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

Abstract

Provided is an active-ray-sensitive or radiation-sensitive resin composition having excellent resolution properties and bridge margin, an active-ray-sensitive or radiation-sensitive film using said composition, a pattern formation method, and a method for manufacturing an electronic device. The active-ray-sensitive or radiation-sensitive resin composition includes a resin (A) which has a specific repeating unit and the polarity of which increases under the action of an acid, and an acidic compound (F) having an iodine atom, the resin (A) and the acidic compound (F) being separate compounds, and the acidic compound (F) being a non-ionic compound.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which are suitably used in ultramicrolithography processes applicable to the manufacturing processes of ultra-large-scale integrations (ULSIs) and high-capacity microchips, nanoimprint mold creation processes, and high-density information recording media, as well as other photofabrication processes. [Background technology]

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

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

[0004] For example, Patent Documents 1 and 2 describe resist compositions containing compounds having iodine atoms. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2018 / 180049 [Patent Document 2] Japanese Patent Publication No. 2021-67934 [Overview of the project] [Problems that the invention aims to solve]

[0006] Patent documents 1 and 2 describe how the sensitivity of a resist composition can be improved by using a compound containing an iodine atom. However, in recent years, the performance requirements for resist compositions have become even higher due to factors such as the miniaturization of patterns. In particular, further improvements are needed in terms of resolution and bridge margin.

[0007] The present invention aims to provide a photosensitive or radiation-sensitive resin composition that exhibits excellent resolution and bridge margin. Furthermore, the present invention aims to provide a photosensitive or radiation-sensitive film, a pattern-forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0008] The inventors have found that the above problem can be solved by the following configuration. <1> A photosensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases upon the action of an acid, and an acidic compound (F) having an iodine atom, The above resin (A) and the above acidic compound (F) are different compounds. The above acidic compound (F) is a nonionic compound and has the following general formula (FA3) or (FA4) It is a compound represented by the following: The content of the above-mentioned acidic compound (F) is 0.1 to 10% by mass, based on the total solid content of the above-mentioned photosensitive or radiation-sensitive resin composition. A photosensitive or radiation-sensitive resin composition wherein the above resin (A) has repeating units represented by the following general formula (3). [ka] In general formula (3), R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L2 is Arrene base represent. R8~R 10 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R8~R 10 Two of them may combine to form a ring. 。 [ka] In the general formula (FA3), j represents either 0 or 1. Q 3 This represents a nitro group. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m6 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA3). [ka] In the general formula (FA4), j represents either 0 or 1. Q 4 This represents a nitro group. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m7 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA4). < 2 > The above resin (A) has repeating units represented by the following general formula (A2), <1 >The actinic ray-sensitive or radiation-sensitive resin composition according to

Chemical Formula

[0009] [1] A photosensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases upon the action of an acid, and an acidic compound (F) having an iodine atom, The above resin (A) and the above acidic compound (F) are different compounds. The above acidic compound (F) is a nonionic compound, A photosensitive or radiation-sensitive resin composition wherein the resin (A) has at least one selected from the group consisting of repeating units represented by the following general formula (3), repeating units represented by the following general formula (6), and repeating units represented by the following general formula (7).

[0010] [ka]

[0011] In general formula (3), R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L2 represents a divalent linking group. R8~R 10 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R8~R 10 Two of them may join together to form a ring.

[0012] [ka]

[0013] In general formula (6), R 22 ~R 24 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L4 represents a single bond or a divalent linking group. Ar1 represents an aromatic group. R 25 ~R 27 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 26 and R 27 It may also combine with another element to form a ring. R 24 or R 25 It may also bind with Ar1.

[0014] [ka]

[0015] In general formula (7), R 28 ~R 30 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L5 represents a single bond or a divalent linking group. R 31 and R 32 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 33 This represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R 32 and R 33 It may also combine with another element to form a ring. [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the above-mentioned acidic compound (F) is a compound having an aromatic group substituted with an iodine atom. [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the above-mentioned acidic compound (F) is a compound represented by the following general formula (FA1).

[0016] [ka]

[0017] In the general formula (FA1), Ar a1 represents an aromatic group. X 1 represents a single bond or a linking group. Q 1 This represents an acidic group. Q 1 and Ar a1 They may combine to form a ring. m1 and m2 each represent an integer between 0 and 5, independently of each other. However, m1+m2 is between 1 and 6. 1 When m² represents a single bond, then m² represents 0. m3 represents either 1 or 2. If m3 represents 2, then two Ar a1 The two X's can be the same or different. 1 They may be the same or different. [4] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the above-mentioned acidic compound (F) is a compound represented by the following general formula (FA2).

[0018] [ka]

[0019] In the general formula (FA2), Ar a1 represents an aromatic group. X 2 represents a single bond or a divalent linking group. Q 1 This represents an acidic group. m4 represents an integer between 1 and 5. [5] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the above-mentioned acidic compound (F) is a compound represented by the following general formula (FA3).

[0020] [ka]

[0021] In the general formula (FA3), j represents either 0 or 1. Q 3 represents a substituent. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m6 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA3). [6] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the above-mentioned acidic compound (F) is a compound represented by the following general formula (FA4).

[0022] [ka]

[0023] In the general formula (FA4), j represents either 0 or 1. Q 4 represents a substituent. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m7 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA4). [7] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the above-mentioned acidic compound (F) is a compound represented by the following general formula (FA5).

[0024] [ka]

[0025] In the general formula (FA5), j represents either 0 or 1. Q4 represents a substituent. E 1 represents a single bond or a divalent linking group. m4 represents an integer between 1 and 5. m8 represents an integer greater than or equal to 0 and less than or equal to (4 + 2j - m4). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA5). [8] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the pKa of the above-mentioned acidic compound (F) is 6 or less. [9] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the molecular weight of the above-mentioned acidic compound (F) is 1000 or less.

[10] The above resin (A) has repeating units represented by the following general formula (A2) and is a photosensitive or radiation-sensitive resin composition according to any one of [1] to [9].

[0026] [ka]

[0027] In general formula (A2), R 101 , R 102 and R 103 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L A This represents a single bond or a divalent linking group. Ar A This represents an aromatic group. k represents an integer between 1 and 5. However, R 102 is Ar A It may also be combined with R 102 and Ar A When they are joined, R 102 represents a single bond or an alkylene group.

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

[10] , comprising a compound that generates acid upon irradiation with active light or radiation.

[12] A photosensitive or radiation-sensitive film formed using a photosensitive or radiation-sensitive resin composition described in any one of [1] to

[11] .

[13] A step of forming a resist film using a photosensitive or radiation-sensitive resin composition described in any one of [1] to

[11] , The process of exposing the above-mentioned resist film, The above-mentioned exposed resist film is developed using a developer solution, A pattern forming method having the following characteristics.

[14] A method for manufacturing an electronic device, including the pattern formation method described in

[13] . [Effects of the Invention]

[0028] The present invention provides a photosensitive or radiation-sensitive resin composition with excellent resolution and bridge margin. Furthermore, the present invention provides a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition. [Modes for carrying out the invention]

[0029] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0030] 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.

[0031] In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0032] The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the general formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0033] 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.

[0034] 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-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0035] In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0036] In this specification, "organic group" means a group containing at least one carbon atom.

[0037] Furthermore, in this specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when we say "may have substituents." The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atom groups excluding hydrogen atoms, and for example, substituents T can be selected from the following.

[0038] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; and arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl. Alkyl groups (e.g., 1-10 carbon atoms); cycloalkyl groups (e.g., 3-20 carbon atoms); aryl groups (e.g., 6-20 carbon atoms); heteroaryl groups; hydroxyl groups; carboxyl groups; Examples include formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; and combinations thereof.

[0039] 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 herein are those calculated using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0040] On the other hand, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in the solvent based on the thermodynamic cycle. + One method involves calculating the dissociation free energy. In this specification, water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when the pKa cannot be determined with water. H + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this method. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0041] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted.

[0042] (Actinic ray-sensitive or radiation-sensitive resin composition) The photosensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is a photosensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases by the action of an acid, and an acidic compound (F) having an iodine atom, Resin (A) and acidic compound (F) are different compounds. Acidic compound (F) is a nonionic compound, The resin (A) is a photosensitive or radiation-sensitive resin composition having at least one selected from the group consisting of repeating units represented by the following general formula (3), repeating units represented by the following general formula (6), and repeating units represented by the following general formula (7).

[0043] [ka]

[0044] In general formula (3), R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L2 represents a divalent linking group. R8~R 10 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R8~R 10 Two of them may join together to form a ring.

[0045] [ka]

[0046] In general formula (6), R 22 ~R 24 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L4 represents a single bond or a divalent linking group. Ar1 represents an aromatic group. R 25 ~R 27 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 26 and R 27 It may also combine with another element to form a ring. R 24 or R 25 It may also bind with Ar1.

[0047] [ka]

[0048] In general formula (7), R 28 ~R 30 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L5 represents a single bond or a divalent linking group. R 31 and R 32 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 33 This represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R 32 and R 33 It may also combine with another element to form a ring.

[0049] The composition of the present invention is preferably a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. It may also be a resist composition for alkaline development or a resist composition for organic solvent development. The composition of the present invention is preferably a positive-type resist composition. The composition of the present invention is preferably a resist composition for alkaline development. Furthermore, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition.

[0050] Conventionally, when resist compositions were exposed using electron beams or EUV, a deterioration of the bridge margin was observed in the high-exposure range. This is thought to be a local decrease in solubility due to some side reaction caused by secondary electron emission from the resin, whose polarity increases due to the action of acids irradiated by electron beams or EUV, and can be considered a fundamental problem. The inventors attempted to improve the bridge margin by using an acidic compound (F) containing an iodine atom, and found that it is possible to achieve both high resolution and a good bridge margin when using repeating units selected from the group consisting of repeating units represented by general formula (3), general formula (6), and general formula (7), which are particularly highly reactive. Although the reason why the composition of the present invention exhibits excellent resolution and bridge margin is not yet fully clear, the inventors have the following hypothesis. The acidic compound (F), which contains iodine atoms and readily absorbs electron beams and EUV light, is thought to efficiently release secondary electrons when added to the composition, replacing the resin whose polarity increases due to the action of the acid. As a result, it is thought that the bridge margin is improved because the side reactions that conventionally occurred with resins whose polarity increases due to the action of the acid can be suppressed. Furthermore, the high solubility of the acidic compound (F) in the developer due to its acidity is considered a factor that makes localized decreases in solubility due to side reactions less likely. Furthermore, the acidic compound (F) showed an effect in improving resolution when used in combination with a highly reactive protecting group. This is presumed to be because, while the highly reactive protecting group has the potential to achieve high resolution, it was not able to fully demonstrate its performance due to side reactions in the resin, where the polarity increased due to the action of the acid.

[0051] [A resin whose polarity increases due to the action of acid] This section describes resin (A) (also referred to as "resin (A)") whose polarity increases due to the action of an acid.

[0052] <Repeating unit with acid-degradable group> Resin (A) is a resin that decomposes and becomes more polar when exposed to acid. Resin (A) contains repeating units having groups that decompose and increase in polarity due to the action of acid (also called "acid-degradable groups"). Resin (A) becomes more polar due to the action of acid, which increases its solubility in alkaline developer and decreases its solubility in organic solvents. In pattern formation using the composition of the present invention containing resin (A), typically, a positive-type pattern is formed when an alkaline developer is used as the developer, and a negative-type pattern is formed when an organic developer is used as the developer.

