferred content.

[0163] The mixing ratio of onium salt compound (I) and onium salt compound (II) in the composition of the present invention is not particularly limited. For example, the mass ratio of onium salt compound (I) to onium salt compound (II) (onium salt compound (I) / onium salt compound (II)) may be 1 / 10 to 100 / 1, or 1 / 3 to 50 / 1.

[0164] [Acid-degradable resin] The composition of the present invention contains an acid-degradable resin. The acid-degradable resin is a resin that decomposes upon the action of an acid, preferably a resin whose polarity changes upon the action of an acid, and more preferably a resin whose polarity increases upon the action of an acid.

[0165] (Repeating units having acid-degradable groups) Acid-degradable resins preferably contain repeating units having acid-degradable groups (hereinafter also referred to as "repeating unit A1"). Acid-degradable groups are groups that decompose and increase in polarity upon the action of an acid, and are typically groups that decompose upon the action of an acid to produce polar groups. Acid-degradable groups preferably have a structure in which the polar group is protected by a group that is left behind upon the action of an acid (leaving group). Acid-degradable resins preferably increase in polarity upon the action of an acid, resulting in increased solubility in alkaline developers and decreased solubility in organic solvents. Examples of the above polar groups include acidic groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0166] Examples of groups that are eliminated by the action of an acid include the groups represented by any of the following formulas: (Y1), (Y2), (Y3), and (Y4). Formula (Y1): -C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (Caution ３７ ) ( OR ３８ ) Formula (Y4): -C(Rn １ ) (Rn ２ ) (H)

[0167] In equations (Y1) and (Y2), Rx １ ~Rx３ Each of these independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an aryl group. １ ~Rx ３ If all of them are alkyl groups, Rx １ ~Rx ３ It is preferable that at least two of them are methyl groups. １ ~Rx ３ These two may combine to form a monocycle or polycycle. Rx １ ~Rx ３ Preferred alkyl groups include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The alkynyl group is preferably an ethynyl group or a propargyl group. Rx １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group.

[0168] 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 ~Rx３ The cycloalkyl group formed by the bonding of these two groups may have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) and the group represented by formula (Y2) are, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group.

[0169] When the composition of the present invention is used as an EUV resist, Rx １ ~Rx ３ Alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and Rx are represented by １ ~Rx ３ The ring formed by the bonding of these two elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0170] In formula (Y3), R ３６ ~R ３８ Each of these independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and alkynyl groups. ３６ It is also preferable that it be a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl group may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. ３８ R may bond with other substituents on the repeating main chain to form a ring. ３８A group formed by the bonding of another substituent having a main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group. When the resist composition of the present invention is used as a resist for EUV, R ３６ ~R ３８ The monovalent organic group represented by, and R ３７ And R ３８ The ring formed by bonding to each other preferably further has a fluorine atom or an iodine atom as a substituent.

[0171] In the formula (Y4), Rn １ Represents an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rn ２ Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rn １ And Rn ２ May bond to each other to form a ring. Rn １ As, an aryl group is preferable. When the composition of the present invention is used as a resist for EUV, Rn １ And the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, or heteroaryl group represented by Rn ２ Preferably also has a fluorine atom or an iodine atom as a substituent.

[0172] From the viewpoint of excellent acid decomposability of the repeating unit, in the leaving group that protects the polar group, when a non-aromatic ring is directly bonded to the polar group (or its residue), among the non-aromatic rings, the ring member adjacent to the ring member atom directly bonded to the polar group (or its residue) Preferably does not have a halogen atom such as a fluorine atom as a substituent.

[0173] The group that dissociates by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group) such as a 1,1,4,4-tetramethylcyclohexyl group.

[0174] As the repeating unit A1, repeating units represented by formula (A-I) and repeating units represented by formula (A-II) are also preferred.

[0175]

[0176] In equation (A-I), Xa １ Rx represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. １ ~Rx ３ Rx in equation (Y1) １ ~Rx ３ It is the same as. In equation (A-II), Xa １ And T is Xa in equation (A-I). １ And is the same as T, and Rn １ and Rn ２ Rn in equation (Y4) １ and Rn ２ It is the same as this.

[0177] Xa １ Examples of alkyl groups that may have substituents, represented by , include a methyl group or -CH ２ -R １１ The group represented by R is an example. １１ R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. １ Preferably, the group is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0178] Examples of divalent linking groups for T include alkylene groups, aromatic groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ -, - (CH ２ ) ２ - or - (CH ２ ) ３ - is preferable.

