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

Abstract

The present invention pertains to: an actinic ray-sensitive or radiation-sensitive resin composition which comprises a resin, a compound that generates an acid when being irradiated with an actinic ray or radiation, and a solvent, and in which the resin exhibits a P (10%) of 0.40 or more as represented by formula (A) in the specification and determined by an integral molecular weight distribution curve obtained using a gel permeation chromatography measurement; and a resist film, a pattern formation method, and a method for manufacturing an electronic device, in all of which said actinic ray-sensitive or radiation-sensitive resin composition is used.

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] Patent Document 1 describes a resist composition comprising a resin having an acid-unstable group, an acid generator, and a compound having multiple specific acid-unstable groups.

[0005] Japanese Patent Application Laid-Open No. 2022-41917

[0006] Recently, the required performance of resist compositions and patterning methods has been increasing, but due to the progress of fineness and the like, the difficulty of satisfying such requirements has been increasing.

[0007] Under the above circumstances, an object of the present invention is to provide a chemically amplified photoresist or radiation-sensitive resin composition capable of forming an extremely fine pattern (for example, a line width of 20 nm or less) with excellent resolution. Another object of the present invention is to provide a resist film formed using the chemically amplified photoresist or radiation-sensitive resin composition, a patterning method using the chemically amplified photoresist or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

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

[0009] [1] A chemically amplified photoresist or radiation-sensitive resin composition containing a resin, a compound that generates an acid upon irradiation with actinic light or radiation, and a solvent, wherein the resin has a P(10%) of 0.40 or more represented by the following formula (A) determined from an integral molecular weight distribution curve obtained by gel permeation chromatography measurement. Formula (A): P(10%) = (molecular weight at a concentration fraction of 10%) ÷ weight average molecular weight [2] A chemically amplified photoresist or radiation-sensitive resin composition containing a resin, a compound that generates an acid upon irradiation with actinic light or radiation, and a solvent, wherein the resin has a P(90%) of 1.70 or less represented by the following formula (B) determined from an integral molecular weight distribution curve obtained by gel permeation chromatography measurement. Formula (B): P(90%) = (molecular weight at a concentration fraction of 90%) ÷ weight average molecular weight

[0010] [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin has a P (10%) represented by formula (A) of 0.50 or more. [4] The photosensitive or radiation-sensitive resin composition according to [2] or [3], wherein the resin has a P (90%) represented by formula (B) of 1.50 or less. [5] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin has a P (90%) represented by the following formula (B) of 1.70 or less. Formula (B): P (90%) = (Molecular weight at 90% concentration fraction) ÷ Weight-average molecular weight

[0011] [6] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin has repeating units represented by the following formula (i).

[0012]

[0013] In formula (i), X １ L represents a hydrogen atom or substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. n1 represents an integer greater than or equal to 1.

[0014] [7] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin comprises a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxyl group. [8] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin comprises an iodine atom.

[0015] [9] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the content of a compound that generates acid upon irradiation with the above-mentioned active light or radiation is 10% by mass or more with respect to the total solid content of the photosensitive or radiation-sensitive resin composition.

[10] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the resin contains more than 50 mol% of repeating units having acid-degradable groups with respect to the total repeating units.

[0016]

[11] The photosensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , wherein the compound that generates acid upon irradiation with the above-mentioned active light or radiation comprises a fluorine atom or an iodine atom.

[12] The photosensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , wherein the compound that generates acid upon irradiation with the above-mentioned active light or radiation comprises a cation having a fluorine atom.

[0017]

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

[12] , wherein the compound that generates acid upon irradiation with the above-mentioned active light or radiation comprises an anion having an iodine atom.

[14] A resist film formed using the photosensitive or radiation-sensitive resin composition according to any one of [1] to

[13] .

[0018]

[15] A pattern forming method comprising: (1) forming a film using the photosensitive or radiation-sensitive resin composition according to claim 1 or 2; (2) exposing the film; and (3) developing the exposed film with an organic processing solution containing butyl acetate and a hydrocarbon having 9 to 12 carbon atoms.

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

[15] .

[0019] The present invention provides a photosensitive or radiation-sensitive resin composition capable of forming patterns with excellent resolution. Furthermore, the present invention provides a resist film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device.

[0020] This diagram shows the results of gel permeation chromatography (GLA) measurements of a resin, along with an illustrative diagram of the integrated molecular weight distribution curve obtained by GLA.

[0021] The present invention will now be described in detail. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0022] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure with emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, and EUV, but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. In this specification, "~" is used to mean that the values ​​written before and after it are included as the lower and upper limits.

[0023] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Also, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0024] 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 gel permeation chromatography (GPC) measurement using a GPC 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).

[0025] 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.

[0026] (Substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkyloxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, and metactyl groups. Examples of substituents include acyl groups such as liloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; 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.

[0027] 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".

[0028] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0029] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate it by calculating the dissociation free energy. ＋ The dissociation free energy can be calculated using, for example, the Density Functional Theory (DFT), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT, such as Gaussian 16.

[0030] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett substituent constants and known literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above. However, if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0031] In this specification, "solids" means components contained in a photosensitive or radiation-sensitive resin composition that form a photosensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component contained in a photosensitive or radiation-sensitive resin composition that forms a photosensitive or radiation-sensitive film shall be considered a solid, even if its state is liquid.

[0032] [Photosensitive or Radiation-Sensitive Resin Composition] The photosensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") comprises a resin, a compound that generates acid upon irradiation with active light or radiation, and a solvent, wherein the resin has a P (10%) value of 0.2 or higher, which is expressed by the following formula (A) obtained from the integral molecular weight distribution curve obtained by gel permeation chromatography. Formula (A): P (10%) = (Molecular weight at a concentration fraction of 10%) ÷ Weight-average molecular weight

[0033] Another embodiment of the resist composition comprises a resin, a compound that generates acid upon irradiation with active light or radiation, and a solvent, wherein the resin has a P(90%) value of 2.4 or less, as expressed by the following formula (B) obtained from the integrated molecular weight distribution curve obtained by gel permeation chromatography. Formula (B): P(90%) = (Molecular weight at 90% concentration fraction) ÷ Weight-average molecular weight

[0034] Although the mechanism by which the resist composition of the present invention provides the above-mentioned effects is not fully understood, the inventors have hypothesized the following: In the first embodiment of the resin contained in the resist composition, P (10%) represented by formula (A) above is 0.2 or more. This reduces the content ratio of low molecular weight components contained in the resin, and when the film formed by the resist composition is exposed and developed, the penetration and swelling of the developer into film regions that are not intended to be removed by development, which originate from the low molecular weight components, is suppressed, and a pattern with excellent resolution can be formed. In the second embodiment of the resin contained in the resist composition, P (90%) represented by formula (B) above is 2.4 or less. This reduces the content ratio of high molecular weight components contained in the resin, and when the film formed by the resist composition is exposed and developed, development residues originating from the high molecular weight components are less likely to occur, and a pattern with excellent resolution can be formed.

[0035] The resist composition may be a positive-type resist composition or a negative-type resist composition, but a negative-type resist composition is preferred. Furthermore, the resist composition is preferably a resist composition for organic solvent development. The resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition, but a chemically amplified resist composition is preferred. The various components of the resist composition will be described in detail below.

[0036] <Resin (P)> The resin contained in the resist composition (also called "Resin (P)") is described below. The first aspect of Resin (P) (also called Resin (P1)) is that P(10%), expressed by the following formula (A) obtained from the integrated molecular weight distribution curve obtained from gel permeation chromatography measurement ("GPC measurement"), is 0.40 or higher. Formula (A): P(10%) = (Molecular weight at a concentration fraction of 10%) ÷ Weight-average molecular weight

[0037] First, let's explain P(10%). As mentioned above, P(10%) can be determined from the integrated molecular weight distribution curve obtained from gel permeation chromatography measurements.

[0038] Gel permeation chromatography (GPC) measurements are performed using a Gel Permeation Chromatography (GPC) instrument (HLC-8120GPC, manufactured by Tosoh Corporation) under the following conditions: 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.

[0039] Based on the GPC measurement results, a molecular weight calibration curve created using a polystyrene standard sample is used, and an integrated molecular weight distribution curve is created using EcoSEC data analysis software (manufactured by Tosoh Corporation), with molecular weight on the x-axis and concentration fraction on the y-axis.

[0040] P (10%) can be calculated by dividing the molecular weight at a concentration fraction of 10%, obtained from the integrated molecular weight distribution curve, by the weight-average molecular weight (Mw) obtained as a polystyrene equivalent value by performing gel permeation chromatography under the same conditions.

[0041] When P (10%) is 0.40 or higher, when the film formed by the resist composition is exposed and developed, the penetration and swelling of the developer into film regions that are not intended to be removed by development, which originate from the low molecular weight components contained in the resin (P), is suppressed, and a pattern with excellent resolution can be formed. In resin (P1), P (10%) is 0.40 or higher, preferably 0.50 or higher, more preferably 0.60 or higher, and even more preferably 0.70 or higher. Furthermore, in resin (P1), the upper limit of P (10%) is, for example, 2.00 or less, preferably 1.50 or less, and more preferably 1.00 or less.

[0042] The means of achieving P (10%) within the above range are not particularly limited, but examples include subjecting a resin obtained by a conventional method such as radical polymerization to a preparative apparatus such as a preparative GPC apparatus to remove low molecular weight components, or removing low molecular weight components by reprecipitation purification.

[0043] The second aspect of resin (P) (also called resin (P2)) is characterized by a P(90%) value of 1.70 or less, which is expressed by the following formula (B) obtained from the integrated molecular weight distribution curve obtained from GPC measurement. Formula (B): P(90%) = (Molecular weight at 90% concentration fraction) ÷ Weight-average molecular weight

[0044] Let's explain P(90%). As mentioned above, P(90%) can be determined from the integrated molecular weight distribution curve obtained from gel permeation chromatography measurements.

[0045] Gel permeation chromatography measurement and the creation of the integrated molecular weight distribution curve are performed in the same manner as described in the calculation of P(10%). P(90%) can be calculated by dividing the molecular weight at a concentration fraction of 90% obtained from the integrated molecular weight distribution curve by the weight-average molecular weight (Mw) obtained as a polystyrene equivalent value by performing gel permeation chromatography measurement under the same conditions.

[0046] When P(90%) is 1.70 or less, development residue derived from high molecular weight components contained in the resin (P) is less likely to occur when exposing and developing the film formed by the resist composition, and a pattern with excellent resolution can be formed. In resin (P2), P(90%) is 1.70 or less, preferably 1.60 or less, more preferably 1.50 or less, and even more preferably 1.40 or less. Furthermore, in resin (P2), the lower limit of P(90%) is, for example, 1.00 or more, preferably 1.10 or more, and more preferably 1.20 or more.