[0053] The acid-degradable group is preferably a group that decomposes upon the action of an acid to produce a polar group. The acid-degradable group is preferably a structure in which the polar group is protected by a leaving group that is removed upon the action of an acid. In other words, the resin (A) preferably has repeating units having a group that decomposes upon the action of an acid to produce a polar group. Preferred polar groups include alkali-soluble groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. The polar groups mentioned above are preferably carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups, with carboxyl groups or phenolic hydroxyl groups being more preferred. In other words, the acid-degradable groups are preferably groups that decompose upon the action of an acid to produce a carboxyl group, or groups that decompose upon the action of an acid to produce a phenolic hydroxyl group. It is preferable that the resin (A) has repeating units having at least one acid-degradable group selected from the group consisting of groups that decompose by the action of an acid to produce a carboxyl group and groups that decompose by the action of an acid to produce a phenolic hydroxyl group.

[0054] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0055] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of the Rx1 to Rx3 elements may bond to each other to form a ring (which may be a monoring or polyring).

[0056] Preferred alkyl groups for Rx1 to Rx3 are C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Preferred cycloalkyl groups for Rx1 to Rx3 are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. The aralkyl groups Rx1 to Rx3 are preferably groups in which one hydrogen atom in the alkyl group Rx1 to Rx3 is replaced with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), such as a benzyl group. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3.

[0057] A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 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, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, 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 preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above.

[0058] 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. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. Also, R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group.

[0059] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0060] [ka]

[0061] Here, L1 and L2 each independently represent 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). M represents a single bond or a divalent linking group. Q 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 is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 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. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl or adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, which ensures film strength and suppresses fogging.

[0062] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0063] From the standpoint of excellent acid decomposition properties of repeating units, in the case of 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.

[0064] The leaving group that leaves by the action of an acid may alternatively be a 2-cyclopentenyl group having a substituent (such as an alkyl group) like a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group) like a 1,1,4,4-tetramethylcyclohexyl group.

[0065] Resin (A) has at least one selected from the group consisting of a repeating unit represented by the following general formula (3), a repeating unit represented by the following general formula (6), and a repeating unit represented by the following general formula (7).

[0066]

Chemical Formula

[0067] In general formula (3), R5 to R7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L2 represents a divalent linking group. R8 to R 10 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R8 to R 10 may be bonded to each other to form a ring.

[0068]

Chemical Formula

[0069] In general formula (6), R 22 to R 24 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L4 represents a single bond or a divalent linking group. Ar1 represents an aromatic group. R 25 to R 27 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 26 and R 27 may combine to form a ring. R 24 or R 25 may bond to Ar1.

[0070]

Chemical Formula

[0071] In general formula (7), R 28 to R 30 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L5 represents a single bond or a divalent linking group. R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 33 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 32 and R 33 may combine to form a ring.

[0072] Hereinafter, the repeating unit represented by general formula (3) will be described. The repeating unit represented by general formula (3) is a repeating unit having an acid-decomposable group.

[0073] The alkyl group represented by R5, R6, and R7 may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. Preferable examples of the cycloalkyl group represented by R5, R6, and R7 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Examples of halogen atoms represented by R5, R6, and R7 include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or iodine atoms being preferred. The alkyl groups contained in the alkoxycarbonyl groups represented by R5, R6, and R7 may be linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred.

[0074] Examples of divalent linking groups represented by L2 include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these groups.

[0075] R8~R 10 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. R8 to R 10 The alkyl group represented by may have a methylene group substituted with at least one of -CO- and -O-. R8~R 10 The cycloalkyl groups represented by are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. R8~R 10 A phenyl group is preferred as the aryl group represented by . R8~R 10 The aralkyl groups represented by the above-mentioned R8~R 10 A preferred group is one in which one hydrogen atom in the alkyl group represented by is replaced with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms, for example, a benzyl group. R8~R 10 A vinyl group is preferred as the alkenyl group represented by . R8~R 10A cycloalkyl group is preferred as the ring formed by the bonding of these two elements. R8~R 10 The cycloalkyl group formed by the bonding of these two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with a monocyclic cycloalkyl group having 5 to 6 carbon atoms being more preferred. R8~R 10 The cycloalkyl group formed by the bonding of these two groups may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0076] Each of the above groups in general formula (3) may have substituents, and examples of substituents include the substituent T.

[0077] The repeating unit represented by general formula (6) will be explained below. The repeating unit represented by general formula (6) is a repeating unit having an acid-degradable group.

[0078] R 22 , R 23 , and R 24 This is equivalent to R5, R6, and R7 in general formula (3), and the preferred embodiment is the same. Examples of divalent linking groups when L4 represents a divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these groups. The aromatic group represented by Ar1 is not particularly limited, but examples include a phenylene group or a naphthylene group, with the phenylene group being preferred. R 25 ~R 27The alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups represented by are R8 to R8 in the general formula (3) described above. 10 Examples of groups similar to alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups are represented by [the given formula]. R 25 ~R 27 The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by the above may have substituents, and examples of substituents include the substituent T.

[0079] R 26 and R 27 Ar1 and R 24 , and R 25 A cycloalkyl group is preferred as the ring formed by the bonding of Ar1 and R. 26 and R 27 Ar1 and R 24 , and R 25 The cycloalkyl group formed by the bonding of Ar1 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. R 26 and R 27 Ar1 and R 24 , and R 25 The cycloalkyl group formed by the bonding of Ar1 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0080] The repeating unit represented by general formula (7) will be explained below. The repeating unit represented by general formula (7) is a repeating unit having an acid-degradable group.

[0081] R 28 , R 29 , and R 30 , and L5 are R in general formula (6) 22 , R 23 , R 24 This is synonymous with L4, and the preferred embodiment is the same. R 31 , R 32 , and R 33 The alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups represented are R8 to R8 in the general formula (3) described above. 10 Examples of groups similar to alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups are represented by [the given formula]. R 31 , R 32 , and R 33 The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by the above may have substituents, and examples of substituents include the substituent T. R 32 and R 33 A cycloalkyl group is preferred as the ring formed by the bonding of these atoms. 32 and R 33 The cycloalkyl group formed by the bonding of these 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 monocyclic cycloalkyl groups having 5 to 6 carbon atoms being more preferred. R 32 and R 33 The cycloalkyl group formed by the bonding of these groups may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0082] The repeating unit selected from the group consisting of the repeating unit represented by general formula (3), the repeating unit represented by general formula (6), and the repeating unit represented by general formula (7) may or may not contain halogen atoms, but it is preferable that it does not contain halogen atoms.

[0083] The content of repeating units selected from the group consisting of repeating units represented by general formula (3), repeating units represented by general formula (6), and repeating units represented by general formula (7) (total content if there are multiple types) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, and most preferably 25 mol% or more, relative to the total number of repeating units in resin (A). Furthermore, the content of repeating units selected from the group consisting of repeating units represented by general formula (3), repeating units represented by general formula (6), and repeating units represented by general formula (7) (total content if there are multiple types) is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, particularly preferably 80 mol% or less, and most preferably 75 mol% or less, relative to the total repeating units in resin (A).

[0084] Specific examples of repeating units represented by general formula (3) are shown below, but are not limited to these.

[0085] [ka]

[0086] Specific examples of repeating units represented by general formula (6) are shown below, but are not limited to these.

[0087] [ka]

[0088] Specific examples of repeating units represented by general formula (7) are shown below, but are not limited to these. In the following structural formulas, Xa1 represents one of H, CH3, CF3, and CH2OH, and Rxa represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Resin (A) may have repeating units selected from the group consisting of repeating units represented by general formula (3), repeating units represented by general formula (6), and repeating units represented by general formula (7), in addition to repeating units having other acid-degradable groups. When resin (A) has the above-mentioned repeating units having other acid-degradable groups, the content of the above-mentioned repeating units having other acid-degradable groups (total content if there are multiple types) is preferably 1 mol% to 50 mol%, and more preferably 3 mol% to 40 mol%, relative to the total repeating units in resin (A).

[0093] The following are specific examples of repeating units having other acid-degradable groups, which are not selected from the group consisting of repeating units represented by general formula (3), repeating units represented by general formula (6), and repeating units represented by general formula (7), but are not limited to these. In the following structural formulas, Xa1 represents one of H, CH3, CF3, and CH2OH, and Rxa represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] <Repeating unit represented by general formula (A2)> The resin (A) preferably has repeating units represented by the following general formula (A2).

[0103] [ka]

[0104] In general formula (A2), R 101 , R 102 and R 103Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L A This represents a single bond or a divalent linking group. Ar A This represents an aromatic group. k represents an integer between 1 and 5. However, R 102 is Ar A It may also be combined with R 102 and Ar A When they are joined, R 102 represents a single bond or an alkylene group.

[0105] R in general formula (A2) 101 , R 102 and R 103 The alkyl group represented by is not particularly limited, but alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 8 carbon atoms are more preferred, and alkyl groups having 1 to 3 carbon atoms are even more preferred. Specific examples of the alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, and the like.

[0106] R in general formula (A2) 101 , R 102 and R 103 When represents a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic. Preferred cycloalkyl groups are monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups.

[0107] R in general formula (A2) 101 , R 102 and R 103 Examples of halogen atoms when represents a halogen atom include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred.

[0108] R in general formula (A2) 101 , R 102 and R103 When R1 represents an alkoxycarbonyl group, the specific examples and preferred ranges of alkyl groups included in the alkoxycarbonyl group are the same as those described above for alkyl groups when R1, R2, and R3 represent alkyl groups.

[0109] If each of the above-described groups can have one or more further substituents, then it may have one or more additional substituents. The additional substituents are not particularly limited, but examples include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups. The number of carbon atoms of the additional substituents is preferably 8 or less.

[0110] R in general formula (A2) 101 and R 102 It is preferable that it is a hydrogen atom. R in general formula (A2) 103 It is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0111] Ar in general formula (A2) A The symbol represents an aromatic group, more specifically, a (k+1) valent aromatic group. When k is 1, preferred divalent aromatic groups are, for example, C6-C18 arylene groups such as phenylene, torylene, naphthylene, and anthracenylene groups, or divalent aromatic groups containing heterocycles such as thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. The above aromatic groups may have substituents.

[0112] Specific examples of (k+1) valency aromatic groups when k is an integer greater than or equal to 2 include groups obtained by removing (k-1) arbitrary hydrogen atoms from the above-mentioned specific examples of divalent aromatic groups. The (k+1) valent aromatic group may have further substituents.

[0113] The substituents that a (k+1) valent aromatic group may have are not particularly limited, but include, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; and aryl groups such as phenyl groups.

[0114] Ar A It is preferable that represents an aromatic group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.

[0115] L in general formula (A2) A represents a single bond or a divalent linking group. L A The divalent linking group when represents a divalent linking group is not particularly limited, but for example, -COO-, -CONR 64 -, alkylene groups, or groups formed by combining two or more of these groups. The above R 64 represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene, are preferred. R 64 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.

[0116] The repeating unit represented by general formula (A2) preferably has a hydroxystyrene structure. That is, Ar A It is preferable that this represents a benzene ring group. k is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0117] Specific examples of repeating units represented by general formula (A2) are shown below. In the structural formulas of the specific examples below, a represents 1, 2, or 3. Furthermore, paragraphs

[0068] to

[0072] of International Publication No. 2018 / 193954 can be consulted as specific examples of repeating units represented by general formula (A2), and these contents are incorporated into the present specification.