[0179] Rx １ ~Rx ３ Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ The preferred cycloalkyl group is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The alkynyl group is preferably an ethynyl group or a propargyl group. Rx １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group.

[0180] Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. Rx １ ~Rx ３The cycloalkyl group formed by the bonding of these two may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by vinylene groups. In formula (AI), 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.

[0181] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms of the substituent is preferably 8 or less.

[0182] The repeating unit represented by formula (AI) is an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (Xa １ A repeating unit in which represents a hydrogen atom or a methyl group, and T represents a single bond, is preferred.

[0183] Specific examples of repeating unit A1 (a repeating unit having an acid-degradable group) are shown below, but are not limited to these. Furthermore, for specific examples of repeating unit A1, refer to, for example, the descriptions in

[0029] to

[0071] of International Publication No. 2022 / 024928, which are incorporated herein by reference. As monomers corresponding to repeating unit A1, M-c-1 to M-c-20 described in the examples below are also preferred.

[0184] Note that the monomer corresponding to the repeating unit is one whose structure, when its polymerizable group undergoes a polymerization reaction, is the same as the structure of the repeating unit. It is not necessary for the repeating unit to have been actually obtained using that monomer (for example, the repeating unit may be obtained by performing a polymerization reaction using another monomer and then changing its structure through a chemical reaction). Examples of polymerizable groups of monomers include groups containing carbon-carbon double bonds, such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups. Examples of polymerization reactions include addition polymerization. An example of a repeating unit and the monomer corresponding to that repeating unit is the repeating unit represented by the following formula (RM-1) and the monomer represented by the following formula (RM-2), which is the monomer corresponding to it.

[0185]

[0186] In formulas (RM-1) and (RM-2), R １００ R represents a hydrogen atom or substituent. １０１ * represents a substituent. １ and * ２ The symbol indicates the connection position.

[0187]

[0188] The content of repeating unit A1 is preferably 15 mol% or more, more preferably 40 mol% or more, and even more preferably 60 mol% or more, relative to the total repeating units in the acid-degradable resin. Furthermore, the content of repeating unit A1 is preferably less than 100 mol%, more preferably 95 mol% or less, and even more preferably 90 mol% or less, relative to the total repeating units in the acid-degradable resin. The acid-degradable resin may contain one type of repeating unit A1 or two or more types. If the acid-degradable resin contains two or more types of repeating unit A1, it is preferable that their total content is within the range of the above preferred content.

[0189] (Repeating units having acidic groups) Acid-degradable resins preferably contain repeating units having acidic groups (hereinafter also simply referred to as "repeating unit A2"). Repeating unit A2 is preferably a different repeating unit from the above repeating unit A1 (repeating unit having an acid-degradable group). Repeating unit A2 may also have a fluorine atom or an iodine atom. Preferred acidic groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Among these, repeating unit A2 is preferably a repeating unit having a phenolic hydroxyl group. The above hexafluoroisopropanol group may have one or more fluorine atoms (preferably 1 to 2) substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As for the acidic group, the -C(CF) formed in this way ３ ) (OH)-CF ２ - is also preferable. In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom, -C(CF ３ ) (OH)-CF ２ A ring containing - may be formed.

[0190] The repeating unit A2 is preferably a repeating unit represented by the following formula (Pa1), and the acid-degradable resin preferably contains the repeating unit represented by the following formula (Pa1).

[0191]

[0192] In formula (Pa1), R ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ Ar represents a single bond or a divalent linking group. ａ１ Ar represents an aromatic group with (m+n+1) valency. ａ１ And, R ａ２ or L ａ１ This may be a single bond or a bond via a linking group. Ｘ represents a substituent other than a hydroxyl group. n represents an integer between 1 and 9 (inclusive). m represents an integer between 0 and 8 (inclusive).

[0193] In the above formula (Pa1), R ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituent represented is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ and R ａ２ The alkyl group represented by may be linear or branched, and may have substituents. 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 even more preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. ａ１ and R ａ２ The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group may have substituents. ａ１ and R ａ２ Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms, with fluorine or iodine atoms being preferred. ａ１ and R ａ２ The alkyl group contained in the alkoxycarbonyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. The alkoxycarbonyl group may have substituents.

[0194] In the above formula (Pa1), L ａ１ L represents a single bond or a divalent linking group. ａ１ Examples of divalent linking groups represented by include -COO- and -CONR ａ３ -, alkylene groups, or groups formed by combining two or more of these groups.ａ３ R represents a hydrogen atom or an alkyl group. Preferred alkylene groups include C1-C8 alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, and octylene. The alkylene group may have substituents. ａ３ Examples of alkyl groups that represent an alkyl group include alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or fewer carbon atoms being preferred.