[0047] The means of achieving P (90%) within the above range are not particularly limited, but include, for example, subjecting a resin obtained by a conventional method such as radical polymerization to a preparative apparatus such as a preparative GPC apparatus to remove high molecular weight components, or removing high molecular weight components by reprecipitation purification.

[0048] The resin (P1) described above preferably has a P(90%) value of 1.70 or less, represented by the formula (B) described above. That is, the resin (P) preferably has a P(10%) value of 0.40 or more and a P(90%) value of 1.70 or less. More preferably, the resin (P) has a P(10%) value of 0.50 or more, even more preferably, a P(10%) value of 0.60 or more, and particularly preferably, a P(10%) value of 0.70 or more. Furthermore, the resin (P) preferably has a P(90%) value of 1.60 or less, even more preferably, a P(90%) value of 1.50 or less, and particularly preferably, a P(90%) value of 1.40 or less.

[0049] Figure 1 shows the results of gel permeation chromatography measurement of the resin and an illustrative diagram of the integrated molecular weight distribution curve obtained by gel permeation chromatography. The vertical axis of the integrated molecular weight distribution curve represents the concentration fraction (%). As shown in Figure 1, P(10%) and P(90%) can be determined.

[0050] The resin (P) typically contains groups that decompose and increase in polarity due to the action of acid (also called "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups containing unsaturated bonds are preferred as the repeating units having acid-degradable groups. In a pattern formation method using a resist composition, typically, when an organic developer is used as the developer, a negative-type pattern is suitably formed.

[0051] (Repeating Unit Having Acid-Degradable Group) Resin (P) preferably contains a repeating unit having an acid-degradable group. An acid-degradable group is a group that decomposes by the action of an acid and increases in polarity. An acid-degradable group is typically a group that decomposes by the action of an acid to generate a polar group. It is preferable that the acid-degradable group has a structure in which a polar group is protected by a group (detachable group) that detaches by the action of an acid. It is preferable that resin (P) increases in polarity by the action of an acid and decreases in solubility in an organic solvent. Examples of the above polar group include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group and the like. Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

[0052] Examples of the group that detaches by the action of an acid include groups represented by formula (Y1) to (Y4). Formula (Y1): -C(Rx １ )(Rx ２ )(Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ )(Rx ２ )(Rx ３ ) Formula (Y3): -C(R ３６ )(R ３７ )(OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0053] In formula (Y1) and formula (Y2), Rx １ to Rx ３Each of these independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ If all of them are alkyl groups (linear or branched), then Rx １ ~Rx ３ It is preferable that at least two of them are methyl groups. In particular, Rx １ ~Rx ３ Each preferably independently represents a linear or branched alkyl group, and Rx １ ~Rx ３ It is more preferable that each of these independently represents a linear alkyl group. １ ~Rx ３ These two may combine to form a monocycle or polycycle. Rx １ ~Rx ３ Preferred alkyl groups include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ A cycloalkyl group is preferred as the ring formed by the bonding of these two. Rx １ ~Rx ３The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with a monocyclic cycloalkyl group having 5 to 6 carbon atoms being more preferred. １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups may have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded to form the above-mentioned cycloalkyl group. When the photosensitive or radiation-sensitive resin composition is, for example, an EUV exposure resist composition, Rx １ ~Rx ３ Alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and Rx are represented by １ ~Rx ３ The ring formed by the bonding of these two elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0054] In formula (Y3), R ３６ ~R ３８ Each of these independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. ３６It is also preferable that the atom is a hydrogen atom. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. ３８ R may bond with other substituents on the repeating main chain to form a ring. ３８ The group formed by the bonding of the repeating unit main chain with another substituent is preferably an alkylene group such as a methylene group. When the photosensitive or radiation-sensitive resin composition is, for example, an EUV exposure resist composition, R ３６ ~R ３８ A monovalent organic group represented by, and R ３７ and R ３８ The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0055] The base represented by formula (Y3-1) below is preferred for formula (Y3).

[0056]

[0057] Here, L Ｙ１ and L Ｙ２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). Ｙ１ This represents a single bond or a divalent linking group. Q Ｙ１This represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which may contain a heteroatom such as a carbonyl group which may contain a heteroatom. Ｙ１ and L Ｙ２ Preferably, one of the groups is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group. Ｙ１ M Ｙ１ , and L Ｙ１ At least two of these may be joined to form a ring (preferably a five-membered or six-membered ring). In terms of pattern refinement, L Ｙ２ It is preferable that the group is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging. In formula (Y3-1), * represents the bond position.

[0058] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar.

[0059] From the standpoint of excellent acid decomposition properties of repeating units, in a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0060] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0061] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0062]

[0063] L １ R represents a divalent linking group which may have a fluorine atom or an iodine atom. １ R represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. ２ This represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. However, L １ , R １ , and R ２ At least one of them has a fluorine atom or an iodine atom. １ Divalent linking groups that may have a fluorine atom or an iodine atom, represented by -CO-, -O-, -S-, -SO-, -SO ２ - Hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linked groups formed by linking multiple thereof. Among these, L １The alkylene group is preferably -CO-, an arylene group, or an -arylene group-an alkylene group having a fluorine or iodine atom, and more preferably -CO-, or an -arylene group-an alkylene group having a fluorine or iodine atom. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine and iodine atoms in the alkylene group having a fluorine or iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0064] R １ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0065] R ２ Examples of leaving groups that may have a fluorine atom or an iodine atom, represented by the formulas (Y1) to (Y4) described above, include leaving groups that have a fluorine atom or an iodine atom.

[0066] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0067]

[0068] In equation (AI), Xa １ Rx represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. １ ~Rx ３Each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, Rx １ to Rx ３ If all of them are alkyl groups (linear or branched), at least two of Rx １ to Rx ３ are preferably methyl groups. Two of Rx １ to Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0069] The alkyl group optionally having a substituent represented by Xa １ includes, for example, a methyl group or a group represented by -CH ２ -R １１ . R １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples of the monovalent organic group represented by R １１ include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom. An alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. Xa １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0070] The divalent linking group of T includes an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ - group, -(CH ２ ) ２ - group, or -(CH ２ ) ３ - group is more preferred.

[0071] Rx １ to Rx ３Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Rx ３ The preferred cycloalkyl group is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. １ ~Rx ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Rx ３ A vinyl group is preferred as the alkenyl group. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. Rx １ ~Rx ３ The cycloalkyl group formed by the bonding of these two groups may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by vinylene groups. The repeating unit represented by formula (AI) is, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group.

[0072] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0073] 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.

[0074] The resin (P) may have repeating units having acid-degradable groups, specifically repeating units having acid-degradable groups containing unsaturated bonds. The repeating units having acid-degradable groups containing unsaturated bonds are preferably those represented by formula (B).

[0075]

[0076] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. １ ~Ry ３ Each of these independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, Ry １ ~Ry ３ At least one of these represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ These two may combine to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.) structure.

[0077] Examples of optionally substituted alkyl groups represented by Xb include a methyl group or -CH ２ -R １１ The group represented by R is an example. １１Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0078] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. As for L, -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO- are preferred. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0079] Ry １ ~Ry ３ Preferred alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. １ ~Ry ３ The cycloalkyl group is preferably 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 ~Ry ３ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. １ ~Ry ３ A vinyl group is preferred as the alkenyl group. １ ~Ry ３ As the alkynyl group, an ethynyl group is preferred. １ ~Ry ３As the cycloalkenyl group, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. １ ~Ry ３ The cycloalkyl group formed by the bonding of these two groups is preferably 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. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ A cycloalkyl group or cycloalkenyl group formed by the bonding of these two elements may, for example, have one of the methylene groups constituting the ring be a heteroatom such as an oxygen atom, a carbonyl group, or -SO ２ -Base and -SO ３ - These groups may be replaced by groups containing heteroatoms such as - groups, vinylidene groups, or combinations thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane or cycloalkene ring may be replaced by vinylene groups. The repeating unit represented by formula (B) is, for example, Ry １ is a methyl group, ethyl group, vinyl group, allyl group, or aryl group, R ２ and Ry ３ A preferred embodiment is one in which the two are bonded together to form the aforementioned cycloalkyl group or cycloalkenyl group.

[0080] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0081] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0082] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond include, for example, the repeating units described in

[0067] to

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

[0083] As for the repeating units having acid-degradable groups, repeating units represented by the following formula (Ga1) are preferred. That is, the resin (P) preferably contains repeating units represented by the following formula (Ga1).

[0084]

[0085] In formula (Ga1), X Ｇ１ represents a hydrogen atom, halogen atom, or hydrocarbon group. A Ｇ１ Y represents a single bond or an aromatic ring group. Ｇ１ represents -COO- or -O-. Ｇ１ , R Ｇ２ and R Ｇ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryl group. Ｇ１ , R Ｇ２ and R Ｇ３ Two of them may be joined to form a ring. However, R Ｇ１ , R Ｇ２ and R Ｇ３ The molecular weight of the compound represented by the following formula (Ga2), which includes [the specified compound], is 125 or greater.

[0086]

[0087] In formula (Ga2), R Ｇ１ , RＧ２ and R Ｇ３ These are R in equation (Ga1), respectively. Ｇ１ , R Ｇ２ and R Ｇ３ It expresses the same meaning.

[0088] X in equation (Ga1) Ｇ１ X represents a hydrogen atom, halogen atom, or hydrocarbon group. Ｇ１ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Ｇ１ The hydrocarbon group represented is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and more preferably an alkyl group. Ｇ１ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 4. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents. Ｇ１ 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. One or more methylene groups constituting the ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the ring of the cycloalkyl group may be replaced with a vinylene group. The cycloalkyl group may have substituents. Ｇ１ The alkenyl group represented by can be an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 5 carbon atoms. Examples of alkenyl groups include vinyl groups and allyl groups. The alkenyl group may have substituents. Ｇ１The aryl group represented is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, or an anthyl group. The aryl group may have substituents.

[0089] A in equation (Ga1) Ｇ１ This represents a single bond or an aromatic ring group, and a single bond is preferred. A Ｇ１ The aromatic ring group represented by is preferably a divalent aromatic ring group. The divalent aromatic ring group may be, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a torylene group, a naphthylene group, anthrylene group, or a biphenylene group. Alternatively, the divalent aromatic ring group may be a divalent aromatic ring group containing a heterocycle that includes at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Ｇ１ The aromatic ring group represented by may have substituents. A Ｇ１ When is an aromatic ring group, it is preferable to represent an arylene group, more preferably an arylene group having 6 to 12 carbon atoms, even more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

[0090] Y in equation (Ga1) Ｇ１ The symbol represents -COO- (ester bond) or -O- (ether bond), and it is preferable that it represents -COO-.