[0118] [ka]

[0119] When resin (A) contains repeating units represented by general formula (A2), the content of repeating units represented by general formula (A2) is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, relative to the total repeating units in resin (A). Furthermore, the content of repeating units represented by general formula (A2) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, relative to the total repeating units in resin (A).

[0120] <Other repeating units> The resin (A) may contain other repeating units besides those described above. If resin (A) contains other repeating units besides those described above, the content of the other repeating units is not particularly limited, but is preferably 1 mol% to 60 mol%, more preferably 3 mol% to 50 mol%, and even more preferably 5 mol% to 40 mol% relative to the total repeating units in resin (A).

[0121] (Repeating unit with an acidic group) In addition to the repeating units described above, resin (A) may also have repeating units having acidic groups. Preferred acidic groups include, for example, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, and isopropanol groups. Furthermore, one or more fluorine atoms (preferably one to two) in the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (for example, an alkyloxycarbonyl group). The -C(CF3)(OH)-CF2- formed in this way is also preferred as an acidic group. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. For specific examples of repeating units having acidic groups, see, for example, paragraph

[0205] of International Publication No. 2019 / 054282, which are incorporated into this specification. However, repeating units having acidic groups are not limited to these.

[0122] (A repeating unit containing a fluorine atom or an iodine atom that does not exhibit acid decomposition.) In addition to the repeating units described above, resin (A) may also have repeating units that contain fluorine atoms or iodine atoms and do not exhibit acid decomposition.

[0123] Examples of repeating units having a fluorine atom or an iodine atom and not exhibiting acid decomposition are given below, but are not limited to these.

[0124] [ka]

[0125] (Repeating units having a lactone group, sultone group, or carbonate group) In addition to the repeating units described above, resin (A) may further have repeating units having lactone groups, sultone groups, or carbonate groups.

[0126] 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 preferable. The resin (A) preferably has repeating units having lactone groups or sultone groups obtained by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). Furthermore, lactone groups or sultone groups may be directly bonded to the main chain. For example, ring member atoms of lactone groups or sultone groups may constitute the main chain of resin (A).

[0127] [ka]

[0128] The lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or greater, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring. For specific examples of repeating units having a lactone structure, refer to paragraph

[0088] of International Publication No. 2018 / 193954, for example, and these contents are incorporated into the present specification. However, repeating units having a lactone structure are not limited to these.

[0129] A cyclic carbonate ester group is preferred as the carbonate group.

[0130] (Repeating unit with photoacid-generating group) The resin (A) may have repeating units having photoacid generating groups. Examples of repeating units having photoacid generating groups can be found in paragraphs

[0090] to

[0096] of International Publication No. 2018 / 193954, the details of which are incorporated into this specification.

[0131] (Other repeating units) In addition to the repeating units described above, resin (A) may have various repeating units for purposes such as adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. Other recurring units not mentioned above can be found in paragraphs

[0097] to

[0100] and

[0102] to

[0133] of International Publication No. 2018 / 193954, the contents of which are incorporated into this specification.

[0132] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). The weight-average molecular weight of resin (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. The degree of dispersion (molecular weight distribution) of resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and even more preferably 1.0 to 2.0.

[0133] The content of resin (A) in the composition of the present invention is not particularly limited, but is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, and even more preferably 70 to 95.0% by mass, relative to the total solid content of the composition of the present invention. The term "solids" refers to the components of a composition excluding the solvent; any component other than the solvent, even if it is a liquid, is considered to be part of the solids. The resin (A) contained in the composition of the present invention may be one type or two or more types.

[0134] [Acidic compounds containing an iodine atom (F)] The composition of the present invention contains an acidic compound (F) having an iodine atom (also referred to as "acidic compound (F)"). The acidic compound (F) is a different compound from the aforementioned resin (A). In other words, the acidic compound (F) and resin (A) are different components. Acidic compound (F) is a nonionic compound.

[0135] The pKa of the acidic compound (F) is preferably 10 or less, more preferably 7 or less, even more preferably 6 or less, particularly preferably 4 or less, and most preferably 3 or less. The pKa of the acidic compound (F) is preferably -1 or higher, more preferably 0 or higher, even more preferably 1 or higher, and particularly preferably 2 or higher.

[0136] The number of iodine atoms in the acidic compound (F) is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 5, and particularly preferably 1 to 4.

[0137] The molecular weight of the acidic compound (F) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 800 or less. The molecular weight of the acidic compound (F) is preferably 200 or more.

[0138] The acidic compound (F) is preferably a compound having an aromatic group substituted with an iodine atom. The presence of the iodine atom substituted on the aromatic group is preferable from the viewpoint of stability. When the acidic compound (F) has an aromatic group substituted with an iodine atom, the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but it is preferable that it be an aromatic hydrocarbon group. The aromatic group may be a monocyclic aromatic group or a polycyclic aromatic group. The aromatic group may have a structure in which an aromatic ring and a non-aromatic ring are fused together. The aromatic group may have further substituents other than the iodine atom.

[0139] The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms, and even more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the above-mentioned aromatic hydrocarbon groups include groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene. The above aromatic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and more preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0140] The above aromatic heterocyclic group is preferably an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms, and more preferably an aromatic heterocyclic group containing one or more nitrogen atoms. Examples of the above-mentioned aromatic heterocyclic groups include groups obtained by removing one or more hydrogen atoms from five-membered aromatic heterocyclic compounds containing one or more nitrogen atoms, such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, and triazole; and groups obtained by removing one or more hydrogen atoms from six-membered aromatic heterocyclic compounds containing one or more nitrogen atoms, such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The carbon atoms included as ring members in the above aromatic heterocyclic group may be substituted with oxo groups (=O).

[0141] The acidic compound (F) is preferably a compound represented by the following general formula (FA1).

[0142] [ka]

[0143] In the general formula (FA1), Ar a1 represents an aromatic group. X 1 represents a single bond or a linking group. Q 1 This represents an acidic group. Q 1 and Ar a1 They may combine to form a ring. m1 and m2 each represent an integer between 0 and 5, independently of each other. However, m1+m2 is between 1 and 6. 1 When m² represents a single bond, then m² represents 0. m3 represents either 1 or 2. If m3 represents 2, then two Ar a1 The two X's can be the same or different. 1 They may be the same or different.

[0144] Ar in the general formula (FA1) a1 represents an aromatic group. Ar a1 The description, specific examples, and preferred range of the aromatic group represented by are the same as those described above.

[0145] X in the general formula (FA1) 1 represents a single bond or a linking group. X 1 When represents a linking group, a divalent linking group is preferred. However, the above divalent linking group may be substituted with m2 iodine atoms. X 1 When - represents a divalent linking group, the divalent linking groups are -O-, -CO-, -COO-, -S-, -SO-, -SO2-, and -NQ 2 -, -NQ 2 Examples include CO-, hydrocarbon groups, or divalent linking groups formed by linking multiple of these. 2 represents a hydrogen atom or substituent. X 1 When -O- represents a divalent linking group, the divalent linking groups are -O-, -CO-, -COO-, and -NQ. 2 -, -NQ 2It is preferable that the group is a CO- group, a hydrocarbon group, or a divalent linking group formed by linking multiple of these groups.

[0146] X 1 When represents a divalent linking group containing a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and more preferably 1 to 10. Examples of hydrocarbon groups include alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups.

[0147] The alkylene group may be linear or branched. The alkylene group may also have substituents. Preferably, the alkylene group is a C1-C10 alkylene group such as a methylene group, ethylene group, n-propylene group, isopropylene group, or n-butylene group, and more preferably a C1-C6 alkylene group.

[0148] The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. The cycloalkylene group may also have substituents. Examples of the cycloalkylene group include a cyclopentylene group and a cyclohexylene group.

[0149] The above-mentioned arylene group may be a monocyclic arylene group or a polycyclic arylene group. Furthermore, the above-mentioned arylene group may have substituents. The above-mentioned arylene group is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms, for example, a phenylene group, a naphthylene group, etc.

[0150] The above alkenylene group may be linear or branched. Furthermore, the alkenylene group may have substituents. The alkenylene group is preferably a carbon-2 to carbon-10 alkenylene group such as a vinylene group, and more preferably a carbon-2 to carbon-6 alkenylene group.

[0151] Q 2 represents a hydrogen atom or substituent. Q 2 The substituents are not particularly limited when represents a substituent, but are preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. Q 2 When represents an organic group, the organic group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

[0152] Q 2 When represents an alkyl group, the alkyl group may be linear or branched. Furthermore, the alkyl group may have substituents. Preferably, the alkyl group is a C1-C10 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group, and more preferably an alkyl group having 1-C6.

[0153] Q 2 When represents a cycloalkyl group, the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The number of carbon atoms in the above cycloalkyl group is preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. The above cycloalkyl group may also have substituents. As the above cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are preferred.

[0154] Q 2 The aryl group represented by aryl may be a monocyclic aryl group or a polycyclic aryl group. Furthermore, the aryl group may have substituents. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and examples include a phenyl group, a naphthyl group, and an anthyl group.

[0155] Q 2 When represents an alkenyl group, the alkenyl group may be linear or branched. Furthermore, the alkenyl group may have substituents. The alkenyl group is preferably a C2-C10 alkenyl group such as a vinyl group, and more preferably a C2-C6 alkenyl group.

[0156] Q 2 When represents a heterocyclic group, it is preferable that the heterocyclic group be an aromatic heterocyclic group or a non-aromatic heterocyclic group.

[0157] Q 2 When represents an aromatic heterocyclic group (heteroaryl group), the aromatic heterocyclic group is preferably one containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms, and more preferably one or more aromatic heterocyclic groups containing nitrogen atoms. Examples of aromatic heterocyclic groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds containing one or more nitrogen atoms, such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, and triazole, and groups obtained by removing one hydrogen atom from six-membered aromatic heterocyclic compounds containing one or more nitrogen atoms, such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. Furthermore, the aromatic heterocyclic group may be a group obtained by removing one hydrogen atom from a compound (e.g., indole, quinoline, isoquinoline, etc.) which is fused with at least one selected from the group consisting of the above five-membered aromatic heterocyclic compound, the above six-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds, six-membered non-aromatic heterocyclic compounds, etc., described later). The above aromatic heterocyclic group may have substituents. The carbon atoms included as ring members in the above aromatic heterocyclic group may be substituted with oxo groups (=O).

[0158] Q 2 When represents a non-aromatic heterocyclic group (aliphatic heterocyclic group), a non-aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms is preferred, and a non-aromatic heterocyclic group containing one or more nitrogen atoms is more preferred. Examples of non-aromatic heterocyclic groups include groups obtained by removing one hydrogen atom from five-membered non-aromatic heterocyclic compounds containing one or more nitrogen atoms, such as pyrrolidine, pyrroline, and 2-oxazolidone, and groups obtained by removing one hydrogen atom from six-membered non-aromatic heterocyclic compounds containing one or more nitrogen atoms, such as morpholine, piperidine, and piperazine. Furthermore, the non-aromatic heterocyclic group may be a group obtained by removing one hydrogen atom from a compound in which the above-mentioned five-membered ring non-aromatic heterocyclic compound or the above-mentioned six-membered ring non-aromatic heterocyclic compound is fused with at least one selected from the group consisting of the above-mentioned five-membered ring non-aromatic heterocyclic compound, the above-mentioned six-membered ring non-aromatic heterocyclic compound, and cycloalkanes (e.g., cyclopentane, cyclohexane, etc.). The above non-aromatic heterocyclic group may have substituents. The carbon atoms included as ring members in the above non-aromatic heterocyclic group may be substituted with oxo groups (=O).