[0195] In the above formula (Pa1), Ar ａ１ Ar represents an aromatic group with (m+n+1) valency. ａ１ The aromatic group represented by may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferred aromatic hydrocarbon groups include groups containing aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. Preferred aromatic heterocyclic groups include groups containing aromatic heterocycles with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0196] Ar ａ１ And, R ａ２ or L ａ１ These may be bonded via single bonds or linking groups. Examples of linking groups include -O-, -S-, -CO-, and -CO ２ -, -SO-, -SO ２ - Examples include alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have substituents.

[0197] In the above formula (Pa1), R Ｘ R represents substituents other than hydroxyl groups. ＸExamples of substituents represented by include carboxyl groups, sulfo groups, cyano groups, halogen atoms, hydrocarbon groups, amino groups, nitro groups, and groups formed by combining two or more of these. Ｘ Examples of hydrocarbon groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 5 to 15 carbon atoms), and alkenyl groups (preferably having 2 to 10 carbon atoms). Ｘ The hydrocarbon group represented by may have substituents. Also, R Ｘ The hydrocarbon group represented is -CH ２ If it contains -, -CH ２ At least one of the following is -O-, -CO-, -S-, and -SO ２ - May be replaced by at least one selected from the group consisting of -. Ｘ The substituent represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom.

[0198] In the above formula (Pa1), n ​​represents an integer between 1 and 9, preferably between 1 and 5, and more preferably between 1 and 4. m represents an integer between 0 and 8, preferably between 0 and 4, and more preferably between 0 and 3. Specific examples of repeating unit A2 include, for example, the repeating unit described in

[0079] to

[0110] of International Publication No. 2022 / 024928, which is incorporated herein by reference. M-a-1 to M-a-13, described in the examples below, are also preferred monomers corresponding to repeating unit A2.

[0199] When the acid-degradable resin contains repeating units A2, the content of repeating units A2 is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in the acid-degradable resin. Furthermore, the content of repeating units A2 is preferably less than 60 mol%, and more preferably 50 mol% or less, relative to the total repeating units in the acid-degradable resin.

[0200] (Repeating units having lactone groups, sultone groups, or carbonate groups) Acid-degradable resins may have repeating units (hereinafter also simply referred to as "repeating unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that repeating unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0201] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. More preferably, the 5-7 membered ring lactone structure is fused with another ring structure in the form of a bicyclo or spiro structure, or the 5-7 membered ring sultone structure is fused with another ring structure in the form of a bicyclo or spiro structure. For units containing a lactone group or sultone group, refer to, for example, the descriptions in International Publication No. 2022 / 024928

[0119] to

[0126] and

[0132] to

[0133] , which are incorporated herein by reference.

[0202] A cyclic carbonate ester group is preferred as the carbonate group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in

[0127] to

[0133] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0203] When the acid-degradable resin contains repeating units Y, the content of repeating units Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in the acid-degradable resin. Furthermore, the upper limit is preferably less than 40 mol%, and more preferably 35 mol% or less, relative to the total repeating units in the acid-degradable resin.

[0204] (Repeating units having photoacid generating groups) Acid-degradable resins may contain repeating units (also called "repeating unit P") that have groups that generate acid upon irradiation with active light or radiation (also called "photoacid generating groups"), but it is also preferable that acid-degradable resins do not contain repeating units having photoacid generating groups.

[0205] Specific examples of repeating units P include, for example, the repeating units described in

[0094] to

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

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

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

[0206] When the acid-degradable resin contains repeating units P, the content of repeating units P is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the total repeating units in the acid-degradable resin. Furthermore, the content of repeating units P is preferably less than 40 mol%, more preferably 30 mol% or less, and even more preferably 20 mol% or less, relative to the total repeating units in the acid-degradable resin.

[0207] (Repeating units represented by formula (V-1) or formula (V-2)) Acid-degradable resins may have repeating units represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating units represented by formula (V-1) and the following formula (V-2) are different from the repeating units described above.

[0208]

[0209] In equation (V-1) and equation (V-2) below, R ６ and R ７ Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ n represents an integer between 0 and 6. ４ X represents an integer between 0 and 4. ４represents a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954, which are incorporated herein by reference.