[0091] R in equation (Ga1) Ｇ１ , R Ｇ２ and R Ｇ３ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryl group. Ｇ１ , R Ｇ２ and R Ｇ３The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 4. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents. Ｇ１ , R Ｇ２ and R Ｇ３ 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. One or more methylene groups constituting the ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Also, one or more ethylene groups constituting the ring of the cycloalkyl group may be replaced with a vinylene group. The cycloalkyl group may have substituents. Ｇ１ , R Ｇ２ and R Ｇ３ Examples of alkenyl groups represented by include alkenyl groups having 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms, and more preferably alkenyl groups having 2 to 5 carbon atoms. Examples of alkenyl groups include vinyl groups and allyl groups. The alkenyl group may have substituents. Ｇ１ , R Ｇ２ and R Ｇ３ The alkoxy group represented by may be linear or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but 1 to 10 is preferred, 1 to 7 is more preferred, and 1 to 4 is particularly preferred. Examples of alkoxy groups include methoxy groups and ethoxy groups. The alkoxy group may have substituents. Ｇ１ , R Ｇ２ and R Ｇ３The aryl group represented is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, or an anthyl group. The aryl group may have substituents.

[0092] R Ｇ１ , R Ｇ２ and R Ｇ３ It is preferable that it has a halogen atom. Ｇ１ , R Ｇ２ and R Ｇ３ The halogen atoms present are preferably fluorine atoms or iodine atoms, and more preferably iodine atoms.

[0093] R Ｇ１ , R Ｇ２ and R Ｇ３ Two of them may combine to form a ring. Ｇ１ , R Ｇ２ and R Ｇ３ The ring formed by the bonding of two of these groups may be monocyclic or polycyclic. The number of carbon atoms in the ring is preferably 3 to 20, and more preferably 4 to 15. A cycloalkane ring is preferred as the ring. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing 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 a vinylene group. The ring may have substituents.

[0094] R Ｇ１ , R Ｇ２ and R Ｇ３ It may or may not contain an acid-degradable group, but R Ｇ１ , R Ｇ２ and R Ｇ３ It is preferable that it does not contain acid-degradable groups.

[0095] However, R Ｇ１ , R Ｇ２ and R Ｇ３ The molecular weight of the compound represented by formula (Ga2) containing is 125 or more. That is, formula (Ga1) is such that the molecular weight of the compound represented by formula (Ga2) is 125 or more. Ｇ１ , RＧ２ and R Ｇ３ It has R Ｇ１ , R Ｇ２ and R Ｇ３ When the molecular weight of the compound represented by formula (Ga2) containing is 125 or more, the Ohnishi parameter for the repeating unit (total number of atoms in the repeating unit / (number of carbon atoms in the repeating unit - number of nitrogen atoms in the repeating unit)) tends to decrease, and the carbon density tends to increase. This is thought to increase the strength of the resist film and further improve etching resistance. The molecular weight of the compound represented by formula (Ga2) is preferably 125 or more and 500 or less, more preferably 150 or more and 400 or less, and even more preferably 175 or more and 300 or less.

[0096] Specific examples of repeating units having acid-degradable groups are shown below, but are not limited to these. Repeating units having acid-degradable groups described in the examples below are also preferred.

[0097]

[0098]

[0099] The content of repeating units having acid-degradable groups is more than 50 mol%, preferably 60 mol% or more, and more preferably 65 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units having acid-degradable groups is preferably 100% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less, relative to the total repeating units in the resin (P). The resin (P) may contain one type of repeating unit having acid-degradable groups or two or more types. If the resin (P) contains two or more types of repeating units having acid-degradable groups, it is preferable that their total content is within the range of the above preferred content.

[0100] (Repeating units having acidic groups) The resin (P) preferably contains repeating units having acidic groups. Preferred acidic groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. One or more (preferably 1 to 2) fluorine atoms in the hexafluoroisopropanol group may be 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 is preferred. ３ ) (OH)-CF ２ - is also preferable. In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom, -C(CF ３ ) (OH)-CF ２ A ring containing a - may be formed. The repeating unit having an acidic group is preferably a different repeating unit from the repeating unit having the aforementioned acid-degradable group. The repeating unit having an acidic group may have a fluorine atom or an iodine atom. Specific examples of repeating units having an acidic group include, for example, the repeating units described in

[0088] to

[0089] and

[0103] to

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

[0101] The repeating unit having an acidic group is preferably a repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is preferably a different repeating unit from the repeating unit having an acid-degradable group as described above.

[0102] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa1). The resin (P) preferably contains the repeating unit represented by the following formula (Pa1).

[0103]

[0104] 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. ａ１Ar represents an aromatic ring group. ａ１ And, R ａ２ or L ａ１ The bonds may be single bonds or via linking groups. 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).

[0105] R in equation (Pa1) ａ１ and R ａ２ Each of these independently represents a hydrogen atom or a substituent. ａ１ and R ａ２ The substituent represented by 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. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents. 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 either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. The alkoxycarbonyl group may have substituents.

[0106] L in equation (Pa1) ａ１ L represents a single bond or a divalent linking group. ａ１ The divalent linking group represented by is not particularly limited, but for example, -COO-, -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. The alkylene group is not particularly limited, but C1-C8 alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, and octylene are preferred. 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.

[0107] Ar in equation (Pa1) ａ１ Ar represents an aromatic ring group, specifically an aromatic ring group with (m+n+1) valency. ａ１ The aromatic ring group represented by may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferably, the aromatic hydrocarbon group is a group containing aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. Preferably, the aromatic heterocyclic group contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as a ring member. Preferably, the aromatic heterocyclic group is a group containing aromatic heterocyclic rings with 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0108] Ar ａ１ And, R ａ２ or L ａ１ These may be bonded by a single bond or via a linking group. 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.

[0109] R in equation (Pa1) Ｘ R represents substituents other than hydroxyl groups. Ｘ Examples 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 substituent represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. 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 -.

[0110] Rx may have the above-described configuration of acid-degradable groups.

[0111] In formula (Pa1), n ​​represents an integer between 1 and 9, preferably between 1 and 5, and more preferably between 1 and 4.

[0112] In formula (Pa1), m represents an integer between 0 and 8, preferably between 0 and 4, and more preferably between 0 and 3.

[0113] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa2). The resin (P) preferably contains the repeating unit represented by the following formula (Pa2).

[0114]

[0115] In formula (Pa2), R ａ４ L represents a hydrogen atom or an alkyl group. ａ２ R represents a single bond or -COO-. Ｘ１ represents a halogen atom, haloalkyl group, or hydrocarbon group. n1 represents an integer between 1 and 5. m1 represents an integer between 0 and 4. r represents an integer between 0 and 3.

[0116] R in equation (Pa2) ａ４ R represents a hydrogen atom or an alkyl group. ａ４ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The alkyl group may have substituents.

[0117] L in equation (Pa2) ａ２ The symbol represents a single bond or a -COO-, and it is preferable that it represents a single bond.

[0118] In formula (Pa2), r represents an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 0. In formula (Pa2), the aromatic ring is benzene when r is 0, naphthalene when r is 1, anthracene when r is 2, and naphthacene when r is 3.

[0119] R in equation (Pa2) Ｘ１ R represents a halogen atom or a hydrocarbon group. Ｘ１ The halogen atom represented by is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Ｘ１ 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). ＸThe hydrocarbon group represented by preferably has a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. Ｘ１ The hydrocarbon group represented by may have substituents. Also, R Ｘ１ 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 -.

[0120] In formula (Pa2), n1 represents an integer between 1 and 5, preferably an integer between 1 and 4.

[0121] In formula (Pa2), m1 represents an integer between 0 and 4, preferably an integer between 0 and 3.

[0122] In another preferred embodiment, the repeating unit having an acid group is preferably a repeating unit represented by the following formula (i). The resin (P) preferably has a repeating unit represented by the following formula (i).

[0123]

[0124] In formula (i), X １ L represents a hydrogen atom or substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. n1 represents an integer greater than or equal to 1.

[0125] X in equation (i) １ R in the above formula (Pa1) is ａ１ This is synonymous, and similar examples can be given. １ In particular, it is preferable that the element represents a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

[0126] L in equation (i) １ L in the above formula (Pa1) is ａ１ This is synonymous with, and similar examples can be given. １ In particular, it is preferable that it represents a single bond or -COO-.

[0127] Ar represents an aromatic ring group, specifically an (n1+1) valent aromatic ring group. The aromatic ring group represented by Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Preferably, the aromatic hydrocarbon group is a group containing aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. Preferably, the aromatic heterocyclic group contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as a ring member. Preferably, the aromatic heterocyclic group is a group 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.

[0128] Ar and L １ These may be bonded by a single bond or via a linking group. 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.

[0129] Ar is preferably a group containing an aromatic hydrocarbon having 6 to 12 carbon atoms. Ar may also have substituents other than an OH group (hydroxyl group). Examples of substituents 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. Examples of hydrocarbon groups 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). The substituents are preferably halogen atoms. Preferred halogen atoms are fluorine atoms or iodine atoms, with iodine atoms being more preferred. The hydrocarbon group may also have substituents. Furthermore, the hydrocarbon group may be -CH ２ If it contains -, -CH ２At 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 -.

[0130] Ar may have the above-described configuration of acid-degradable groups.

[0131] n1 represents an integer greater than or equal to 1, preferably an integer between 1 and 9, more preferably an integer between 1 and 5, even more preferably an integer between 1 and 4, and particularly preferably 1 or 2.

[0132] Specific examples of repeating units having an acid group are shown below, but are not limited to these. In the following structural formula, G １ and G ２ Each of these independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxyl group, or a hydroxymethyl group. f1 represents an integer from 1 to 3. Repeating units having acid groups, as described in the examples below, are also preferred.

[0133]

[0134] When the resin (P) contains repeating units having acidic groups, the content of repeating units having acidic groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units having acidic groups is preferably less than 45 mol%, and more preferably 35 mol% or less, relative to the total repeating units in the resin (P).

[0135] (Repeating units having aromatic rings) The resin (P) preferably has repeating units having aromatic rings. The aromatic ring may be an aromatic hydrocarbon or an aromatic heterocycle. The aromatic hydrocarbon is preferably an aromatic hydrocarbon having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, and naphthacene. The aromatic heterocycle group preferably contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as a ring member. The aromatic heterocycle is preferably an aromatic heterocycle having 4 to 20 ring member atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. The repeating unit having an aromatic ring is not particularly limited, but an example is the repeating unit represented by the above formula (Pa1).

[0136] (Repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom) In addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above, the resin (P) may also have repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). The <repeating units that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom> referred to here are preferably different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0137] As the unit X, a repeating unit represented by formula (C) is preferred.

[0138]

[0139] L ５ R represents a single bond or an ester group. ９ R represents an alkyl group which may have a hydrogen atom, or a fluorine atom or an iodine atom. １０This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof. Specific examples of repeating units having a fluorine atom or an iodine atom include, for example, the repeating units described in

[0116] to

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

[0140] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the upper limit is preferably less than 45 mol%, and more preferably 35 mol% or less, relative to the total repeating units in the resin (P).