[0159] X 1 It is preferable that this represents a single bond.

[0160] Q in the general formula (FA1) 1 This represents an acidic group. The acidic group is not particularly limited, but phenolic hydroxyl groups, carboxyl groups, thiol groups, fluorinated alkyl alcohol groups (e.g., hexafluoroisopropanol groups), sulfonamide groups, or sulfonimide groups are preferred, and phenolic hydroxyl groups or carboxyl groups are more preferred.

[0161] Q in the general formula (FA1) 1and Ar a1 They may combine to form a ring.

[0162] In the general formula (FA1), m1 and m2 each independently represent integers from 0 to 5. However, m1 + m2 is from 1 to 6. 1 When m² represents a single bond, then m² represents 0. m1 preferably represents an integer between 1 and 5, and more preferably represents an integer between 1 and 4. m2 preferably represents an integer between 0 and 3, and more preferably represents an integer between 0 and 2. It is more preferable to represent 0 or 1, and particularly preferable to represent 0. m1 + m2 preferably represents 1 to 4.

[0163] In the general formula (FA1), m3 represents either 1 or 2. If m3 represents 2, then two Ar a1 The two X's can be the same or different. 1 They may be the same or different. m3 preferably represents 1.

[0164] The acidic compound (F) is more preferably a compound represented by the following general formula (FA2).

[0165] [ka]

[0166] In the general formula (FA2), Ar a1 represents an aromatic group. X 2 represents a single bond or a divalent linking group. Q 1 This represents an acidic group. m4 represents an integer between 1 and 5.

[0167] Ar in the general formula (FA2) a1 and Q 1 These are the Ar in the general formula (FA1), respectively. a1 and Q 1This expresses the same meaning, and the explanations, specific examples, and preferred ranges for each component are also the same.

[0168] X in the general formula (FA2) 2 represents a single bond or a divalent linking group. X 2 The explanation, specific examples, and preferred range when represents a divalent linking group is as follows: 1 This is the same as the description when it represents a divalent linking group. X 2 It is preferable that this represents a single bond.

[0169] In the general formula (FA2), m4 represents an integer from 1 to 5, preferably an integer from 1 to 4.

[0170] The acidic compound (F) is also preferably a compound represented by the following general formula (FA3).

[0171] [ka]

[0172] In the general formula (FA3), j represents either 0 or 1. Q 3 represents a substituent. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m6 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA3).

[0173] In the general formula (FA3), j represents either 0 or 1, and it is preferable that j represents 0. When j represents 0, the aromatic hydrocarbon listed in general formula (FA3) represents benzene. When j represents 1, the aromatic hydrocarbon listed in general formula (FA3) represents naphthalene.

[0174] Q in the general formula (FA3)3 represents a substituent. Q 3 The substituent represented is not particularly limited, but alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, fluorinated alkyl groups, acyl groups, or alkoxycarbonyl groups are preferred.

[0175] Q 3 When represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, the description, specific examples, and preferred range of each group are as follows: 2 The descriptions are the same as those for each group when it represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group.

[0176] Q 3 When represents a fluorinated alkyl group, the fluorinated alkyl group may be linear or branched. A fluorinated alkyl group having 1 to 10 carbon atoms is preferred, and a fluorinated alkyl group having 1 to 6 carbon atoms is more preferred. The fluorinated alkyl group may have substituents. The fluorinated alkyl group is preferably a perfluoroalkyl group.

[0177] Q 3 When represents an acyl group, the acyl group is preferably an alkylcarbonyl group, and may be linear or branched. The alkyl group contained in the alkylcarbonyl group is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group, and more preferably an alkyl group having 1 to 6 carbon atoms. The acyl group may have substituents.

[0178] Q 3When represents an alkoxycarbonyl group, the alkoxycarbonyl group may be linear or branched. The alkyl group contained in the alkoxycarbonyl group is preferably a C1-C10 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group, and more preferably a C1-C6 alkyl group. The alkoxycarbonyl group may have substituents.

[0179] Q 3 It is preferable that this represents a cyano group, a nitro group, a fluorinated alkyl group, an acyl group, or an alkoxycarbonyl group, and more preferably a nitro group.

[0180] In the general formula (FA3), m4 represents an integer from 1 to 5, preferably an integer from 1 to 4. m5 represents an integer between 1 and (6 + 2j - m4), preferably 1 or 2, and more preferably 1. m6 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5), preferably an integer between 0 and 2, and more preferably 1.

[0181] The acidic compound (F) is also preferably a compound represented by the following general formula (FA4).

[0182] [ka]

[0183] In the general formula (FA4), j represents either 0 or 1. Q 4 represents a substituent. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m7 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA4).

[0184] In the general formula (FA4), j represents either 0 or 1, and it is preferable that j represents 0. When j represents 0, the aromatic hydrocarbon listed in general formula (FA4) represents benzene. When j represents 1, the aromatic hydrocarbon listed in general formula (FA4) represents naphthalene.

[0185] Q in the general formula (FA4) 4 represents a substituent. Q 4 The substituent represented is not particularly limited, but alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxyl groups, cyano groups, nitro groups, fluorinated alkyl groups, acyl groups, or alkoxycarbonyl groups are preferred.

[0186] Q 4 When represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, the description, specific examples, and preferred range of each group are as follows: 2 The descriptions are the same as those for each group when it represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group.

[0187] Q 4 When represents a fluorinated alkyl group, acyl group, or alkoxycarbonyl group, the description, specific examples, and preferred range of each group are as follows: 3 The descriptions are the same as those for each group when it represents a fluorinated alkyl group, an acyl group, or an alkoxycarbonyl group.

[0188] Q 4 It is preferable that this represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a hydroxyl group, and more preferably an alkyl group or a hydroxyl group.

[0189] In the general formula (FA4), m4 represents an integer from 1 to 5, preferably an integer from 1 to 4. m5 represents an integer between 1 and (6 + 2j - m4), preferably 1 or 2, and more preferably 1. m7 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5), preferably an integer between 0 and 3, and more preferably an integer between 0 and 2.

[0190] The acidic compound (F) is also preferably a compound represented by the following general formula (FA5).

[0191] [ka]

[0192] In the general formula (FA5), j represents either 0 or 1. Q 4 represents a substituent. E 1 represents a single bond or a divalent linking group. m4 represents an integer between 1 and 5. m8 represents an integer greater than or equal to 0 and less than or equal to (4 + 2j - m4). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA5).

[0193] In the general formula (FA5), j represents either 0 or 1, and it is preferable that j represents 0. When j represents 0, the aromatic hydrocarbon listed in general formula (FA5) represents benzene. When j represents 1, the aromatic hydrocarbon listed in general formula (FA5) represents naphthalene.

[0194] Q in the general formula (FA5) 4 represents a substituent. Q 4 The description, specific examples, and preferred range of the substituent represented by Q in general formula (FA4) are given by Q 4 This is similar to what was described earlier.

[0195] E in the general formula (FA5) 1 This represents a single bond or a divalent linking group, and it is preferable to represent a divalent linking group. E 1When - represents a divalent linking group, the divalent linking groups are -CO-, -COO-, -S-, -SO-, -SO2-, and -NQ 2 -, -NQ 2 Examples include CO-, hydrocarbon groups, or divalent linking groups formed by linking multiple of these. 2 represents a hydrogen atom or substituent. The above hydrocarbon group and Q 2 The explanation, specific examples, and preferred ranges are given by X in general formula (FA1), respectively. 1 hydrocarbon groups and Q 2 This is similar to what was described earlier. E 1 When represents a divalent linking group, the divalent linking group is preferably -CO- or -SO2-.

[0196] In the general formula (FA5), m4 represents an integer from 1 to 5, preferably an integer from 1 to 4. m8 represents an integer between 0 and (4 + 2j - m4), preferably an integer between 0 and 2.

[0197] Specific examples of acidic compounds (F) are shown below, but the present invention is not limited to these.

[0198] [ka]

[0199] In the composition of the present invention, the acidic compound (F) may be used alone or in combination of two or more.

[0200] In the composition of the present invention, the content of acidic compound (F) (total if multiple types exist) is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and even more preferably 0.1 to 10% by mass, based on the total solid content of the composition of the present invention. Note that "solid content" refers to the components of a composition excluding the solvent; any component other than the solvent, even if it is a liquid component, will be considered as solid content.

[0201] Acidic compound (F) can be synthesized by referring to conventionally known methods (for example, "Organic Synthesis of Bromine and Iodine Compounds: Reagents and Synthesis Methods (2017), Maruzen Publishing," supervised by Fumi Suzuki, Manac Co., Ltd. Research Institute), or commercially available products can be used.

[0202] [Compounds that generate acid upon irradiation with active light or radiation (photoacid generators)] The photosensitive or radiation-sensitive resin composition of the present invention preferably contains a compound that generates acid upon irradiation with active light or radiation (photoacid generator). Compounds that generate acid upon irradiation with active light or radiation are also called "compound (B)" or "photoacid generator (B)".

[0203] Compound (B) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer (e.g., resin (A)). Alternatively, both the form of a low molecular weight compound and the form incorporated as part of a polymer (e.g., resin (A)) may be used in combination. If compound (B) is in the form of a low molecular weight compound, the molecular weight of compound (B) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. If compound (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). Compound (B) is preferably a low-molecular-weight compound.

[0204] For example, compound (B) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned 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 acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0205] The molecular weight of the acid generated by compound (B) is preferably 240 or more, more preferably 250 or more, even more preferably 260 or more, particularly preferably 270 or more, and most preferably 280 or more.

[0206] <Organic cations> "M + X - In the compound represented by ", M + This represents an organic cation. The structure of the organic cation described above is not particularly limited. Furthermore, the valency of the organic cation may be 1 or 2 or more. The above organic cation is preferably a cation represented by the following general formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the following general formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0207] [ka]

[0208] In the general formula (ZaI), R 201 , R 202 , and R 203 Each of these independently represents an organic group. In the general formula (ZaII), R 204 and R 205 Each of these independently represents an organic group. The above general formulas (ZaI) and (ZaII) will be described in detail below, but the R in the above general formula (ZaI) 201 , R 202 , and R 203 At least one of them is an aryl group, or R in the above general formula (ZaII) 204 and R 205 It is preferable that at least one of the groups is an aryl group. The aryl group may have substituents, and the substituents are preferably halogen atoms (preferably fluorine atoms or iodine atoms) or organic groups. Furthermore, R in the above general formula (ZaI) 201 , R 202 , and R 203 At least one of them has an acid-degradable group, or R in the above general formula (ZaII) 204 and R 205 It is also preferable that at least one of them has an acid-degradable group. The acid-degradable group is the same as that in resin (A). R in the above general formula (ZaI) 201 , R 202 , and R 203 As a form in which at least one of them has an acid-degradable group, R 201 , R 202 , and R 203 It is preferable that at least one of the groups is an aryl group substituted with an organic group containing an acid-degradable group. 204 and R 205 As a form in which at least one of them has an acid-degradable group, R 204 and R 205 Preferably, at least one of the groups is an aryl group substituted with an organic group containing an acid-degradable group.

[0209] Let's explain cations (ZaI). R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is usually 1 to 30, and preferably 1 to 20. Also, R 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 -CH2-CH2-O-CH2-CH2-.