[0210] (Repeating units to reduce the mobility of the main chain) Acid-degradable resins are preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern breakdown during development. For repeating units to reduce the mobility of the main chain, refer to the contents of

[0144] to

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

[0211] (Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) Acid-degradable resins may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in acid-degradable resins include the repeating units described above for repeating unit Y. Preferred content is also as described for repeating unit Y.

[0212] The acid-degradable resin may have repeating units having a hydroxyl group or a cyano group. This improves substrate adhesion. The repeating units having a hydroxyl group or a cyano group are preferably repeating units having a saturated hydrocarbon group having a hydroxyl group or a cyano group (substituted with a hydroxyl group or a cyano group). Alternatively, they may be repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating units having a hydroxyl group or a cyano group are preferably not having an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group include the repeating units described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921, and the above description is incorporated herein by reference.

[0213] The acid-degradable resin may have repeating units having alkali-soluble groups. The inclusion of repeating units having alkali-soluble groups in the acid-degradable resin increases the resolution in contact hole applications. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. Examples of repeating units having alkali-soluble groups include the repeating units described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921, the above description is incorporated herein by reference.

[0214] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Acid-degradable resins may have repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. This reduces the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0215] (Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group) Acid-degradable resins may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0216]

[0217] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or -CH ２ -O-Ra ２ It represents the base. In the formula, Ra ２represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-098921, which are incorporated herein by reference.

[0218] (Other Repeating Units) Furthermore, the acid-degradable resin may have other repeating units besides those described above. For example, refer to the descriptions in

[0141] to

[0143] and

[0169] to

[0170] of International Publication No. 2022 / 024928, which are incorporated herein by reference.

[0219] In addition to the repeating structural units described above, acid-degradable resins may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0220] A preferred embodiment of the present invention is that the acid-degradable resin has at least one selected from the group consisting of lactone groups, carbonate groups, sultone groups, and saturated hydrocarbon groups having hydroxyl groups. Having at least one selected from the group consisting of lactone groups, carbonate groups, sultone groups, and saturated hydrocarbon groups having hydroxyl groups further improves etching resistance and LWR performance.

[0221] In a preferred embodiment of the present invention, the acid-degradable resin contains repeating units having iodine atoms. By including repeating units having iodine atoms in the acid-degradable resin, the absorption rate of EUV light and the like is increased, the effects of shot noise can be reduced, and the LWR performance is further improved.

[0222] In one preferred embodiment of the present invention, the acid-degradable resin contains repeating units having an aromatic ring. The repeating units containing the aromatic ring may be any of the repeating units described above. Furthermore, it is preferable that the acid-degradable resin contains repeating units having a hydroxyl group bonded to the aromatic ring. In particular, it is preferable that the repeating unit A2 contains a repeating unit having a hydroxyl group bonded to the aromatic ring.

[0223] Acid-degradable resins can be synthesized according to conventional methods (e.g., radical polymerization). As polystyrene equivalent values ​​obtained by the GPC method, the weight-average molecular weight (Mw) of the acid-degradable resin is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Mw / Mn) of the acid-degradable resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.8. Lower dispersion results in better resolution and resist shape, smoother sidewalls of the resist pattern, and superior roughness.

[0224] The content of the acid-degradable resin in the composition of the present invention is preferably 20 to 99% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 85% by mass, based on the total solid content of the composition of the present invention. The composition of the present invention may contain one type of acid-degradable resin or two or more types. If the composition of the present invention contains two or more types of acid-degradable resins, it is preferable that their total content is within the range of the above preferred content.

[0225] [Acid Diffusion Control Agent (A)] The composition of the present invention may further contain a compound that is neither an onium salt compound (I) nor an onium salt compound (II), and that functions as an acid diffusion control agent (also referred to as "acid diffusion control agent (A)"). Examples of acid diffusion control agent (A) include basic compounds (AA), low molecular weight compounds (AB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (AC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compound (AC) include onium salt compounds (AD) of acids that are relatively weak acids with respect to the acid generated from a photoacid generator, and basic compounds (AE) whose basicity is reduced or lost by irradiation with active light or radiation. Specific examples of basic compounds (AA) include, for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (AE) 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 (AB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

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

[0305] to

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

[0226] In addition to the above, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents.

[0227] The molecular weight of the acid diffusion control agent (A) is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0228] When the composition of the present invention contains an acid diffusion control agent (A), the content of the acid diffusion control agent (A) is not particularly limited, but may be 0.001 to 30% by mass, 0.01 to 20% by mass, or 0.1 to 10% by mass, relative to the total solid content of the composition of the present invention. Only one type of acid diffusion control agent (A) may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content. It is also preferable that the composition of the present invention does not contain an acid diffusion control agent (A).