[0141] The total content of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom among the repeating units of the resin (P) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of the resin (P). There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of the resin (P). Examples of repeating units having at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.

[0142] (Repeating units having lactone groups, sultone groups, or carbonate groups) The resin (P) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0143] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferred. The resin (P) preferably has repeating units having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, ring member atoms of a lactone group, sultone group, or carbonate group may constitute the main chain of the resin (P). The lactone group, sultone group, and carbonate group may have substituents.

[0144] R in the following structural formula Ｌ R represents a substituent. Ｌ If multiple R Ｌ They can be the same or they can be different. Ｌ Examples include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. If there are multiple e1s, they may be the same or different. If e1 is 2 or more, there may be multiple R Ｌ The Rs may be the same or different, and there may be multiple Rs. Ｌ They may join together to form a ring.

[0145]

[0146] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include the repeating unit represented by the following formula (AI-2).

[0147]

[0148] In formula (AI-2), Rb ０ Rb represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ The alkyl group may have substituents. Rb ０ Preferred substituents that the alkyl group may have include a hydroxyl group and a halogen atom. Rb ０ Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ０ Ab is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these. In particular, Ab can be a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. Ab １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate ester structure represented by any of formulas (CC1-1) to (CC1-2).

[0149] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0150] A cyclic carbonate ester group is preferred as the carbonate group. For repeating units having a cyclic carbonate ester group, see, for example, the descriptions in

[0127] to

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

[0151] When the resin (P) contains unit Y, the content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in the resin (P). 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 resin (P).

[0152] (Repeating units having photoacid generating groups) The resin (P) may contain repeating units having groups that generate acid upon irradiation with active light or radiation (also called "photoacid generating groups"). Examples of repeating units having photoacid generating groups include the repeating unit represented by formula (4).

[0153]

[0154] R ４１ L represents a hydrogen atom or a methyl group. ４１ L represents a single bond or a divalent linking group. ４２ R represents a divalent linking group. ４０ This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain.

[0155] L ４１ represents a single bond or a divalent linking group, preferably a single bond or an ester bond (-COO-).

[0156] L ４２ These are alkylene groups, cycloalkylene groups, arylene groups, -O-, -CO-, -S-, -SO-, -SO ２It is preferable that the linking group consists of at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, cycloalkyl group, or aryl group). The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred. The cycloalkylene group may be a monocyclic or polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but 3 to 20 is preferred, and 5 to 15 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 20 is preferred, and 6 to 10 is more preferred. The alkylene group, cycloalkylene group and arylene group may have substituents, and the substituent T mentioned above is an example of a substituent.

[0157] R ４０ Preferably, the group is represented by the following formula (S4-1).

[0158]

[0159] In equation (S4-1), Q － represents an acid residue, M ＋ * represents a cation. * represents L ４１ This indicates the bonding position. An acid residue is a group formed when a proton dissociates from an acid. Q － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or sulfonamide group (N － -SO ２ R Ｎ１ It is represented by R Ｎ１ represents an organic group, and examples include organic groups having 1 to 10 carbon atoms, with alkyl groups, fluoroalkyl groups, or aryl groups being preferred. A sulfonate anion group is more preferred. ＋ The explanation, specific examples, and preferred ranges are described in the M section of the description of the photoacid generator (A) described later. ＋ It is the same as this.

[0160] Specific examples of repeating units having photoacid generating groups include, for example, the repeating units described in

[0094] to

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

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

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

[0161] Examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of International Publication No. 2018 / 193954.

[0162] When the resin (P) contains repeating units having photoacid-generating groups, the content of repeating units having photoacid-generating groups is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, relative to the total repeating units in the resin (P). Furthermore, the content of repeating units having photoacid-generating groups is preferably less than 40 mol%, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, relative to the total repeating units in the resin (P). It is also preferable that the resin (P) does not contain repeating units having photoacid-generating groups.

[0163] (Repeating units represented by formula (V-1) or formula (V-2)) The resin (P) may have repeating units represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating units represented by the following formulas (V-1) and (V-2) are different from the repeating units described above.

[0164]

[0165] In the formula, R ６ and R ７Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ n represents an integer between 0 and 6. ４ X represents an integer between 0 and 4. ４ This is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are given below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

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

[0166] (Repeating units to reduce the mobility of the main chain) The resin (P) is preferably given a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern breakdown during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of polymers such as resin (P) (hereinafter referred to as "Tg of repeating units") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated. Next, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Biceranno method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). The calculation of Tg using the Biceranno method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0167] For repeating units that reduce the mobility of the main chain, refer to the contents of International Publication No. 2022 / 024928, paragraphs

[0144] to

[0160] .

[0168] (Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (P) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in the resin (P) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0169] The resin (P) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion. The repeating units having hydroxyl groups or cyano groups are preferably repeating units having saturated hydrocarbon groups (substituted with hydroxyl groups or cyano groups) that have hydroxyl groups or cyano groups. Alternatively, they may be repeating units having an alicyclic hydrocarbon structure substituted with hydroxyl groups or cyano groups. The repeating units having hydroxyl groups or cyano groups are preferably not having acid-degradable groups. Examples of repeating units having hydroxyl groups or cyano groups are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0170] The resin (P) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in the resin (P) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

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

[0171] (Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) The resin (P) may have repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0172] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) The resin (P) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0173]

[0174] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or -CH ２ -O-Ra ２ It represents the base. In the formula, Ra ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group are those described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-098921.

[0175] (Other Repeating Units) Furthermore, the resin (P) may have other repeating units besides those described above. For example, the resin (P) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0176] In addition to the repeating structural units described above, the resin (P) 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.

[0177] As for the resin (P), in particular when the resist composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0178] A preferred embodiment of the present invention is that the resin (P) has at least one selected from the group consisting of lactone groups, sultone groups, carbonate groups, sulfonyl groups, alcoholic hydroxyl groups, and carboxyl groups. Having at least one selected from the group consisting of lactone groups, sultone groups, carbonate groups, sulfonyl groups, alcoholic hydroxyl groups, and carboxyl groups further improves etching resistance and LWR performance. An alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It is preferable that the carbon atom to which the hydroxyl group is bonded, or a carbon atom adjacent thereto, is not substituted with an electron-withdrawing group such as a fluorine atom.

[0179] In a preferred embodiment of the present invention, the resin (P) contains repeating units having a group that generates acid (photoacid generating group) upon irradiation with active light or radiation. By including repeating units having a photoacid generating group in the resin (P), the uniformity of the material distribution is increased, variations in acid concentration are reduced, and LWR performance is further improved.

[0180] In a preferred embodiment of the present invention, the resin (P) contains iodine atoms, and more preferably, contains repeating units having iodine atoms. By including repeating units having iodine atoms in the resin (P), 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.

[0181] The resin (P) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight (Mw) of the resin (P), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution, Mw / Mn) of the resin (P) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. A lower degree of dispersion results in better resolution and resist shape, smoother sidewalls of the resist pattern, and superior roughness.

[0182] The content of resin (P) in the resist composition is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 90.0% by mass, and even more preferably 50.0 to 80.0% by mass, based on the total solid content of the resist composition. Resin (P) may be used alone or in combination of two or more types. When two or more types are used, it is preferable that their total content is within the above preferred content range.

[0183] <Photoacid Generator (A)> The resist composition contains a compound that generates acid upon irradiation with active light or radiation (hereinafter also referred to as "photoacid generator (A)" or "compound (A)").

[0184] The photoacid generator (A) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer. Alternatively, both the low molecular weight compound form and the form incorporated into a polymer may be used in combination. When the photoacid generator (A) is in the form of a low molecular weight compound, its molecular weight is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000. When the photoacid generator (A) is incorporated into a polymer, it may be incorporated into a resin (P), or into a resin different from resin (P). If resin (P) does not contain the repeating units having the aforementioned photoacid generating group, the resist composition preferably contains the photoacid generator (A), which is a compound different from resin (P). If resin (P) contains repeating units having the photoacid generating group, the resist composition may or may not contain the photoacid generator (A).

[0185] For example, the photoacid generator (A) is "M ＋ X － Examples of compounds represented by '' (onium salts) include compounds that generate organic acids upon exposure. Examples of organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imide acid, and tris(alkylsulfonyl)methidic acid.

[0186] "M ＋ X － In the compound represented by ", M ＋ The symbol represents a cation, preferably an organic cation. The organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0187]

[0188] In the above formula (ZaI), R ２０１ , R ２０２ , and R２０３ Each of these independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH ２ -CH ２ -O-CH ２ -CH ２ - is one example.

[0189] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0190] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ It is an arylsulfonium cation in which at least one of the groups is an aryl group. ２０１ ~R ２０３ All of them may be aryl groups, or R ２０１ ~R ２０３ A portion of it may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ One of them is an aryl group, R ２０１ ~R ２０３ The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３Examples of groups formed by the bonding of two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH ２ -CH ２ -O-CH ２ -CH ２ Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0191] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, with methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group being more preferred.

[0192] R ２０１ ~R ２０３Preferred substituents on the aryl group, alkyl group, and cycloalkyl group include alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferable that the above substituents form an acid-degradable group in any combination. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a group that leaves upon the action of an acid. The polar group and leaving group are as described above.

[0193] 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.

[0194] R ２０１ ~R ２０３Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). ２０１ ~R ２０３ R may be further substituted with halogen atoms, alkoxy groups (e.g., C1-C5), hydroxyl groups, cyano groups, or nitro groups. ２０１ ~R ２０３ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0195] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0196]

[0197] In formula (ZaI-3b), R １ｃ ~R ５ｃ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0198] 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.

[0199] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of groups formed by the bonding include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0200] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and also, R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙThe rings formed by the bonding of these elements to each other may have substituents.

[0201] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0202]

[0203] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. １３ R represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. １４ R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. １４ If multiple instances exist, each independently represents one of the above groups, such as a hydroxyl group. １５ Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ They may bond to each other to form a ring. Two R １５ When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R １５ It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R １５ The ring formed by the bonding of these elements may have substituents.

[0204] In equation (ZaI-4b), R １３ , R１４ , and R １５ The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. １３ ~R １５ , and also, R ｘ and R ｙ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0205] Next, we will explain equation (ZaII). In equation (ZaII), R ２０４ and R ２０５ Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. ２０４ and R ２０５ The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0206] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. ２０４ and R ２０５Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0207] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0208]

[0209]

[0210] "M ＋ X － In the compound represented by ", X － The symbol represents an anion. The anion is not particularly limited, and examples include anions with 1 or 2 or more valent values. The anion is preferably one with a remarkably low ability to undergo nucleophilic reactions, and more preferably a non-nucleophilic anion. The anion is preferably an organic anion.

[0211] 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.

[0212] 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).

[0213] 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.

[0214] 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).

[0215] 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.