[0210] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0211] 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. Aryl sulfonium cations are R 201 ~R 203 All of them may be aryl groups, or R 201 ~R 203 A portion of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-) 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. Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0212] 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, etc. 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 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, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0213] R 201 ~R 203 The substituents that the aryl group, alkyl group, and cycloalkyl group may have are, independently, preferably alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and 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, forming a halogenated alkyl group such as a trifluoromethyl group. Furthermore, it is preferable that the above substituents form an acid-degradable group in any combination. Furthermore, an acid-degradable group is defined as 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 leaving group that is removed upon the action of an acid. The polar group and leaving group are as described above.

[0214] 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 is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 Organic groups that do not have an aromatic ring generally have 1 to 30 carbon atoms, with 1 to 20 carbon atoms being preferred. R 201 ~R 203 Each of these is preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group.

[0215] R 201 ~R 203 Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 This may be further substituted with halogen atoms, alkoxy groups (e.g., C1-C5), hydroxyl groups, cyano groups, or nitro groups. Also, R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0216] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0217] [ka]

[0218] In the 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. R 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. R 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. Also, R 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.

[0219] 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 bond 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-mentioned 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, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0220] 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 of these atoms 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. R 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.

[0221] R 1c ~R 5c , R 6c , R 7c , R x , R y , and also, R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The rings formed by the bonding of these elements to each other may have substituents.

[0222] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0223] [ka]

[0224] In the formula (ZaI-4b), l represents an integer between 0 and 2. r represents an integer between 0 and 8. R 13 This 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 that partially contains a cycloalkyl group). These groups may have substituents. R 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-mentioned groups, such as a hydroxyl group. R 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.

[0225] In equation (ZaI-4b), R 13 , R 14 , and R 15The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is more preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. Also, R 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.

[0226] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an organic group, preferably an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with a 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. R 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).

[0227] 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., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 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.

[0228] M + Specific examples of organic cations represented by are shown below, but the present invention is not limited to these.

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] <Organic Anions> "M + X - In the compound represented by ", X - This represents an organic anion. The organic anion is not particularly limited and can be any organic anion with one or more valents. As for the organic anion, anion with a remarkably low ability to undergo nucleophilic reactions is preferred, and non-nucleophilic anions are more preferred.

[0234] Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid 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.

[0235] 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 described above may be, for example, a fluoroalkyl group (which may have substituents other than a fluorine atom; it may also be a perfluoroalkyl group).

[0236] 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.

[0237] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. While the substituents are not particularly limited, specific examples include nitro groups, halogen atoms such as fluorine or 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).

[0238] In aralkyl carboxylic acid anions, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0239] An example of a sulfonylimid anion is the saccharin anion.

[0240] For bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure. This increases the acid strength.

[0241] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4) - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0242] 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 with 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.

[0243] A preferred example of a non-nucleophilic anion is the anion represented by the following formula (AN4).

[0244] [ka]

[0245] In formula (AN4), R 1 ~R 3 Each of these independently represents an organic group or a hydrogen atom. L represents a divalent linking group.

[0246] In formula (AN4), L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0247] L is preferably a group represented by the following formula (AN4-2). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN4-2)

[0248] In formula (AN4-2), * a R in equation (AN4) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN4) 1 )(R 2)- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. 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 -SO2-* B It represents. However, X+Y in equation (AN4-2) is 1 or greater, and R in equation (AN4-2) 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 -SO2-* B It represents. * A R in equation (AN4) 3 This indicates the connection position on the side, * B -SO3 in equation (AN4) - This indicates the connection point on the side.

[0249] In formula (AN4), R 1 ~R 3 Each of these independently represents an organic group. The above organic group is not 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 atoms, sulfur atoms, and / or nitrogen atoms, etc.). Examples of the above organic groups include substituents that are not electron-withdrawing groups. Examples of substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Furthermore, preferred substituents that are not electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0250] 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. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0251] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN4). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0252] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0253] [ka]

[0254] In equation (AN1), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0255] Xf represents a fluorine atom or an organic group. The organic group may be an organic group substituted with at least one fluorine atom, or it may be an organic group that does not have a fluorine atom. The number of carbon atoms in the organic group (preferably an alkyl group) is preferably 1 to 10, and more preferably 1 to 4. Furthermore, as the organic group substituted with at least one fluorine atom (preferably an alkyl group), a perfluoroalkyl group is preferred. At least one Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0256] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If there are multiple R4 and R5, they may be the same or different. The alkyl groups represented by R4 and R5 preferably have 1 to 4 carbon atoms. The alkyl groups may have substituents. Hydrogen atoms are preferred for R4 and R5. Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (AN1).

[0257] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0258] 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. The alicyclic group 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.

[0259] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. Furthermore, the heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic 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.

[0260] The above 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. Furthermore, two or more substituents may bond to each other to form a ring. For example, two alkoxy groups, or a hydroxyl group and an alkoxy group, may bond to each other to form a ring having a cyclic acetal structure. This ring may have 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).

[0261] The anion represented by formula (AN1) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’-W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q, and W are the same as in equation (AN1). q' represents an integer from 0 to 10.

[0262] The following embodiments (AN2) and (AN3) are also preferred as anions represented by formula (AN1). Appearance (AN2): In formula (AN1), o represents 2, p represents 0, and -SO3 - The two Xf atoms bonded to the carbon atom directly bonded to (hereinafter, this carbon atom will also be called "carbon atom Z1") each independently represent an organic group that does not contain a hydrogen atom or a fluorine atom, and the two Xf atoms bonded to the carbon atom adjacent to the above carbon atom (hereinafter, this carbon atom will also be called "carbon atom Z2") each independently represent a hydrogen atom or an organic group. Preferred embodiments of q, L, and W are the same as those described above. The two Xf atoms bonded to carbon atom Z1 are preferably hydrogen atoms. Preferably, at least one of the two Xf atoms bonded to carbon atom Z2 is a fluorine atom or an organic group having a fluorine atom; more preferably, both are a fluorine atom or an organic group having a fluorine atom; and even more preferably, both are fluorine-substituted alkyl groups.

[0263] Embodiment (AN3): In formula (AN1), one of the two Xfs independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the other independently represents a hydrogen atom or an organic group without a fluorine atom. Preferred embodiments of o, p, q, R4, R5, L, and W are the same as those described above.

[0264] 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.

[0265] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN5) is also preferred.

[0266] [ka]

[0267] In formula (AN5), Ar represents an aryl group (such as a phenyl group), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group.

[0268] n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0269] 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 of these.

[0270] B represents a hydrocarbon group.

[0271] B is preferably an aliphatic hydrocarbon structure. B is more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may have a substituent (such as a tricyclohexylphenyl group). Furthermore, B also has "-(L) q The substituent may be represented by "-W". L, q, and W have the same meanings as L, q, and W in formula (AN1) above, and the specific examples and preferred ranges are also the same.

[0272] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, Rq R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. 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.

[0273] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0274] [ka]

[0275] [ka]

[0276] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have substituents (for example, a hydroxyl group).

[0277] 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). Z 2c The hydrocarbon group in the above may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member 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 also be carbonyl carbons. Also, in equation (d1-2) "Z 2c-SO3 - 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 -SO3 - 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, -SO3 - Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0278] 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.

[0279] 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.

[0280] Organic anions may be used individually or in combination of two or more.

[0281] The resist composition preferably contains two or more compounds (B), or compound (B) may be at least one selected from the group consisting of the following compounds (I) and (II).

[0282] <Compound (I) and Compound (II)> Compound (B) is also preferably at least one selected from the group consisting of the following compounds (I) and (II).

[0283] (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 a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural part X: Anion part A1 - and cation site M1 + It consists of the above, and upon irradiation with active light or radiation, it forms a structural site that forms a first acidic site represented by HA1. Structural site Y: Anionic site A2 - and cation site M2 + It consists of the above, and upon irradiation with active light or radiation, a structural site which forms a second acidic site represented by HA2. Cation site M1 + and cation site M2 + Each of these preferably represents an organic cation independently, and specific examples and preferred ranges are as described above in M + This is similar to the organic cation represented by [formula]. Furthermore, the above compound (I) satisfies the following condition I.

[0284] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation portion M2 in the structural portion Y + to H + The compound PI obtained by replacing the above structural site X is the above cation site M1 + to H + The acid dissociation constant a1 derived from the acidic site represented by HA1, which is replaced by the above-mentioned cation site M2 in the above-mentioned structural site Y + to H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, which is replaced by the above acid dissociation constant a1, and the above acid dissociation constant a2 is greater than the above acid dissociation constant a1.

[0285] 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 falls under the category of "a compound having HA1 and HA2". To explain more specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of the compound having the above characteristics is the acid dissociation constant a2.

[0286] Furthermore, 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 falls under the category of "a compound having two HA1 and one HA2". When the acid dissociation constant of such compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the acid dissociation constant when a compound having one A1 - A compound having one HA1 and one HA2 is "two A1 - The acid dissociation constant when forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. Also, "two A1 - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation site M1 corresponds to the acid dissociation constant a2. In other words, in the case of such a compound PI, the above-mentioned cation site M1 in the above-mentioned structural site X + to H + When a compound PI has multiple acid dissociation constants derived from the acidic site represented by HA1, the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1. -when a compound having one HA1 and one HA2 is formed, let the acid dissociation constant be aa, and "one A1 - and a compound having one HA1 and one HA2" becomes "two A1 - and a compound having one HA2", when the acid dissociation constant is defined as ab, the relationship between aa and ab satisfies aa < ab.

[0287] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the acid dissociation constant measurement method described above. The above compound PI corresponds to an acid generated when compound (I) is irradiated with an actinic ray or radiation. When compound (I) has two or more structural sites X, the structural sites X may each be the same or different. Further, two or more of the above A1 - , and two or more of the above M1 + may each be the same or different. Further, in compound (I), the above A1 - and the above A2 - , and the above M1 + and the above M2 + may each be the same or different, but the above A1 - and the above A2 - are preferably different from each other.

[0288] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (when a plurality of acid dissociation constants a1 exist, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (when a plurality of acid dissociation constants a1 exist, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, and is, for example, 16 or less.

[0289] In the above compound PI, the acid dissociation constant a2 is, for example, 20 or less, preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or more.

[0290] Furthermore, 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.

[0291] Anion part A1 - and anion part A2 - This refers to 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 part A1 - Preferably, the acidic site can form an acidic site 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 part A2 - For example, Anion part A1 - It is preferable that the material can form an acidic site with a larger acid dissociation constant than the other material, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position.

[0292] [ka]

[0293] [ka]

[0294] The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later.

[0295] - Compound represented by formula (Ia-1) - In the following, we will first discuss the compound represented by formula (Ia-1).

[0296] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0297] The compound represented by formula (Ia-1) is HA when irradiated with active light or radiation. 11 -L1-A 12 It produces an acid represented by H.

[0298] In formula (Ia-1), M 11 + and M 12 + Each of these independently represents an organic cation. A 11 - and A 12 - Each of these independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12 + These may be the same or different. A 11 - and A 12 - These elements may be the same or different, but it is preferable that they are different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + The compound PIa(HA) is formed by replacing it with PIa(HA) 11 -L1-A 12 In H), A 12 The acid dissociation constant a2, which originates from the acidic site represented by H, is HA 11It is greater than the acid dissociation constant a1 derived from the acidic site represented by (Ia-1). The preferred values ​​for the acid dissociation constants a1 and a2 are as described above. Furthermore, the acid generated from compound PIa and the compound represented by formula (Ia-1) upon irradiation with active light or radiation is the same. Also, M 11 + M 12 + , A 11 - , A 12 - , and at least one of L1 may have an acid-degradable group as a substituent.