[0229] [Hydrophobic Resin] The composition of the present invention may contain a hydrophobic resin different from an acid-degradable resin. 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.

[0230] 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 substructure has one or more of these substructures, and more preferably two or more. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

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

[0231] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and even more preferably 0.1 to 5.0% by mass, based on the total solid content of the composition of the present invention. Only one type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0232] [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.

[0233] 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 resist composition. 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.

[0234] [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). 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. The content of the solvent in the composition of the present invention is not particularly limited, but it is preferably set so that the solid content concentration of the composition of the present invention is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0235] [Other Additives] The composition of the present invention may further contain, as other additives, at least one selected from the group consisting of dissolution inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer (for example, phenol compounds with a molecular weight of 1000 or less, or alicyclic or aliphatic compounds containing a carboxyl group). The above-mentioned "dissolution inhibitor" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer.

[0236] The content of other additives is not particularly limited, but may be 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, relative to the total solid content of the composition of the present invention. Only one type of other additive may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0237] Furthermore, the composition of the present invention may contain water as an impurity. When water is present as an impurity, a smaller amount of water is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total composition of the present invention. Furthermore, the composition of the present invention may contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are present as impurities, a smaller amount of residual monomers is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total solid content of the composition of the present invention.

[0238] [Resist film, pattern formation method] The present invention also relates to a resist film formed using the composition of the present invention. The pattern formation method of the present invention includes the steps of: (1) forming a resist film on a substrate using the composition of the present invention; (2) exposing the resist film; and (3) developing the exposed resist film using a developer to form a pattern. Each of the above steps will be described in detail below.

[0239] [Step (1)] Step (1) is a step of forming a resist film on a substrate using the composition of the present invention. Details of the composition of the present invention used in step (1) are as described above.

[0240] One method for forming a resist film on a substrate using the composition of the present invention is to coat the substrate with the composition of the present invention (also referred to as the "resist composition"). If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but if it is a polymer, it is preferably made of polyolefins such as polyethylene (PE) and polypropylene (PP) (including high density and ultra-high molecular weight); polyamides such as nylon 6 and nylon 66; polyimide (PI); polyamideimide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimide, polyesters, polysulfones, cellulose, polyfluorocarbons and their derivatives. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0241] The resist composition may be filtered using one filter or a combination of two or more filters. If two or more filters are used, they may be the same filter or different filters. The resist composition may also be circulated and filtered repeatedly using the same filter.

[0242] The resist composition can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The preferred rotation speed when spin coating using a spinner is 1000 to 3000 rpm (rotations per minute). After applying the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films, etc.) may be formed in the layer below the resist film.

[0243] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in at least one of a normal exposure machine and a developer machine, and may also be carried out using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0244] 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.

[0245] A topcoat may be formed on the upper layer of the resist film using a topcoat composition. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be contained in the resist composition.

[0246] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). Methods of exposure include irradiating the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0247] It is preferable to bake (heat) the image after exposure but before developing. This step is also called post-exposure baking. Baking promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. The baking temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The baking time is not particularly limited, but is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using means provided in at least one of a normal exposure machine and a developer, and may also be done using a hot plate or the like.

[0248] [Step (3)] Step (3) is a step in which the resist film exposed in step (2) is developed using a developer to form a pattern. By performing step (3), a resist pattern (also simply called a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (hereinafter also called an organic developer). Examples of development methods include immersing the substrate in a tank filled with developer for a certain period of time (dip method), puddling the developer on the substrate surface using surface tension and letting it stand for a certain period of time to develop (paddle method), spraying the developer onto the substrate surface (spray method), and continuously dispensing the developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). The development time is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C. In step (3), a step of stopping the development process while substituting with another solvent may be performed.

[0249] 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.

[0250] 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.

[0251] The above organic solvents may be mixed in multiple quantities, or mixed with solvents other than the above organic solvents or with water. The water content of the organic developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the organic developer.

[0252] The organic developer preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having 9 to 12 carbon atoms. The hydrocarbon having 9 to 12 carbon atoms contained in the organic developer may be just one type or two or more types. The hydrocarbon having 9 to 12 carbon atoms is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes and cycloalkanes, more preferably an alkane, even more preferably at least one selected from the group consisting of nonanes, decanes, undecanes and dodecanes, particularly preferably at least one selected from the group consisting of undecanes and dodecanes, and most preferably undecanes. The hydrocarbon having 9 to 12 carbon atoms may also contain structural isomers.