[0216] An example of a sulfonylimid anion is the saccharin anion.

[0217] 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.

[0218] 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.

[0219] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably having 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0220] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0221]

[0222] In formula (AN1), R１ and R ２ Each of these independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', and -NH. ２ ,-NR' ２ -NHR' or -NHCOR' are preferred. R' is a monovalent hydrocarbon group.

[0223] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. １ and R ２ Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0224] L represents a divalent linking group. If there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of divalent linking groups include alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining multiples thereof. Among these, examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ２ - or -COO-alkylene group- is more preferred.

[0225] 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)

[0226] In formula (AN1-1), * ａ R in equation (AN1) ３ This indicates the connection point with [the other element]. * ｂ -C(R) in equation (AN1) １ ) (Caution ２ ) - Represents the connection position with . X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3. R ２ａ and R ２ｂ Each of these independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ If there are multiple instances of each, then there are multiple instances of R ２ａ and R ２ｂ These can be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) １ ) (Caution ２ )- and CR that bind directly ２ｂ ２ In R ２ｂ is anything other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents the condition where X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) ２ａ and R ２ｂ If all of them are hydrogen atoms, then Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or, * Ａ -SO ２ - * Ｂ This represents. * Ａ R in equation (AN1) ３ This indicates the connection position on the side, * Ｂ This is -SO in equation (AN1). ３ － This indicates the connection point on the side.

[0227] In formula (AN1), R ３ represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0228] Among them, R ３Preferably, the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have substituents. Preferably, the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). The heteroatoms may be substituted for one or more carbon atoms forming the cyclic structure. Preferably, the organic group having a cyclic structure is a cyclic hydrocarbon group, a lactone ring group, and a sultone ring group. Among these, a cyclic hydrocarbon group is preferred. Preferably, the cyclic hydrocarbon group is a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.) and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably, for example, a group 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 formulas (SL1-1) to (SL1-3) described above.

[0229] R ３ It is preferable that it contains a halogen atom. ３ The halogen atoms included are preferably fluorine atoms and iodine atoms, with iodine atoms being particularly preferred. When used as an EUV resist, a larger number of halogen atoms is preferable from the viewpoint of EUV light absorption efficiency. When iodine atoms are present, a structure in which they are directly bonded to carbon atoms on the aromatic ring is preferred. As a preferred embodiment of the anion represented by formula (AN1), the one described in

[0040] to

[0044] of Japanese Patent Application Publication No. 2018-155908 can be cited.

[0230] 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.

[0231] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0232]

[0233] 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.

[0234] 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.

[0235] 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.

[0236] L represents a divalent linking group. The definition of L is the same as the L in formula (AN1).

[0237] 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.

[0238] 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.

[0239] 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.

[0240] W preferably contains halogen atoms. Preferred halogen atoms in W are fluorine atoms and iodine atoms, with iodine atoms being particularly preferred. When used as an EUV resist, a larger number of halogen atoms is preferable from the viewpoint of EUV light absorption efficiency. If iodine atoms are present, a structure in which they are directly bonded to carbon atoms on an aromatic ring is preferred.

[0241] 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.

[0242] Preferred embodiments of the anion represented by formula (AN2) include those described in International Publication No. 2023 / 157455

[0076] , Japanese Patent Publication No. 2021-81708

[0071] to

[0089] , Japanese Patent Publication No. 2018-5224

[0033] to

[0045] , and Japanese Patent Publication No. 2018-25789

[0031] to

[0039] .

[0243] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0244]

[0245] 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.

[0246] 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.

[0247] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group or an aromatic 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).

[0248] It is preferable that B contains halogen atoms. Preferred halogen atoms in B are fluorine atoms and iodine atoms, with iodine atoms being particularly preferred. When used as an EUV resist, a larger number of halogen atoms is preferable from the viewpoint of EUV light absorption efficiency. If iodine atoms are present, a structure in which they are directly bonded to carbon atoms on an aromatic ring is preferred.

[0249] Preferred embodiments of the anion represented by formula (AN3) include those described in

[0029] to

[0034] of Japanese Patent Application Publication No. 2018-159744 and

[0045] of Japanese Patent Application Publication No. 2018-155908.

[0250] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions include, for example, N － (SO ２ -R ｑ ) ２ This is an anion represented by R. Here, R ｑ R represents an alkyl group which may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. ｑ They may be joined to each other to form a ring. Two R ｑ The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0251] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0252]

[0253]

[0254] In formula (d1-1), R ５１ represents a hydrocarbon group (e.g., an aryl group such as a phenyl group) which may have substituents (e.g., a hydroxyl group).

[0255] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). ２ｃThe hydrocarbon group in formula (d1-2) may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member carbon atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have substituents. The carbon atoms forming the norbornyl group may be carbonyl carbons. Also, the "Z" in formula (d1-2) ２ｃ -SO ３ － It is preferable that the anion is different from the anion represented by the above formulas (AN4), (AN1), or (AN5). For example, Z ２ｃ It is preferable that it is not an aryl group. Also, for example, Z ２ｃ In, -SO ３ － For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z ２ｃ is, -SO ３ － Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0256] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0257] In formula (d1-4), R ５３ ~R ５４ R represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ ~R ５４ They may be joined to each other to form a ring.

[0258] Anions may be used individually or in combination of two or more types.

[0259] The photoacid generator (A) is preferably at least one selected from the group consisting of compounds (I) to (II).

[0260] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural site X: Anionic site A １ － and cation site M １ ＋ It consists of and is irradiated with active light or radiation, HA １ Structural site that forms the first acidic site represented by Structural site Y: Anionic site A ２ － and cation site M ２ ＋ It consists of and is irradiated with active light or radiation, HA ２ The structural site (I) that forms the second acidic site represented by satisfies the following condition I.

[0261] Condition I: In the above compound (I), the above cation site M in the above structural site X. １ ＋ and the cation portion M in the structural portion Y. ２ ＋ to H ＋ The compound PI obtained by replacing the above structural site X is the cation site M １ ＋ to H ＋ HA is obtained by replacing it with １ The acid dissociation constant a1 originates from the acidic site represented by the above structure site Y, and the cation site M in the above structural site Y. ２ ＋ to H ＋ HA is obtained by replacing it with ２ It has an acid dissociation constant a2 derived from the acidic site represented by the above, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0262] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "HA １ and HA ２This falls under the category of "compounds having the above characteristics". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, compound PI is "A １ － and HA ２ The pKa at which the compound becomes "a compound having " is the acid dissociation constant a1, and the above "A １ － and HA ２ Compounds having "A" １ － and A ２ － The pKa value at which the compound becomes "a compound having the above characteristics" is the acid dissociation constant a2.

[0263] If compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI is "two HA １ and one HA ２ This falls under the category of "compounds having one A". When the acid dissociation constant of compound PI is determined, compound PI is "a compound having one A １ － and one HA １ and one HA ２ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２ The acid dissociation constant when a compound having the two A's is obtained corresponds to the aforementioned acid dissociation constant a1. １ － and one HA ２ Compounds having "two A １ － and A ２ － The acid dissociation constant when a compound has the above-mentioned structure corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the above-mentioned cation site M in the above-mentioned structural site X. １ ＋ to H ＋ HA is obtained by replacing it with １When a compound has multiple acid dissociation constants originating from the acidic site represented by , the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1. １ － and one HA １ and one HA ２ Let aa be the acid dissociation constant when a compound having " １ － and one HA １ and one HA ２ Compounds having "two A １ － and one HA ２ When the acid dissociation constant for a compound having the above is denoted as ab, the relationship between aa and ab satisfies aa < ab.

[0264] The acid dissociation constants a1 and a2 are determined by the acid dissociation constant measurement method described above. The compound PI mentioned above corresponds to the acid generated when compound (I) is irradiated with active light or radiation. If compound (I) has two or more structural sites X, the structural sites X may be the same or different. Also, two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different. In compound (I), the above A １ － and A above ２ － , and the above M １ ＋ and the above M ２ ＋ These may be the same or different, but A above １ － and A above ２ － It is preferable that they are all different.

[0265] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. There is no particular upper limit to the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2, but for example, it is 16 or less.

[0266] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0267] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0268] Anion part A １ － and anion part A ２ － This is a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion site A １ － Preferably, it is an acidic moiety that can form an acidic moiety with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion moiety A ２ － For example, Anion part A １ － It is preferable that the acidic site can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6) below, * represents the bond position. In formula (AA-2), R Ａ R represents a monovalent organic group. ＡThe monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0269]

[0270]

[0271] Cation site M １ ＋ and cation site M ２ ＋ This refers to a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the aforementioned M. ＋ Examples of organic cations represented by the following are given.

[0272] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acid

[0273] Definition of structural site X in compound (II), and A １ － and M １ ＋ The definition of is the definition of structural site X in compound (I) as described above, and A １ － and M １ ＋ This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0274] In the above compound (II), the above cation moiety M in the above structural moiety X. １ ＋ to H ＋ In compound PII, which is obtained by replacing the above structural site X, the above cation site M １ ＋ to H ＋ HA is obtained by replacing it with １The preferred range for the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in compound PI. Note that if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, then compound PII is "two HA １ This falls under the category of "a compound having one A". When the acid dissociation constant of this compound PII is determined, compound PII is "a compound having one A １ － and one HA １ The acid dissociation constant when a compound having " and " is formed, and " １ － and one HA １ Compounds having "two A １ － The acid dissociation constant when the compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0275] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. Compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. The two or more structural sites X may be the same or different. Two or more of the above A １ － , and two or more of the above M １ ＋ These may be the same or different.

[0276] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably a site containing a group that can electrostatically interact with a proton, or a functional group that has electrons. Examples of groups that can electrostatically interact with a proton, or functional groups that have 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.

[0277]

[0278] 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.

[0279] Examples of non-cationic sites that compound (I) and compound (II) may have are given below.

[0280]

[0281]

[0282] The photoacid generator (A) may be an intramolecular salt. Examples of intramolecular salts include the aforementioned "M ＋ X － The M of the compound represented by " ＋ Examples of compounds include those having a structure in which an anionic moiety is bonded to a cation represented by the formula (AA-1) to (AA-3) and (BB-1) to (BB-6). Examples of anionic moieties include groups containing structural moieties selected from the group consisting of the formulas (AA-1) to (AA-3), with groups containing structural moieties selected from the group consisting of the formulas (AA-1) to (AA-3) being preferred.

[0283] When the photosensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is preferable that the photoacid generator (A) contains a fluorine atom or an iodine atom. In particular, it is preferable that the photoacid generator (A) contains a cation having a fluorine atom, or that the photoacid generator (A) contains an anion having an iodine atom.