[0299] In formula (Ia-1), M1 + and M2 + The organic cation represented by is as described above.

[0300] A 11 - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group including A. 12 - The monovalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a monovalent group that includes [the specified element]. A 11 - and A 12 - The monovalent anionic functional group represented by is preferably a monovalent anionic functional group containing any of the anionic moieties of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) described above, and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). 11 - Among the monovalent anionic functional groups represented by (AX-1) to (AX-3), it is preferable that they be monovalent anionic functional groups represented by any of the formulas (AX-1) to (AX-3). 12 -Among the monovalent anionic functional groups represented by (BX-1) to (BX-7), a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is preferred, and a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is more preferred.

[0301] [ka]

[0302] In formulas (AX-1) to (AX-3), R A1 and R A2 Each of these independently represents a monovalent organic group. * represents a bond position.

[0303] R A1 Examples of monovalent organic groups represented by include cyano groups, trifluoromethyl groups, and methanesulfonyl groups.

[0304] R A2 The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0305] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, and perfluoroalkyl groups being more preferred.

[0306] In equations (BX-1) to (BX-4) and (BX-6), RB represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. While the substituents are not particularly limited, fluorine atoms or cyano groups are preferred, with fluorine atoms being more preferred. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atoms that become the bonding positions in the alkyl group (for example, in the cases of formulas (BX-1) and (BX-4), the carbon atoms directly bonded to the -CO- explicitly stated in the formula of the alkyl group; in the cases of formulas (BX-2) and (BX-3), the carbon atoms directly bonded to the -SO2- explicitly stated in the formula of the alkyl group; and in the case of formula (BX-6), the carbon atoms explicitly stated in the formula of the alkyl group) - This refers to the carbon atom that is directly bonded to it. If the atom has substituents, it is also preferable that the substituents are other than a fluorine atom or a cyano group. Furthermore, the alkyl group may have carbon atoms substituted with carbonyl carbons.

[0307] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents include fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), cyano groups, alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), and fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups are more preferred.

[0308] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited and may be -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent aliphatic heterocyclic group (having at least one N, O, S, or Se atom in the ring structure). Examples include 5-10 membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings, divalent aromatic heterocyclic groups (5-10 membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic hydrocarbon ring groups (6-10 membered rings, and even more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms) are preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0309] In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1).

[0310] [ka]

[0311] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -NH-, -O-, -SO-, -SO2-, optionally substituted alkylene groups (preferably having 1 to 6 carbon atoms, and may be linear or branched), optionally substituted cycloalkylene groups (preferably having 3 to 15 carbon atoms), optionally substituted aryl groups (preferably having 6 to 10 carbon atoms), and divalent linking groups formed by combining several of these. The substituent is not particularly limited and includes, for example, halogen atoms. p represents an integer between 0 and 3, preferably between 1 and 3. v represents an integer, either 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. In particular, Xf1 and Xf2 are preferably independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. It is especially preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the connection position. L in equation (Ia-1) 11 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 The side joint (*) is A in equation (Ia-1). 12 - It is preferable to combine it with this.

[0312] - Compounds represented by formulas (Ia-2) to (Ia-4) - Next, we will explain the compounds represented by formulas (Ia-2) to (Ia-4).

[0313] [ka]

[0314] In equation (Ia-2), A 21a - and A 21b - Each of these independently represents a monovalent anionic functional group. Here, A 21a - and A 21b - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 21a - and A 21b - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - A represents a divalent anionic functional group. Here, A 22 - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group containing A. 22 - Examples of divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below include the divalent anionic functional groups represented by the formulas (BX-8) to (BX-11).

[0315] [ka]

[0316] M 21a + M 21b + , and M 22 + Each of these independently represents an organic cation.21a + M 21b + , and M 22 + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 21 and L 22 Each of these independently represents a divalent organic group.

[0317] Furthermore, in the above equation (Ia-2), M 21a + M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, which is obtained by substituting A, 22 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 21a Acid dissociation constants a1-1 and A derived from H 21b It is greater than the acid dissociation constant a1-2, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 mentioned above. Note A 21a - and A 21b - They may be the same or different from each other. Also, M 21a + M 21b + , and M 22 + They may be the same or different from one another. Also, M 21a + M 21b + M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of these may have an acid-degradable group as a substituent.

[0318] In equation (Ia-3), A 31a - and A 32 - Each of these independently represents a monovalent anionic functional group. 31a - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - This is synonymous with the same thing, and the preferred embodiment is also the same. A 32 - The monovalent anionic functional group represented by is the anionic moiety A2 described above. - This refers to a monovalent group containing A. 32 - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - A represents a divalent anionic functional group. Here, A 31b - The divalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a divalent group containing A. 31b - Examples of divalent anionic functional groups represented by the formula (AX-4) shown below include the divalent anionic functional group represented by the formula (AX-4).

[0319] [ka]

[0320] M 31a + M 31b + , and M 32 + Each of these independently represents a monovalent organic cation. 31a + M 31b + , and M 32 +The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 31 and L 32 Each of these independently represents a divalent organic group.

[0321] Furthermore, in the above equation (Ia-3), M 31a + M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, which is obtained by substituting A, 32 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 31a Acid dissociation constants a1-3 and A, derived from the acidic site represented by H. 31b It is larger than the acid dissociation constant a1-4, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 mentioned above. Note A 31a - and A 32 - They may be the same or different from each other. Also, M 31a + M 31b + , and M 32 + They may be the same or different from one another. Also, M 31a + M 31b + M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of these may have an acid-degradable group as a substituent.

[0322] In equation (Ia-4), A 41a - , A 41b - , and A42 - Each of these independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - It is synonymous with A. 42 - The definition of a monovalent anionic functional group represented by is A in formula (Ia-3) above. 32 - This is synonymous with the same thing, and the preferred embodiment is also the same. M 41a + M 41b + , and M 42 + Each of these independently represents an organic cation. L 41 This represents a trivalent organic group.

[0323] Furthermore, in the above equation (Ia-4), M 41a + M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, which is obtained by substituting A, 42 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 41a Acid dissociation constants a1-5 and A, derived from the acidic site represented by H. 41b It is larger than the acid dissociation constant a1-6, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-5 and a1-6 correspond to the acid dissociation constant a1 mentioned above. Note A 41a - , A 41b - , and A 42 - They may be the same or different from each other. Also, M 41a + M 41b+ , and M 42 + They may be the same or different from one another. Also, M 41a + M 41b + M 42 + , A 41a - , A 41b - , A 42 - , and L 41 At least one of these may have an acid-degradable group as a substituent.

[0324] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is not particularly limited and includes, for example, -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent organic groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0325] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is preferably, for example, the divalent organic group represented by the following formula (L2).

[0326] [ka]

[0327] In equation (L2), q represents an integer between 1 and 3. * indicates the joining position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0328] L A This represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6 to 10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining several of these. Furthermore, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0329] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Herein, Ph is a phenylene group which may have substituents, and is preferably a 1,4-phenylene group. The substituents are not particularly limited, but alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), or alkoxycarbonyl groups (for example, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are preferred). L in equation (Ia-2) 21 and L 22 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-2). 21a - and A 21b - It is preferable to combine it with this. Also, L in equation (Ia-3) 31 and L 32 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-3). 31a - and A 32 - It is preferable to combine it with this.

[0330] - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5).

[0331] [ka]

[0332] In equation (Ia-5), A 51a - , A 51b -, and A 51c - Each of these independently represents a monovalent anionic functional group. Here, A 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - A represents a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group containing A. 22 - Examples of divalent anionic functional groups represented by the above formulas (BX-8) to (BX-11) include divalent anionic functional groups selected from the group.

[0333] M 51a + M 51b + M 51c + M 52a + , and M 52b + Each of these independently represents an organic cation. 51a + M 51b + M 51c + M 52a + , and M 52b+ As the organic cation represented by + , it has the same definition as the above-mentioned M1, and preferred embodiments are also the same. L 51 and L 53 each independently represent a divalent organic group. As the divalent organic group represented by L 51 and L 53 , it has the same definition as L in the above-mentioned formula (Ia-2), 21 and L 22 , and preferred embodiments are also the same. L 52 represents a trivalent organic group. As the trivalent organic group represented by L 52 , it has the same definition as L in the above-mentioned formula (Ia-4), 41 and preferred embodiments are also the same.

[0334] Further, in the above formula (Ia-5), M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + , in compound PIa-5 obtained by replacing the organic cation represented by with H + , the acid dissociation constant a2-1 derived from the acidic site represented by A 52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A 52b H are larger than the acid dissociation constant a1-1 derived from A 51a H, the acid dissociation constant a1-2 derived from the acidic site represented by A 51b H, and the acid dissociation constant a1-3 derived from the acidic site represented by A 51c H. Note that the acid dissociation constants a1-1 to a1-1 correspond to the above-mentioned acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above-mentioned acid dissociation constant a2. Note that A 51a - , A 51b - , and A 51c - may be the same as or different from each other. Further, A 52a- and A 52b - They may be the same or different from each other. Also, M 51a + M 51b + M 51c + M 52a + , and M 52b + They may be the same or different from one another. Also, M 51b + M 51c + M 52a + M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of these may have an acid-degradable group as a substituent.

[0335] (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, and is a compound that 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 acids.

[0336] Definition of structural site X in compound (II), and A1 - and M1 + The definition is the definition of structural site X in compound (I) described above, and A1 - and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0337] In the above compound (II), the above cation moiety M1 in the above structural moiety X +to H + In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic moiety represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII corresponds to "one A1 - The acid dissociation constant when a compound having "one HA1" is formed, and "one A1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0338] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. Also, two or more of the above A1 - , and two or more of the above M1 + These may be the same or different.

[0339] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably, for example, a site that can electrostatically interact with a proton or a site that contains an electron-containing functional group. Examples of functional groups that can electrostatically interact with protons, or that have electrons, include functional groups having a macrocyclic structure such as cyclic polyethers, 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.

[0340]

Chem.

[0341] Examples of the partial structure of a functional group having a group that can electrostatically interact with protons or having electrons include a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Among these, a primary to tertiary amine structure is preferable.

[0342] Compound (II) is not particularly limited, and examples thereof include compounds represented by the following formula (IIa-1) and the following formula (IIa-2).

[0343]

Chem.

[0344] In the above formula (IIa-1), A 61a - and A 61b - each have the same definition as A 11 - in formula (Ia-1) described above, and preferred embodiments thereof are also the same. Further, M 61a + and M 61b + each have the same definition as M 11 + in formula (Ia-1) described above, and preferred embodiments thereof are also the same. In the above formula (IIa-1), L 61 and L 62 each have the same definition as L1 in formula (Ia-1) described above, and preferred embodiments thereof are also the same.

[0345] In formula (IIa-1), R 2X represents a monovalent organic group. R 2XThe monovalent organic group represented by is not particularly limited, and examples include alkyl groups (preferably having 1 to 10 carbon atoms; may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms), in which -CH2- may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. Furthermore, the alkylene group, the cycloalkylene group, and the alkenylene group may have substituents. The substituents are not particularly limited, but examples include halogen atoms (preferably fluorine atoms).

[0346] Furthermore, in the above equation (IIa-1), M 61a + and M 61b + The organic cation represented by H + In compound PIIa-1, which is obtained by substituting A, 61a Acid dissociation constants a1-7 and A, derived from the acidic site represented by H. 61b The acid dissociation constants a1-8, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 61a + and M 61b + to H + Compound PIIa-1, which is obtained by replacing HA, 61a -L 61 -N(R 2X )-L 62 -A 61b H is the corresponding element. Furthermore, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with active light or radiation are the same. Also, M 61a + M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R2X At least one of these may have an acid-degradable group as a substituent.