[0253] The butyl acetate content in the organic developer is preferably 65% ​​to 99% by mass, more preferably 70% to 95% by mass, and even more preferably 75% to 90% by mass, based on 100% by mass of the entire organic developer. The hydrocarbon content (total amount if multiple hydrocarbons with 9 to 12 carbon atoms are included) in the organic developer is preferably 1% to 35% by mass, more preferably 5% to 30% by mass, and even more preferably 10% to 25% by mass, based on 100% by mass of the entire organic developer.

[0254] The mass ratio of butyl acetate to hydrocarbons having 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having 9 to 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, even more preferably 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0255] Organic developers may contain other components in addition to butyl acetate and hydrocarbons having 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having 9 to 12 carbon atoms, surfactants, antioxidants, and basic compounds.

[0256] [Rinsing Step] After step (3), rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general solvent can be used. The rinsing solution preferably 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.

[0257] The rinsing method is not particularly limited and includes, for example, a method in which rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (rotary coating method), a method in which the substrate is immersed in a tank filled with rinsing liquid for a certain period of time (dip method), and a method in which rinsing liquid is sprayed onto the surface of the substrate (spray method).

[0258] Furthermore, the pattern formation method of the present invention may include a heating step (Post Bake) after step (3). This step removes any developer and rinse solution remaining between and inside the patterns. This step also has the effect of mellowing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250°C (preferably 90 to 200°C) for, for example, 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0259] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step (3) may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate. The method of processing the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step (3) as a mask. Dry etching is not particularly limited, but oxygen plasma etching is preferred.

[0260] In the pattern forming method of the present invention, the developer, resist composition, and other various materials (e.g., solvent, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) used are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 ppt or more. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0261] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as constituent materials for various materials, performing filter filtration on the constituent materials of various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®. Details of filtration using filters are described in paragraph

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

[0262] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0263] [Method for Manufacturing Electronic Devices] This specification relates to a method for manufacturing electronic devices, including the pattern forming method of the present invention described above, and to electronic devices manufactured by this manufacturing method. Preferred embodiments of the electronic devices of this specification include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0264] 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.

[0265] <Components of the Resist Composition> The components used in the preparation of the resist compositions used in the examples and comparative examples are shown below.

[0266] [Acid-degradable resins] The acid-degradable resins to be used (resins P-1 to P-32) are shown below. Acid-degradable resins can be synthesized according to known methods. Table 1 shows the type of repeating unit, the content of repeating units (mol%), the weight-average molecular weight (Mw), and the degree of dispersion (Mw / Mn) for resins P-1 to P-32. The type of repeating unit is indicated by the type of corresponding monomer. The weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (Mw / Mn) of resins P-1 to P-32 are measured as polystyrene equivalent values ​​using GPC (Gel Permeation Chromatography) measurement with a Tosoh Corporation HLC-8120GPC instrument (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector). The repeating unit content is also measured as follows: １３ It is determined by C-NMR (Nuclear Magnetic Resonance).

[0267]

[0268] The structures of monomers M-a-1 to M-a-13, M-b-1 to M-b-13, M-c-1 to M-c-20, and M-d-1 to M-d-4, which correspond to each repeating unit constituting the resin shown in Table 1, are shown below.

[0269]

[0270]

[0271]

[0272]

[0273] [Onium Salt Compound (I) and Comparative Compound] The structures of the onium salt compounds (I) ((I)-1 to (I)-24) and comparative compound ((X)-1) used are shown below. (X)-1 is not an onium salt compound (I). For convenience, (X)-1 is also listed in the column for onium salt compound (I) in Table 2.

[0274]

[0275]

[0276]

[0277]

[0278] [Onium Salt Compounds (II) and Comparative Compounds] The structures of the onium salt compounds (II) ((II)-1 to (II)-24) and comparative compound ((Y)-1) used are shown below. (Y)-1 is not an onium salt compound (II). For convenience, (Y)-1 is also listed in the onium salt compound (II) column in Table 2.

[0279]

[0280]

[0281]

[0282]

[0283] [Acid Diffusion Control Agent (A)] The structures of the acid diffusion control agents (A) (A-1 to A-5) used are shown below.