[0284] The content of photoacid generator (A) is preferably 10% by mass or more, more preferably 20.0% by mass or more, even more preferably 30.0% by mass or more, and particularly preferably 40.0% by mass or more, relative to the total solid content of the resist composition. Furthermore, the content of photoacid generator (A) is preferably 60.0% by mass or less, more preferably 55.0% by mass or less, and even more preferably 50.0% by mass or less, relative to the total solid content of the resist composition. Only one type of photoacid generator (A) may be used, or two or more types may be used. When two or more types of photoacid generator (A) are used, it is preferable that their total content is within the range of the above preferred content.

[0285] <Acid Diffusion Control Agent> The resist composition may contain an acid diffusion control agent. The acid diffusion control agent can act as a quencher that traps the acid generated during exposure, for example from a photoacid generator, and suppresses the reaction of the resin (P) in the unexposed areas due to excess generated acid.

[0286] The acid diffusion control agent preferably contains a carboxylate. The acid diffusion control agent is preferably at least one selected from the group consisting of compounds represented by the following formula (S-1) and compounds represented by the following formula (S-2).

[0287]

[0288] In formula (S-1), R Ｓ１ L represents a hydrogen atom or substituent. Ｓ１ X represents a single bond or a linking group. Ｓ１ M represents a single bond or a linking group. ２ ＋ R represents a sulfonium cation. Ｓ１ , L Ｓ１ and X Ｓ１ At least one of them contains an iodine atom.

[0289] In formula (S-2), R Ｓ２ and R Ｓ３ Each of these independently represents a hydrogen atom or a substituent. Ｓ２ and L Ｓ３ Each of these independently represents a single bond or a linking group. ３ ＋R represents a sulfonium cation. Ｓ２ , R Ｓ３ , L Ｓ２ and L Ｓ３ At least one of them contains an iodine atom.

[0290] L in equation (S-1) Ｓ１ L represents a single bond or a linking group. Ｓ１ The linking group represented by is not particularly limited, but can be -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO ２ -, -SO-, -NQ-, -NQ-CO-, -CO-NQ-CO-, -NQ-SO ２ - Examples include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these. Q represents a hydrogen atom or substituent, and preferably represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an aryl group (preferably having 6 to 15 carbon atoms). Q is R Ｓ１ or X Ｓ１ It may also combine with other elements to form a ring.

[0291] L Ｓ１ The alkylene group represented is not particularly limited, but preferably it is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group, and more preferably an alkylene group having 1 to 6 carbon atoms. Ｓ１ The alkylene group represented by may have substituents.

[0292] L Ｓ１The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, a group having a heteroatom such as an ester bond, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a vinylene group. Ｓ１ The cycloalkylene group represented by may have substituents.

[0293] L Ｓ１ The arylene group represented is not particularly limited, but examples include arylene groups having 6 to 20 carbon atoms, and arylene groups having 6 to 15 carbon atoms are preferred. The arylene group is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferred. Ｓ１ The arylene group represented by may have substituents.

[0294] L Ｓ１ The heteroarylene group represented is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｓ１ The number of ring member atoms of the heteroarylene group represented by is preferably 4 to 20, and more preferably 5 to 15. Ｓ１ The heteroarylene group represented by may have substituents.

[0295] X in equation (S-1) Ｓ１ X represents a single bond or a linking group. Ｓ１The linking group represented by is not particularly limited, but for example, -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO ２ -, -SO-, -NQ １ -, -NQ １ -CO-, -CO-NQ １ -CO-, -NQ １ -SO ２ - Examples include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these. Q １ Q represents a hydrogen atom or substituent, preferably a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an aryl group (preferably having 6 to 15 carbon atoms). １ is R Ｓ１ or L Ｓ１ It may also combine with other elements to form a ring.

[0296] X Ｓ１ The alkylene group represented by is not particularly limited, but preferably it is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group, and more preferably an alkylene group having 1 to 6 carbon atoms. Ｓ１ The alkylene group represented by may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above, and hydroxyl groups, halogen atoms, cycloalkyl groups, aryl groups, etc., are preferred.

[0297] X Ｓ１The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, a group having a heteroatom such as an ester bond, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a vinylene group. Ｓ１ The cycloalkylene group represented by may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above, and hydroxyl groups, halogen atoms, cycloalkyl groups, aryl groups, etc., are preferred.

[0298] X Ｓ１ The arylene group represented by is not particularly limited, but for example, an arylene group having 6 to 20 carbon atoms is possible, and an arylene group having 6 to 15 carbon atoms is preferred. The arylene group is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferred. Ｓ１ The arylene group represented by may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above, and hydroxyl groups, halogen atoms, cycloalkyl groups, aryl groups, etc., are preferred.

[0299] X Ｓ１ The heteroarylene group represented by is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｓ１ The number of ring member atoms of the heteroarylene group represented by is preferably 4 to 20, and more preferably 5 to 15. Ｓ１The heteroarylene group represented by may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above, and hydroxyl groups, halogen atoms, cycloalkyl groups, aryl groups, etc., are preferred.

[0300] R in equation (S-1) Ｓ１ R represents a hydrogen atom or substituent. Ｓ１ The substituent represented by is not particularly limited, but examples include the substituent T mentioned above, and halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, arylthio groups, etc. are preferred.

[0301] R Ｓ１ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom.

[0302] R Ｓ１ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and trifluoromethyl groups. Ｓ１ The explanation, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by are given in the above R. Ｓ１ It is the same as the alkyl group represented by .

[0303] R Ｓ１The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group may have substituents. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, and groups having heteroatoms such as ester bonds, or vinylidene groups. Furthermore, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by vinylene groups. Ｓ１ The explanation, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy group and cycloalkylthio group represented by are given in the above R. Ｓ１ This is the same as the cycloalkyl group represented by .

[0304] R Ｓ１ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents. Ｓ１ The explanation, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by are as follows: Ｓ１ This is the same as the aryl group represented by .

[0305] R Ｓ１ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｓ１The heteroaryl group represented by preferably has 4 to 20 ring member atoms, and more preferably 5 to 15. Examples of heteroaryl groups include pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, and benzothiophenyl group. The heteroaryl group may have substituents.

[0306] However, R in equation (S-1) Ｓ１ , L Ｓ１ and X Ｓ１ At least one of them contains an iodine atom. Ｓ１ , L Ｓ１ and X Ｓ１ The total number of iodine atoms contained is 1 or more, preferably 2 or more. Ｓ１ and X Ｓ１ Preferably, at least one of them contains an iodine atom, R Ｓ１ It is more preferable that it contains an iodine atom. Ｓ１ One embodiment of which contains an iodine atom is R Ｓ１ The manner in which R represents an iodine atom, Ｓ１ One example is a configuration in which the substituent represented by (for example, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, etc.) has an iodine atom.

[0307] M in equation (S-1) ２ ＋ M represents a sulfonium cation. ２ ＋ The description, specific examples, and preferred range of the sulfonium cation represented by are as described above in "M ＋ X － M in the compound represented by " ＋ This is the same as that for sulfonium cations that can be formed.

[0308] Preferred embodiments of the compound represented by formula (S-1) include those described in International Publication No. 2023 / 157455

[0118] and

[0144] , Japanese Patent Publication No. 2018-155902

[0026] to

[0028] , and Japanese Patent Publication No. 2023-108593

[0147] .

[0309] L in equation (S-2) Ｓ２ and L Ｓ３ Each of these independently represents a single bond or a linking group. Ｓ２ and L Ｓ３ The linking group represented by is not particularly limited, but can be -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO ２ -, -SO-, -NQ ２ -, -NQ ２ -CO-, -CO-NQ ２ -CO-, -NQ ２ -SO ２ - Examples include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, and groups formed by combining two or more of these. Q ２ Q represents a hydrogen atom or substituent, preferably a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an aryl group (preferably having 6 to 15 carbon atoms). ２ is R Ｓ２ or R Ｓ３ It may also combine with other elements to form a ring.

[0310] L Ｓ２ and L Ｓ３ The alkylene group represented is not particularly limited, but preferably it is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group, and more preferably an alkylene group having 1 to 6 carbon atoms. Ｓ２ and L Ｓ３ The alkylene group represented by may have substituents.

[0311] L Ｓ２ and L Ｓ３The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One or more methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, a group having a heteroatom such as an ester bond, or a vinylidene group. In addition, one or more ethylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a vinylene group. Ｓ２ and L Ｓ３ The cycloalkylene group represented by may have substituents.

[0312] L Ｓ２ and L Ｓ３ The arylene group represented is not particularly limited, but examples include arylene groups having 6 to 20 carbon atoms, and arylene groups having 6 to 15 carbon atoms are preferred. The arylene group is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferred. Ｓ２ and L Ｓ３ The arylene group represented by may have substituents.

[0313] L Ｓ２ and L Ｓ３ The heteroarylene group represented is not particularly limited, but is preferably a heteroarylene group having 3 to 19 carbon atoms, and more preferably a heteroarylene group having 4 to 14 carbon atoms. The heteroarylene group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｓ２ and L Ｓ３ The number of ring member atoms of the heteroarylene group represented by is preferably 4 to 20, and more preferably 5 to 15. Ｓ２ and L Ｓ３ The heteroarylene group represented by may have substituents.

[0314] R in equation (S-2) Ｓ２ and R Ｓ３ Each of these independently represents a hydrogen atom or a substituent. Ｓ２ and R Ｓ３ The substituent represented by is not particularly limited, but examples include the substituent T mentioned above, and halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, cycloalkyl groups, cycloalkyloxy groups, cycloalkylthio groups, aryl groups, heteroaryl groups, aryloxy groups, arylthio groups, etc. are preferred.

[0315] R Ｓ２ and R Ｓ３ The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom.

[0316] R Ｓ２ and R Ｓ３ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and trifluoromethyl groups. Ｓ２ and R Ｓ３ The explanation, specific examples, and preferred ranges of the alkyl groups included in the alkoxy group and alkylthio group represented by are given in the above R. Ｓ２ and R Ｓ３ It is the same as the alkyl group represented by .

[0317] R Ｓ２ and R Ｓ３The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group may have substituents. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, and groups having heteroatoms such as ester bonds, or vinylidene groups. Furthermore, one or more ethylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced by vinylene groups. Ｓ２ and R Ｓ３ The explanation, specific examples, and preferred ranges of the cycloalkyl groups contained in the cycloalkyloxy group and cycloalkylthio group represented by are given in the above R. Ｓ２ and R Ｓ３ This is the same as the cycloalkyl group represented by .

[0318] R Ｓ２ and R Ｓ３ The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have substituents. Ｓ２ and R Ｓ３ The explanation, specific examples, and preferred ranges of the aryl groups contained in the aryloxy and arylthio groups represented by are as follows: Ｓ２ and R Ｓ３ This is the same as the aryl group represented by .

[0319] R Ｓ２ and R Ｓ３ The heteroaryl group represented by is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a ring member. Ｓ２ and R Ｓ３The number of ring atoms of the heteroaryl group represented is preferably 4 to 20, more preferably 5 to 15. Examples of the heteroaryl group include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, a benzothiophenyl group and the like. The heteroaryl group may have a substituent.