[0347] In the above equation (IIa-2), A 71a - , A 71b - , and A 71c - These are A in equation (Ia-1) described above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 71a + M 71b + , and M 71c + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-2), L 71 , L 72 , and L 73 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0348] Furthermore, in the above equation (IIa-2), M 71a + M 71b + , and M 71c + The organic cation represented by H + In compound PIIa-2, which is obtained by substituting A, 71a Acid dissociation constants a1-9 and A, derived from the acidic site represented by H. 71b Acid dissociation constants a1-10 and A originate from the acidic site represented by H. 71c The acid dissociation constants a1-11, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 71a + M 71b + , and M 71c + to H +Compound PIIa-2, which is obtained by replacing HA, 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b H is the corresponding element. Furthermore, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with active light or radiation are the same. Also, M 71a + M 71b + M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 , and L 73 At least one of these may have an acid-degradable group as a substituent.

[0349] The anionic moieties that compound (I) and compound (II) may have are exemplified, but the present invention is not limited to these.

[0350] [ka]

[0351] [ka]

[0352] As compound (B), it is also preferable to use the photoacid generators disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345.

[0353] The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of compound (B) is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, based on the total solid content of the composition of the present invention. Compound (B) may be used alone or in combination of two or more types.

[0354] [Acid diffusion control agent] The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent traps the acid generated from a photoacid generator or the like during exposure and acts as a quencher to suppress the reaction of resin (A) in the unexposed area due to excess generated acid. Examples of acid diffusion control agents that can be used include basic compounds (DA), basic compounds whose basicity decreases or disappears upon irradiation with active light or radiation (DB), onium salts (DC) that generate an acid that is relatively weaker than the acid generated from the photoacid generator (B), low molecular weight compounds (DD) that have a nitrogen atom and a group that is eliminated by the action of acid, or onium salt compounds (DE) that have a nitrogen atom in the cation portion. In the compositions of the present invention, known acid diffusion control agents can be used as appropriate. For example, 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.

[0355] As the basic compound (DA), a compound having the structure shown in the following general formulas (A) to (E) is preferred.

[0356] [ka]

[0357] In general formulas (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). 201 and R 202 These elements may be joined together to form a ring. R 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.

[0358] The alkyl groups in general formulas (A) and (E) may be substituted or unsubstituted. Regarding the alkyl group mentioned above, preferred alkyl groups having substituents are aminoalkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, or cyanoalkyl groups having 1 to 20 carbon atoms. It is more preferable that the alkyl groups in general formulas (A) and (E) are unsubstituted.

[0359] As basic compounds (DA), thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or compounds having these structures are preferred, and more preferably compounds having a thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure, or pyridine structure, alkylamine derivatives having a hydroxyl group and / or ether linkage, or aniline derivatives having a hydroxyl group and / or ether linkage are preferred.

[0360] Basic compounds (DB) (hereinafter also referred to as "compounds (DB)") whose basicity decreases or disappears upon irradiation with active light or radiation are compounds that have a proton-accepting functional group and decompose upon irradiation with active light or radiation, resulting in a decrease or disappearance of proton-accepting properties, or a change from proton-accepting properties to acidic properties.

[0361] A proton-accepting functional group is a functional group that has a group or electron capable of electrostatically interacting with a proton, such as a functional group having a macrocyclic structure like a cyclic polyether, or a functional group having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom with 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.

[0362] [ka]

[0363] Preferred substructures of the proton-accepting functional group include, for example, crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures.

[0364] Compound (DB) decomposes upon irradiation with active light or radiation, resulting in a decrease or loss of proton-accepting properties, or the generation of compounds that have changed from proton-accepting to acidic. Here, the decrease or loss of proton-accepting properties, or the change from proton-accepting to acidic properties, refers to a change in proton-accepting properties caused by the addition of a proton to a proton-accepting functional group. Specifically, it means that when a proton adduct is formed from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases. Proton-accepting properties can be confirmed by measuring pH.

[0365] The acid dissociation constant pKa of the compound generated by decomposition of compound (DB) upon irradiation with an actinic ray or radiation preferably satisfies pKa < -1, more preferably satisfies -13 < pKa < -1, and still more preferably satisfies -13 < pKa < -3.

[0366] When a photoacid generator (B) and an onium salt (DC) that generates an acid which is relatively weaker than the acid generated from the photoacid generator (B) are used in combination, if the acid generated from the photoacid generator (B) upon irradiation with an actinic ray or radiation collides with the unreacted onium salt (DC) having a weak acid anion, salt exchange occurs to release the weak acid and produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged into a weak acid with lower catalytic activity, so apparently the acid is deactivated, thereby enabling control of acid diffusion.

[0367] As the onium salt (DC), compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

[0368]

Chemical Formula

[0369] In the formula, R 51 is a hydrocarbon group which may have a substituent, Z 2c is a C1-C30 hydrocarbon group which may have a substituent, provided that the carbon adjacent to S is not substituted with a fluorine atom, R 52 is an organic group, Y 3 is a linear, branched or cyclic alkylene group or an arylene group, Rf is a hydrocarbon group containing a fluorine atom, and each M + is independently an ammonium cation, a sulfonium cation or an iodonium cation.

[0370] M + Preferable examples of the sulfonium cation or iodonium cation represented by include the sulfonium cations exemplified in general formula (ZI) and the iodonium cations exemplified in general formula (ZII).

[0371] The onium salt (DC), which is a relatively weak acid with respect to the photoacid generator, may be a compound (hereinafter also referred to as "compound (DCA)") that has both a cationic and anionic moiety within the same molecule and in which the cationic and anionic moieties are covalently linked. As the compound (DCA), a compound represented by any of the following general formulas (C-1) to (C-3) is preferred.

[0372] [ka]

[0373] In general formulas (C-1) to (C-3), R1, R2, and R3 each independently represent a substituent having one or more carbon atoms. L1 represents a divalent linking group or single bond that connects the cation and anion moieties. -X - -COO - , -SO3 - , -SO2 - , and -N - -R4 represents an anionic site selected from R4. R4 represents a monovalent substituent having at least one of the following at the linking site with the adjacent N atom: a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-), and a sulfinyl group (-S(=O)-). R1, R2, R3, R4, and L1 may bond to each other to form a ring structure. In addition, in general formula (C-3), two of R1 to R3 may together represent a single divalent substituent, which may be bonded to the N atom by a double bond.

[0374] Examples of substituents having one or more carbon atoms in R1 to R3 include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyl groups, and arylaminocarbonyl groups. Preferably, alkyl groups, cycloalkyl groups, or aryl groups are used.

[0375] Examples of L1 as a divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these. Preferably, L1 is an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0376] A low molecular weight compound (DD) (hereinafter also referred to as "compound (DD)") having a nitrogen atom and a group that is eliminated by the action of an acid is preferably an amine derivative having the group that is eliminated by the action of an acid on the nitrogen atom. The groups that are removed by the action of an acid are preferably acetal groups, carbonate groups, carbamate groups, tertiary ester groups, tertiary hydroxyl groups, or hemiaminal ether groups, with carbamate groups or hemiaminal ether groups being more preferred. The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

[0377] [ka]

[0378] In general formula (d-1), Each Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may be bonded to each other to form a ring. The alkyl, cycloalkyl, aryl, and aralkyl groups represented by Rb may each be independently substituted with functional groups such as hydroxyl, cyano, amino, pyrrolidino, piperidino, morpholino, or oxo groups, alkoxy groups, or halogen atoms. The same applies to the alkoxyalkyl groups represented by Rb.

[0379] As Rb, linear or branched alkyl groups, cycloalkyl groups, or aryl groups are preferred, and linear or branched alkyl groups, or cycloalkyl groups are more preferred. Examples of rings formed by the interconnection of two Rb molecules include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and their derivatives. Specific structures of the base represented by general formula (d-1) include, but are not limited to, those disclosed in paragraph

[0466] of U.S. Patent Publication US2012 / 0135348A1.

[0380] The compound (DD) preferably has a structure represented by the following general formula (6).

[0381] [ka]

[0382] In general formula (6), l represents an integer between 0 and 2, and m represents an integer between 1 and 3, satisfying the condition l + m = 3. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be linked together with the nitrogen atom in the formula to form a heterocycle. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula. Rb is synonymous with Rb in the general formula (d-1) above, and the preferred example is also the same. In general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may each be independently substituted with a group similar to those described above, which may be substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb.

[0383] Specific examples of the alkyl, cycloalkyl, aryl, and aralkyl groups of Ra (these groups may be substituted with the above groups) are the same groups as those mentioned above for Rb. Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph

[0475] of U.S. Patent Application Publication 2012 / 0135348A1.

[0384] An onium salt compound (DE) having a nitrogen atom in the cation (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cation. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. It is even more preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that electron-withdrawing functional groups (carbonyl groups, sulfonyl groups, cyano groups, halogen atoms, etc.) are not directly bonded to the nitrogen atom. Preferred examples of compound (DE) include, but are not limited to, the compound disclosed in paragraph

[0203] of U.S. Patent Application Publication 2015 / 0309408A1.

[0385] For specific examples of acid diffusion control agents, refer to paragraphs

[0204] to

[0206] of International Publication No. 2018 / 193954, which are incorporated into this specification. However, the acid diffusion control agents that can be used in the present invention are not limited to these.

[0386] Acid diffusion control agents may be used individually or in combination of two or more types. If the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent in the composition of the present invention (total if there are multiple types) is preferably 0.001 to 20% by mass, and more preferably 0.01 to 15% by mass, relative to the total solid content of the composition of the present invention.

[0387] [solvent] The composition of the present invention preferably contains a solvent. In the composition of the present invention, known resist solvents can be used as appropriate. Examples of solvents include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate. With regard to solvents, refer to paragraphs

[0187] to

[0197] of International Publication No. 2019 / 058890, which are incorporated into this specification.

[0388] The solid content concentration of the photosensitive or radiation-sensitive resin composition of the present invention is typically 1.0 to 30% by mass, preferably 1.5 to 10% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied to the substrate. Solid content concentration is the mass percentage of the mass of components other than the solvent, relative to the total mass of the photosensitive or radiation-sensitive resin composition.

[0389] [Surfactants] The composition of the present invention may further contain a surfactant. By including a surfactant, it becomes possible to form a pattern with good sensitivity and resolution, and with less adhesion and development defects, when using an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less. As the surfactant, it is particularly preferable to use a fluorine-based and / or silicone-based surfactant. With regard to surfactants, refer to paragraphs

[0183] to

[0184] of International Publication No. 2019 / 058890, which are incorporated into this specification.

[0390] If the composition of the present invention contains a surfactant, its content is preferably more than 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and even more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.

[0391] [Other additives] In addition to the components described above, the composition of the present invention may appropriately contain carboxylic acids, onium carboxylic acid salts, dissolution inhibitors with a molecular weight of 3000 or less as described in Proceedings of SPIE, 2724,355 (1996), dyes, plasticizers, photosensitizers, light absorbers, antioxidants, and the like.

[0392] In particular, carboxylic acids can be suitably used to improve performance. As carboxylic acids, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred.

[0393] When the composition of the present invention contains a carboxylic acid, the carboxylic acid content is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, based on the total solid content of the composition.