[0284]

[0285] [Surfactants] The surfactants used (B-1 to B-3) are as follows: B-1: Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant) B-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicone-based surfactant) B-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)

[0286] [Solvents] The solvents to be used (C-1 to C-9) are as follows: C-1: Propylene glycol monomethyl ether acetate (PGMEA) C-2: Propylene glycol monomethyl ether (PGME) C-3: Propylene glycol monoethyl ether (PGEE) C-4: Cyclohexanone C-5: Cyclopentanone C-6: 2-Heptanone C-7: Ethyl lactate C-8: γ-Butyrolactone C-9: Propylene carbonate

[0287] [Preparation of Resist Compositions] Dissolve the components shown in Table 2 in the solvents shown in Table 2 and mix so that the solid content concentration is 1.3% by mass. Filter the resulting mixture through a polyethylene filter with a pore size of 0.03 μm to prepare the resist compositions (Re-1 to Re-32, Re-C1 to Re-C3). Solid content refers to all components other than the solvent. The obtained resist compositions are used in the examples and comparative examples. In the table, the "Content" column shows the content (by mass) of each component relative to the total solid content in the resist composition. If two or more types of components are used, separate the types and their contents with a " / ". The order in which the types and contents separated by " / " are listed corresponds. If two or more types of solvents are used, separate the types and their mixing ratios (mass-based ratios when the total solvent is set to 100) with a " / ". The order in which the types and mixing ratios separated by " / " are listed corresponds. If using only one type of solvent, write "100" in the mixing ratio column.

[0288]

[0289] [Examples 1a-32a, Comparative Examples 1a-3a: Pattern Formation and Evaluation by EUV Exposure and Alkaline Development] <Pattern Formation> An underlayer film formation composition AL412 (manufactured by Brewer Science) is applied to a 12-inch diameter silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 3 is applied on top of the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. An EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) is used to irradiate the silicon wafer with the resist film with a pattern so that the average line width of the resulting pattern is 20 nm. As the reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 is used. After exposure, the resist film is baked at 90°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. This is then spin-dried to obtain a positive-type pattern.

[0290] <Evaluation> [Roughness Performance] Roughness performance is evaluated by LWR (Line Width Roughness). Using a resist composition immediately after preparation (within 12 hours of preparation), a 20 nm (1:1) line-and-space pattern is resolved at the optimal exposure amount for resolving a line pattern with an average line width of 20 nm. When observing the resulting pattern from above using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), the line width is observed at an arbitrary point, and its standard deviation (σ) is determined. The measurement variation of the line width is evaluated using 3σ (nm), and 3σ is defined as "LWR (nm)", and evaluated according to the following criteria. The smaller the LWR (nm) value, the better the roughness performance. [Judgment Criteria] A: LWR (nm) < 1.8 B: 1.8 < LWR (nm) < 2.0 C: 2.0 < LWR (nm) < 2.2 D: 2.2 < LWR (nm) < 2.5 E: 2.5 < LWR

[0291] [Resolution] A pattern is formed using the resist composition immediately after preparation (within 12 hours of preparation). In the above <Pattern Formation>, exposure is performed at the optimal exposure amount Eop (mJ / cm²). ２ The exposure is set to (the amount of exposure required for the pattern formed using the resist composition to reproduce the pattern of the mask used for exposure). Next, a test is conducted to form a line-and-space pattern by gradually changing the exposure amount from the optimal exposure amount Eop. At this time, the minimum line width dimension of the pattern that resolves without collapsing is determined using a length-measuring scanning electron microscope (SEM (Hitachi Ltd. S-9380II)), and this is defined as "resolution (nm)" and evaluated according to the following criteria. The smaller the resolution (nm) value, the better the resolution. [Criteria] A: Resolution (nm) < 11 B: 11 ≤ Resolution (nm) < 13 C: 13 ≤ Resolution (nm) < 15 D: 15 ≤ Resolution (nm) < 16 E: 16 ≤ Resolution (nm)

[0292] [Stability over time] Using a resist composition immediately after preparation (within 12 hours of preparation), the irradiation energy required to resolve a 1:1 line-and-space pattern with a line width of 20 nm is defined as sensitivity Eop1 (mJ / cm²). ２Next, the resist composition is stored at room temperature (25°C) for one month. After storage, a pattern is formed using the resist composition in the same manner as above, and the irradiation energy used to resolve a 1:1 line-and-space pattern with a line width of 20 nm is defined as sensitivity Eop2 (mJ / cm²). ２ ) Let the absolute value of the difference between Eop1 and Eop2 be the sensitivity variation (mJ / cm). ２ The following criteria will be used for evaluation. Sensitivity fluctuation will be used as an indicator of the temporal stability of the resist composition. The smaller the sensitivity fluctuation, the better the temporal stability. [Evaluation Criteria] A: Sensitivity fluctuation of 0.5 mJ / cm ２ Less than B: Sensitivity variation of 0.5 mJ / cm ２ Above, 1.0mJ / cm ２ Less than C: Sensitivity variation of 1.0 mJ / cm ２ Above, 1.5mJ / cm ２ Less than D: Sensitivity variation of 1.5 mJ / cm ２ Above, 2.0mJ / cm ２ Less than E: Sensitivity variation of 2.0 mJ / cm ２ bigger

[0293] The results shown in Table 3 below were obtained. Similar results can be obtained by changing the exposure source from EUV to an electron beam.