[0320] However, R in formula (S-2) Ｓ２ , R Ｓ３ , L Ｓ２ and L Ｓ３ includes at least one iodine atom. The total number of iodine atoms contained in R Ｓ２ , R Ｓ３ , L Ｓ２ and L Ｓ３ is 1 or more, preferably 2 or more. It is preferable that at least one of R Ｓ２ and R Ｓ３ contains an iodine atom. Examples of the aspect in which R Ｓ２ and R Ｓ３ contain an iodine atom include an aspect in which R Ｓ２ and R Ｓ３ represent an iodine atom, and an aspect in which the substituents represented by R Ｓ２ and R Ｓ３ (for example, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, etc.) have an iodine atom.

[0321] M in formula (S-2) ３ ＋ represents a sulfonium cation. The description, specific examples and preferred range of the sulfonium cation represented by M ３ ＋ are the same as those of the sulfonium cation that M ＋ X － can take in the compound represented by "". Preferred aspects of the compound represented by formula (S-2) include those described in

[0039] to

[0047] of JP-A No. 2021-128331.

[0322] ​​The acid diffusion control agent is a compound other than the compound represented by formula (S-1) above, and may also be a compound other than the compound represented by formula (S-2) above. The type of acid diffusion control agent is not particularly limited, and examples include basic compounds (DA), low molecular weight compounds (DB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (DC) include onium salt compounds (DD) of acids that are relatively weak acids with respect to the acid generated from the photoacid generator, and basic compounds (DE) whose basicity is reduced or lost by irradiation with active light or radiation.

[0323] (Basic Compounds (DA)) As basic compounds (DA), compounds having the structure shown in the following formulas (A) to (E) are preferred.

[0324]

[0325] In equations (A) and (E), R ２００ , R ２０１ and R ２０２ These may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 20 carbon atoms). ２００ , R ２０１ and R ２０２ At least two of them may be joined to form a ring. ２０３ , R ２０４ , R ２０５ and R ２０６ These may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms. In formulas (B), (C), (D), and (E), * represents a bond position.

[0326] R in equations (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６The alkyl group or cycloalkyl group represented by may have substituents or be unsubstituted. Regarding the alkyl group, preferred substituent groups are C1-C20 aminoalkyl groups, C1-C20 hydroxyalkyl groups, or C1-C20 cyanoalkyl groups. In formulas (A) and (E), R ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by is more preferably unsubstituted.

[0327] Examples of basic compounds (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (DA) may also be a compound having at least one selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (DA) may also be an alkylamine derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one selected from the group consisting of a hydroxyl group and an ether bond.

[0328] The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (DA)) is preferably 1.00 or higher, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. Furthermore, the pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator used, but for example, it is preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0329] (Onium salt compound (DD) of an acid that is a weak acid relative to the acid generated from the photoacid generator) Compound (DD) may be a compound that generates acid upon irradiation with active light or radiation. Preferably, compound (DD) is a compound that generates an acid whose pKa is 1.00 or greater than the acid generated from the photoacid generator. The difference between the pKa of the acid generated from compound (DD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from compound (DD)) is preferably 1.00 or greater, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. Furthermore, the pKa of the acid generated from the compound (DD) varies depending on the type of photoacid generator used, but for example, 0.50 to 10.00 is preferred, 0.80 to 5.00 is more preferred, and 1.00 to 5.00 is even more preferred.

[0330] Compound (DD) is preferably an onium salt compound consisting of an anion and a cation. For example, compound (DD) is "M ＋ X － Examples include compounds represented by " (onium salts). ＋ X represents an organic cation. － M represents an organic anion. ＋ As for M, which was described in the explanation of the photoacid generator ＋ The same thing can be cited as X － Examples include the anions represented by formulas (d1-1) to (d1-4) described in the description of the photoacid generator, with the anion represented by formula (d1-1) or the anion represented by formula (d1-2) being preferred.

[0331] Specific examples of basic compounds (DA) include, for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (DE) whose basicity is reduced or lost upon irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] and paragraph

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

[0156] to

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

[0305] to

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

[0332] 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.

[0333] The molecular weight of the acid diffusion control agent is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0334] The acid diffusion control agent is also preferably a compound that generates an acid with a pKa of 0 or higher upon irradiation with active light or radiation.

[0335] If the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent (total if multiple types exist) is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass, relative to the total solid content of the composition. In the resist composition, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.

[0336] In a preferred embodiment, at least one of the photoacid generator and acid diffusion control agent in the resist composition preferably contains a sulfonium cation and an anion having an iodine atom. The sulfonium cation preferably has a halogen atom. The anion having an iodine atom preferably has two or more iodine atoms.

[0337] Preferably, at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation having a halogen atom and an anion having two or more iodine atoms.

[0338] <Hydrophobic Resin> The resist composition may further contain a hydrophobic resin (also called hydrophobic resin (D)) different from resin (P). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances.

[0339] Hydrophobic resins, in terms of their uneven distribution on the film surface, contain fluorine atoms, silicon atoms, and CH4 atoms in the side chain portion of the resin. ３ It is preferable to have one or more of the substructures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

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

[0340] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the resist composition. 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 above preferred content range.

[0341] <Surfactants> The resist composition 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.

[0342] If the resist composition 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, relative to the total solid content of the resist composition. One type of surfactant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content is within the range of the above preferred content.

[0343] <Solvent> The resist composition 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).

[0344] Combining the aforementioned solvent with the aforementioned resin is preferable in terms of improving the coatability of the resist composition and reducing the number of development defects in the pattern. The aforementioned solvent has a good balance of solubility, boiling point, and viscosity with the aforementioned resin, and can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0345] 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.

[0346] The solvent content in the resist composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably so that it is 1 to 20% by mass. This further improves the coatability of the resist composition.

[0347] <Other Additives> The resist composition may further contain at least one selected from the group consisting of dissolution-inhibiting compounds, 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-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developers.

[0348] 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 resist composition. 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.

[0349] Furthermore, the resist composition may contain water as an impurity. When water is present as an impurity, a lower water content is preferable, but it may be present in an amount of 1 to 30,000 ppm by mass relative to the total resist composition. Furthermore, the resist composition may contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of resin (P)). When residual monomers are present as impurities, a lower residual monomer content 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 resist composition.

[0350] [Resist film, pattern formation method] The present invention also relates to a resist film formed by the photosensitive or radiation-sensitive resin composition of the present invention. The procedure for the pattern formation method of the present invention is not particularly limited, but preferably it is a pattern formation method (hereinafter also referred to as "the pattern formation method of the present invention") that includes: (1) a step of forming a film using the photosensitive or radiation-sensitive resin composition of the present invention; (2) a step of exposing the film; and (3) a step of developing the exposed film with an organic processing solution containing butyl acetate and a hydrocarbon having 9 to 12 carbon atoms.

[0351] By using an organic processing solution containing butyl acetate and hydrocarbons with 9 to 12 carbon atoms as the developer, the concentration of hydrophobic hydrocarbons increases during drying processes such as spin-drying, which reduces the development speed. This suppresses variations in the dissolution of the film areas intended for development removal in the developer, improving the uniformity of the resist film thickness. From this perspective, resolution is expected to be improved. Furthermore, by using the above organic processing solution as the developer, the penetration and swelling of the developer into film areas not intended for development removal is suppressed. This makes it easier to maintain the latent image contrast caused by exposure during the development process, even after pattern formation. From this perspective as well, resolution is expected to be improved.

[0352] The following details each of the above steps.

[0353] [Step (1)] Step (1) is a step of forming a film using the photosensitive or radiation-sensitive resin composition (resist composition) of the present invention.

[0354] Step (1) is preferably a step of forming a resist film on a substrate using a resist composition.

[0355] One method for forming a resist film on a substrate using a resist composition is to coat the resist composition onto the substrate. 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 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] A topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods. For example, a topcoat can be formed based on paragraphs

[0072] to

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

[0360] [Step (2)] Step (2) is a step of exposing the film (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 nm), X-rays, and electron beams.

[0361] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates 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 machine, and may also be done using a hot plate or the like. This process is also called post-exposure baking.

[0362] [Step (3)] Step (3) is a step of developing the film exposed in Step (2) with an organic processing solution containing butyl acetate and a hydrocarbon having 9 to 12 carbon atoms. The hydrocarbon having 9 to 12 carbon atoms contained in the organic processing solution used in Step (3) 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. If structural isomers exist for the hydrocarbon having 9 to 12 carbon atoms, such as undecanes and dodecanes, structural isomers may be included. The hydrocarbon having 9 to 12 carbon atoms contained in the organic processing solution may be only one type or two or more types.

[0363] The content of hydrocarbons having 9 to 12 carbon atoms in the organic treatment liquid (the total amount if multiple types of hydrocarbons having 9 to 12 carbon atoms are included) 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 treatment liquid.

[0364] The organic treatment solution contains butyl acetate (n-butyl acetate). The butyl acetate content in the organic treatment solution 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 treatment solution.

[0365] The mass ratio of butyl acetate to hydrocarbons having 9 to 12 carbon atoms in the organic treatment solution (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.

[0366] The organic processing solution 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, basic compounds, etc. The content of other components in the organic processing solution is preferably 0% to 5% by mass, more preferably 0% to 1% by mass, even more preferably 0% to 0.5% by mass, and particularly preferably 0% by mass (i.e., no other components are present), based on 100% by mass of the entire organic processing solution. Step (3) is a preferred embodiment of the pattern forming method, and the developer of the organic processing solution can also be used.

[0367] The development method in step (3) is not particularly limited, but examples include immersing the resist film in a tank filled with developer (the above-mentioned organic processing solution) for a certain period of time (dip method), piling the developer onto the surface of the resist film by surface tension and leaving it still for a certain period of time for development (paddle method), spraying the developer onto the surface of the resist film (spray method), and continuously dispensing the developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). In addition, after the development process, a step of stopping development while replacing with another solvent may be performed. The development time is not particularly limited as long as it is enough time for the resin of the part to be removed to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is not particularly limited, but 0 to 50°C is preferred, and 15 to 35°C is more preferred.

[0368] Step (3) is performed to form a resist pattern (also simply called a "pattern"). After step (3), rinsing may be performed. Rinsing can be performed using the above-mentioned organic treatment solution, or using a rinsing solution other than the above-mentioned organic treatment solution. The rinsing solution other than the above-mentioned organic treatment solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution other than the above-mentioned organic treatment solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0369] 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).

[0370] 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).

[0371] 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.

[0372] In the pattern forming method of the present invention, the organic processing liquid, resist composition, and various other materials (e.g., solvent, rinse liquid, anti-reflective film forming composition, top coat forming composition, etc.) used preferably do not contain 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 metallic 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.

[0373] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

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

[0374] Furthermore, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon (registered trademark).

[0375] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the manufacturing equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0376] A conductive compound may be added to the organic processing solution and rinsing solution to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit of the amount of conductive compound added is not particularly limited and may be 0.01% by mass or more. As for the chemical piping, for example, various pipes made of SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) coated with antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) coated with antistatic treatment can be used.

[0377] [Method for Manufacturing Electronic Devices] This specification relates to a method for manufacturing electronic devices, including the pattern forming method described above, and to electronic devices manufactured by this manufacturing method. Preferred embodiments of the electronic devices described herein include those mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0378] 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.

[0379] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0380] <Resin (P)> As resin (P), P-1 to P-54 and P-1x are used. However, although P-1x is not resin (P), for convenience it is listed in the "Resin (P)" column in the table below. Resin P-1 is used after the resin is synthesized by the synthesis method described later (synthesis Example 1), and then subjected to a preparative GPC apparatus under the preparative conditions described later to remove high molecular weight and low molecular weight components. Resins P-2 to P-54 are used after the resin is synthesized in accordance with Synthesis Example 1 or by a known method, and then subjected to a preparative GPC apparatus under the same preparative conditions to remove at least one of the high molecular weight and low molecular weight components. Resin P-1x is used as is after being synthesized in accordance with Synthesis Example 1.

[0381] Resins P-1 to P-54 and P-1x contain the repeating units shown in Tables 1 and 2 below in the amounts shown in Tables 1 and 2. The weight-average molecular weight (Mw) of each resin is also listed in Tables 1 and 2. The content of each repeating unit is the molar ratio of each repeating unit to the total repeating units contained in each resin. The weight-average molecular weight (Mw) of the resin is measured using GPC (carrier: tetrahydrofuran (THF)) under the following conditions (polystyrene equivalent). The content of the repeating units is as follows: １３ Measurement is performed using C-NMR (nuclear magnetic resonance).

[0382] Furthermore, Tables 1 and 2 also include the values ​​of P (10%), represented by the following formula (A), and P (90%), represented by the following formula (B), which are obtained from the integrated molecular weight distribution curve obtained from gel permeation chromatography (GPC) measurement. Formula (A): P (10%) = (Molecular weight at a concentration fraction of 10%) ÷ weight-average molecular weight Formula (B): P (90%) = (Molecular weight at a concentration fraction of 90%) ÷ weight-average molecular weight The measurement conditions for gel permeation chromatography and the method for creating the integrated molecular weight distribution curve are as follows.

[0383] Gel permeation chromatography measurement: 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

[0384] Creation of an integrated molecular weight distribution curve: Using the molecular weight calibration curve created with polystyrene standard samples from the measurement results of gel permeation chromatography, a graph (integrated molecular weight distribution curve) is created with molecular weight on the x-axis and concentration fraction on the y-axis using the analysis software EcoSEC data analysisis (manufactured by Tosoh Corporation).

[0385]

[0386]

[0387] The structural formulas of the monomers corresponding to each repeating unit are shown below. Note that M-a-1 to M-a-8 correspond to the raw material monomers of the repeating unit represented by the above formula (Pa1), and M-c-1 to M-c-11, M-a-7, and M-a-8 correspond to the raw material monomers of the repeating unit having an acid-degradable group.

[0388]

[0389]

[0390]

[0391]

[0392] <Preparation of Resin P-1> (Synthesis Example 1: Synthesis of Resin P-1a)

[0393]

[0394] 22 g of propylene glycol monomethyl ether acetate is heated to 85°C under a nitrogen stream. While stirring this solution, a mixed solution of monomer represented by M-a-1A (10 g), monomer represented by M-c-1 (26 g), monomer represented by M-b-3 (15 g), propylene glycol monomethyl ether acetate (84 g), and 2,2'-dimethyl azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (2.8 g) is added dropwise over 6 hours. After the dropwise addition is complete, the reaction solution is stirred at 85°C for a further 2 hours to obtain a polymerization solution. Methanol (100 g) and triethylamine (16 g) are added to the obtained polymerization solution and stirred at 80°C for 10 hours. After stirring is complete, the solution is allowed to cool to room temperature, then ethyl acetate (650 g) and 0.2 mol / L hydrochloric acid aqueous solution (400 mL) are added and stirred for 30 minutes to extract the organic layer. The extracted organic layer is washed five times with distilled water (400 mL). The washed organic layer is reprecipitated with a mixed solution of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. 35 g of resin P-1a is obtained by vacuum drying the resulting solid. The weight-average molecular weight (Mw: polystyrene equivalent) of resin P-1a, determined from the GPC (carrier: tetrahydrofuran (THF)), is 10,000. １３ The molar ratio of repeating units, as measured by 13C NMR (nuclear magnetic resonance), is M-a-1 / M-c-1 / M-b-3 = 20 / 60 / 20.

[0395] (Preparative GPC) Resin P-1a is dissolved in tetrahydrofuran and subjected to preparative GPC (apparatus: LaboACE LC-7080 manufactured by Nippon Analytical Industries, solvent: tetrahydrofuran, column: TSKgel G2000HHR manufactured by Tosoh Corporation (21.5 mm I.D. × 30 cm)) to remove low molecular weight and high molecular weight components, thereby preparing resin P-1.

[0396] <Photoacid Generator (A)> A-1 to A-13 are used as the photoacid generator (A).

[0397]

[0398]

[0399] <Acid Diffusion Control Agents> B-1 to B-11 and C-1 to C-2 are used as acid diffusion control agents.

[0400]

[0401]

[0402] <Hydrophobic Resin (D)> D-1 to D-8 are used as hydrophobic resins. The content of each repeating unit for D-1 to D-8 is listed in Table 3 below. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of each resin are also listed in Table 3. The content of each repeating unit is the ratio (mass%) of each repeating unit to the total repeating units contained in each resin (shown from left to right). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resins are measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). The content of the repeating units is, １３ Measurement is performed using C-NMR (nuclear magnetic resonance).

[0403]

[0404]

[0405] <Surfactants> The surfactants E-1 to E-3 used are as follows: E-1: Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant) E-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicone-based surfactant) E-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)

[0406] <Solvents> The solvents to be used are as follows: F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-Heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene carbonate

[0407] <Developer (organic processing solution)> The developer to be used is shown in Table 4 below.

[0408]

[0409] [Preparation of Resist Composition] Mix the components shown in Tables 5 and 6 so that the solid content concentration is 1.6% by mass. Then, filter the resulting mixture through a polyethylene filter with a pore size of 0.03 μm to prepare the resist composition. Note that "solid content" refers to all components other than the solvent. The obtained resist composition is used in the examples and comparative examples. In the tables, the "Content (mass%)" column shows the content (mass%) of each component relative to the total solid content in the resist composition.

[0410]

[0411]

[0412] [Pattern Formation and Evaluation] [EUV Exposure, Organic Solvent Development] A base layer formation composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205°C for 60 seconds to form a base layer with a thickness of 20 nm. On top of that, the resist compositions shown in Tables 5 and 6 are applied and baked at 100°C for 60 seconds to form a resist film with a thickness of 40 nm. This forms a silicon wafer with a resist film. Pattern irradiation is performed on the silicon wafer with the resist film obtained by the above procedure using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line:space ratio of 1:1 is used as the reticle. After exposure, the resist film is baked at 90°C for 60 seconds, then developed with the developer solutions shown in Tables 7 and 8 for 30 seconds, and finally spin-dried to obtain the pattern.

[0413] [Evaluation] <Resolution> The cross-sectional shape of the obtained pattern is observed using a scanning electron microscope (Hitachi S-9380II). In the exposure and development conditions for forming the resist pattern described above, the exposure amount that reproduces a mask pattern with a line width of 20 nm is defined as the optimal exposure amount. When the line width of the line and space pattern formed by further increasing the exposure amount from the optimal exposure amount is narrowed, the minimum line width at which the pattern can be resolved without breaks is defined as the resolution value (nm). The above resolution value is evaluated using the following index: A: 12 nm or more and less than 14 nm B: 14 nm or more and less than 16 nm C: 16 nm or more and less than 18 nm D: 18 nm or more and less than 20 nm E: 20 nm or more

[0414]

[0415]

[0416] From the above results, it can be seen that the resist composition used in the example can form extremely fine patterns (for example, with a line width of 20 nm or less) with excellent resolution.

[0417] The present invention provides a photosensitive or radiation-sensitive resin composition capable of forming patterns with excellent resolution. Furthermore, the present invention provides a resist film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device.

[0418] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-170472 filed on 30 September 2024, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiation-sensitive resin composition comprising a resin, a compound that generates acid upon irradiation with active light or radiation, and a solvent, wherein the resin has a P (10%) value of 0.40 or higher, as expressed by the following formula (A) obtained from the integrated molecular weight distribution curve obtained by gel permeation chromatography. Formula (A): P (10%) = (Molecular weight at a concentration fraction of 10%) ÷ Weight-average molecular weight 2. A photosensitive or radiation-sensitive resin composition comprising a resin, a compound that generates acid upon irradiation with active light or radiation, and a solvent, wherein the resin has a P (90%) value of 1.70 or less, as determined from the integral molecular weight distribution curve obtained by gel permeation chromatography, represented by the following formula (B). Formula (B): P (90%) = (Molecular weight at 90% concentration fraction) ÷ Weight-average molecular weight 3. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin has a P (10%) represented by formula (A) of 0.50 or more.

4. The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the resin has a P (90%) represented by formula (B) of 1.50 or less.

5. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin has a P (90%) represented by the following formula (B) of 1.70 or less. Formula (B): P (90%) = (Molecular weight at 90% concentration fraction) ÷ Weight-average molecular weight 6. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin has repeating units represented by the following formula (i). In formula (i), X １ L represents a hydrogen atom or substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. n1 represents an integer greater than or equal to 1.

7. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin comprises a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxyl group.

8. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin contains an iodine atom.

9. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the content of a compound that generates acid upon irradiation with the active light or radiation is 10% by mass or more relative to the total solid content of the photosensitive or radiation-sensitive resin composition.

10. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin contains more than 50 mol% of repeating units having acid-degradable groups relative to the total number of repeating units.

11. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound that generates acid upon irradiation with the active light or radiation contains a fluorine atom or an iodine atom.

12. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound that generates acid upon irradiation with the active light or radiation contains a cation having a fluorine atom.

13. The photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound that generates acid upon irradiation with the active light or radiation contains an anion having an iodine atom.

14. A resist film formed using the photosensitive or radiation-sensitive resin composition according to claim 1 or 2.

15. A pattern forming method comprising: (1) forming a film using the photosensitive or radiation-sensitive resin composition described in claim 1 or 2; (2) exposing the film; and (3) developing the exposed film with an organic treatment solution containing butyl acetate and a hydrocarbon having 9 to 12 carbon atoms.

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

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