[0294]

[0295] [Examples 1b to 32b, Comparative Examples 1b to 3b: Pattern formation and evaluation by EUV exposure and organic solvent development] <Pattern formation> An underlayer film formation composition AL412 (manufactured by Brewer Science, Inc.) is applied to a 12-inch diameter silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 5 is applied on top of the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. An EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) is used to irradiate the silicon wafer with the resist film with a pattern so that the average line width of the resulting pattern is 20 nm. As a reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 is used. After exposure, the resist film is baked at 90°C for 60 seconds, then developed with the developer shown in Table 5 for 30 seconds, and then spin-dried to obtain a negative-type pattern.

[0296] Table 4 shows the developers used (R-1 to R-12). The content of the first and second solvents in Table 4 represents the mass ratio of each solvent to the total amount of the developer.

[0297]

[0298] <Evaluation> Roughness performance, resolution, and stability over time will be evaluated using the same method as described above.

[0299] The results shown in Table 5 below were obtained. Similar results can be obtained by changing the exposure source from EUV to an electron beam.

[0300]

[0301] As shown in Tables 3 and 5 above, the resist composition of the present invention exhibits excellent roughness performance, resolution, and stability over time.

[0302] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that is excellent in roughness performance, resolution, and stability over time, a resist film formed from the photosensitive or radiation-sensitive resin composition, a pattern formation method using the photosensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0303] 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. 2025-002723 filed on 8 January 2025, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiation-sensitive resin composition containing an onium salt compound (I) comprising a cation represented by the following formula (a-1) and an organic anion, an onium salt compound (II) comprising an anion represented by the following formula (b-1) and an onium cation, an acid-decomposable resin, and a solvent. In the formula (a-1), X represents a sulfur atom or an iodine atom. R １ represents a monovalent organic group. When there are a plurality of R １ , the plurality of R １ may be the same or different. When there are a plurality of R １ , the plurality of R １ may be bonded. L １ represents a single bond or a divalent linking group. When there are a plurality of L １ , the plurality of L １ may be the same or different. Ar １ and Ar ２ each independently represent an aromatic group. When there are a plurality of Ar １ , the plurality of Ar １ may be the same or different. When there are a plurality of Ar ２ , the plurality of Ar ２ may be the same or different. At least one R １ and at least one Ar １ may be bonded. k and m each independently represent an integer of 1 or more. When m represents an integer of 2 or more, the plurality of k may be the same value or different values. n represents an integer of 0 or more. When X represents a sulfur atom, the sum of m and n is 3. When X represents an iodine atom, the sum of m and n is 2. In the formula (b-1), Ar ３ represents an aromatic group. Y １ represents a monovalent substituent. When there are a plurality of Y １ , the plurality of Y １ may be the same or different. When there are a plurality of Y １ , the plurality of Y １ may be bonded. s represents an integer of 0 or more. t and u each independently represent an integer of 1 or more.

2. R in formula (a-1) １ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the aromatic group is represented.

3. Ar in formula (a-1) １ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the phenylene group is represented.

4. -CO in formula (b-1) ２ － Ar is joined ３ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein at least one -OH group is bonded to a ring member atom adjacent to a ring member atom.

5. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the anion represented by formula (b-1) is the anion represented by the following formula (b-2). In formula (b-2), Y １ represents a monovalent substituent. Y １ If there are multiple Y １ They may be the same or different. Y １ If there are multiple Y １ They may be combined. s represents an integer greater than or equal to 0. t and u each independently represent an integer greater than or equal to 1.

6. L in formula (a-1) １ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein it contains at least one selected from the group consisting of oxygen atoms and sulfur atoms.

7. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the cation represented by formula (a-1) contains at least one fluorine atom.

8. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the organic anion of the onium salt compound (I) contains at least one iodine atom.

9. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the anion represented by formula (b-1) comprises at least one selected from the group consisting of fluorine atoms and iodine atoms.

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

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

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

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