[0394] [Application] The present invention relates to a photosensitive or radiation-sensitive resin composition whose properties change upon irradiation with active light or radiation. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or manufacturing of lithographic printing plates or acid-curable compositions. The patterns formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0395] [Actinic ray-sensitive or radiation-sensitive film] The present invention also relates to a photosensitive or radiation-sensitive film (preferably a resist film) formed by the photosensitive or radiation-sensitive composition of the present invention described above. Such a film is formed, for example, by coating the composition of the present invention onto a support such as a substrate. The thickness of the photosensitive or radiation-sensitive film is not particularly limited, but 0.02 to 0.1 μm is preferred. As for the method of coating onto the substrate, it is coated onto the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, but spin coating is preferred, and the rotation speed is preferably 1000 to 3000 rpm (rotations per minute). The coated film is pre-baked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes to form a thin film. With regard to topcoats that may be provided on substrates, photosensitive or radiation-sensitive films, refer to paragraphs

[0342] to

[0358] of International Publication No. 2017 / 056832, which are incorporated into this specification.

[0396] [Pattern formation method] The present invention A resist film forming step of forming a resist film using the photosensitive or radiation-sensitive resin composition of the present invention, The exposure process involves exposing the resist film, A developing step in which the exposed resist film is developed using a developer, This also relates to pattern formation methods that include this. In the present invention, the exposure is preferably performed using an electron beam (EB), an ArF excimer laser, or extreme ultraviolet light (EUV), and more preferably using an electron beam or extreme ultraviolet light.

[0397] In the manufacturing of precision integrated circuit elements, the exposure (pattern formation process) on the resist film is preferably performed by first irradiating the resist film of the present invention in a patterned manner with an ArF excimer laser, electron beam, or extreme ultraviolet (EUV). The exposure dose is 1 to 100 mJ / cm² in the case of an ArF excimer laser. 2 The degree, preferably 20-60 mJ / cm² 2 For electron beams, the intensity is approximately 0.1 to 20 μC / cm². 2 Degree, preferably 3-10 μC / cm² 2 In the case of extreme ultraviolet radiation, the intensity is 0.1 to 20 mJ / cm². 2 Preferably, 3 to 15 mJ / cm² 2 Expose to the light to achieve the desired level of exposure. Next, post-exposure baking is performed on a hot plate, preferably at 60-150°C for 5 seconds to 20 minutes, more preferably at 80-120°C for 15 seconds to 10 minutes, and even more preferably at 80-120°C for 1 to 10 minutes. Then, the pattern is formed by developing, rinsing, and drying. Here, the post-exposure baking is appropriately adjusted depending on the acid decomposition properties of the repeating units having acid-decomposable groups in resin (A). If the acid decomposition properties are low, it is also preferable that the post-exposure baking temperature be 110°C or higher and the baking time be 45 seconds or higher. The developer can be selected as appropriate, but it is preferable to use an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also called an organic developer). If the developer is an alkaline aqueous solution, development is carried out using a 0.1 to 5% by mass, preferably 2 to 3% by mass alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc., for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as the dip method, puddle method, or spray method. Alcohols and / or surfactants may be added in appropriate amounts to the alkaline developer. In this way, when forming a negative pattern, the film in the unexposed areas dissolves and the film in the exposed areas is difficult to dissolve in the developer, and when forming a positive pattern, the film in the exposed areas dissolves and the film in the unexposed areas is difficult to dissolve in the developer, thereby forming the desired pattern on the substrate.

[0398] The alkali concentration of alkaline developers is typically 0.1 to 20% by mass. The pH of alkaline developers is typically between 10.0 and 15.0. In particular, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is preferred.

[0399] As the rinsing solution used in the rinsing process after alkaline development, pure water can be used with an appropriate amount of surfactant added. Furthermore, after the developing or rinsing process, a process can be performed to remove the developer or rinse solution adhering to the pattern using a supercritical fluid.

[0400] If the pattern forming method of the present invention includes a step of developing using a developer containing an organic solvent, the developer in the above step (hereinafter also referred to as the organic developer) can be a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, or a hydrocarbon solvent. The concentration of the organic solvent (total in the case of a mixture of multiple solvents) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, even more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. Most preferably, the solution consists substantially of an organic solvent. This includes cases where the solution contains trace amounts of surfactants, antioxidants, stabilizers, defoamers, etc. In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0401] Regarding the pattern formation method, refer to paragraphs

[0359] to

[0383] of International Publication No. 2017 / 056832, and these contents are incorporated into the present specification.

[0402] In the present invention, the reactive light-sensitive or radiation-sensitive composition, and the various materials used in the pattern-forming method of the present invention (for example, resist solvent, developer, rinse solution, anti-reflective film-forming composition, top coat-forming composition, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of metal-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 1 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 substantially absent (below the detection limit of the measuring device). Regarding methods for removing impurities such as metals from various materials, refer to paragraphs

[0384] to

[0402] of International Publication No. 2017 / 056832, and these contents are incorporated into the present specification.

[0403] [Manufacturing methods for electronic devices] The present invention also relates to a method for manufacturing an electronic device, including the pattern forming method described above. Electronic devices manufactured by the method for manufacturing an electronic device of the present invention are suitably mounted on electrical and electronic equipment (for example, home appliances, office automation (OA) related equipment, media related equipment, optical equipment, and communication equipment, etc.). [Examples]

[0404] 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.

[0405] <Resin (A)> The structure of the repeating units used in resin (A), their content (molar ratio), weight-average molecular weight (Mw), and dispersion (Pd=Mw / Mn) are shown below. Resin (AX-1) below is not resin (A) because it does not have any of the repeating units represented by general formula (3), general formula (6), or general formula (7), but it is listed in the resin (A) column for convenience.

[0406] [ka]

[0407] [ka]

[0408] [ka]

[0409] <Synthesis Example 1: Synthesis of Resin (A-1)> 57 g of cyclohexanone was heated to 85°C under a nitrogen atmosphere. While stirring, a mixed solution of monomer represented by formula (M-1) (50.5 g), monomer represented by formula (M-2) (37.1 g), cyclohexanone (106 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (8.6 g) was added dropwise over 3 hours to obtain the reaction solution. After the addition was complete, the reaction solution was stirred at 85°C for a further 3 hours. After the obtained reaction solution was allowed to cool, it was reprecipitated with 4100 g of ethyl acetate / heptane (mass ratio 1:9), filtered, and the resulting solid was vacuum-dried to obtain resin (A-1) (86 g).

[0410] [ka]

[0411] Other resins were synthesized in the same manner.

[0412] <Photoacid Generator (B)> The structure of the photoacid generator (B) used is shown below.

[0413] [ka]

[0414] <Acid diffusion control agent> The structure of the acid diffusion control agent used is shown below.

[0415] [ka]

[0416] <Acidic compound (F)> The structure of the acidic compound (F) used is shown below. Compound (FX-1) below does not contain an iodine atom and is therefore not an acidic compound (F), but for convenience it is listed in the acidic compound (F) column.

[0417] [ka]

[0418] The pKa values ​​of the acidic compound (F) are shown in Table 1 below.

[0419] [Table 1]

[0420] <Surfactants> The following surfactants were used. W-1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine-based) W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicone-based) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) W-5: KH-20 (manufactured by Asahi Glass Co., Ltd.) W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0421] <Solvent> The following solvents were used. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether (PGME) SL-6: Cyclohexanone SL-7: γ-Butyrolactone SL-8: Propylene Carbonate

[0422] [Preparation and application of resist composition coating solution] Each component shown in Table 2 was dissolved in the solvent shown in Table 2 in the amounts shown in Table 2 to prepare a solution with a solid content of 2.7% by mass. This solution was then filtered through a polyethylene filter having a pore size of 0.02 μm to obtain resist compositions R-1 to R-14, RX-1, and RX-2. In Table 2 below, when two or more types of each component are used, the type and amount used are separated by a " / ". For example, in Example 11, "(A-11) / (A-1)" indicates that two types of resin (A), (A-11) and (A-1), were used, and "5 / 5" indicates that 5g each of (A-11) and (A-1) was used. The obtained resist composition was coated onto a 6-inch Si (silicon) wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. Furthermore, similar results can be obtained by changing the Si wafer to a chromium substrate.

[0423] [Table 2]

[0424] [EB exposure] The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (Advantest Corporation; F7000S, acceleration voltage 50 keV). During this process, a 1:1 line-and-space pattern was formed. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and then dried. Afterward, the wafer was rotated at 4000 rpm for 30 seconds, followed by baking at 95°C for 60 seconds to dry.

[0425] 〔sensitivity〕 The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-9380II). The exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (E0). A smaller value indicates higher sensitivity.

[0426] [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-9380II). The resolution (nm) was defined as the critical resolution at the exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm (the minimum line width at which lines and spaces (line:space = 1:1) are separated and resolved). A smaller value indicates higher resolution.

[0427] [Bridge margin] When exposing a line pattern with a line width of 25 nm, the "bridge margin" was defined as the space width (nm) at which bridging began to occur in the space between the line patterns when the irradiation dose was reduced from E0. A smaller value indicates better performance.

[0428] The evaluation results are shown in the "EB Evaluation" column of Table 3 below.

[0429] [Extreme ultraviolet (EUV) exposure] 〔sensitivity〕 The obtained resist film was irradiated with EUV (wavelength 13 nm) using an EUV exposure system (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) to form a pattern. Specifically, the exposure dose was 0 to 20.0 mJ / cm². 2 Within the range of 0.1 mJ / cm 2After exposure through a reflective mask with a 1:1 line-and-space pattern and a line width of 100 nm, with the exposure temperature gradually changing, the images were baked at 110°C for 90 seconds. Subsequently, they were developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The sensitivity was defined as the exposure level required to reproduce a line-and-space (line / space = 1 / 1) mask pattern with a line width of 100 nm. A smaller value indicates higher sensitivity.

[0430] [Resolution] The resolution (nm) is defined as the critical resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure levels that exhibit the above sensitivity. A smaller value indicates higher resolution.

[0431] [Bridge margin] When exposing a line pattern with a line width of 25 nm, the space width (nm) at which bridging begins to occur in the space between the line patterns when the irradiation dose is reduced from the sensitivity level described above was used as an indicator of "bridge margin". A smaller value indicates better performance.

[0432] The evaluation results are shown in the "EUV Evaluation" column of Table 3 below.

[0433] [Table 3]

[0434] The results shown in Table 3 indicate that the resist compositions of Examples 1 to 14 exhibit excellent resolution and bridge margin. The resist composition of Comparative Example 1 used a resin (AX-1) that did not have any of the repeating units represented by general formula (3), general formula (6), or general formula (7), and therefore its resolution and bridge margin were inferior to those of the resist composition of the example. The resist composition of Comparative Example 2 used a compound (FX-1) that did not contain an iodine atom, and therefore its resolution and bridge margin were inferior to those of the resist composition of the Example.

Claims

1. A photosensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases upon the action of an acid, and an acidic compound (F) having an iodine atom, The resin (A) and the acidic compound (F) are different compounds. The acidic compound (F) is a nonionic compound and is a compound represented by the following general formula (FA3) or (FA4), The content of the acidic compound (F) is 0.1 to 10% by mass, based on the total solid content of the photosensitive or radiation-sensitive resin composition. A photosensitive or radiation-sensitive resin composition wherein the resin (A) has repeating units represented by the following general formula (3). 【Chemistry 1】 In general formula (3), R ５ ~R ７ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L ２ This represents an arylene group. R ８ ~R １０ Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ８ ~R １０ Two of them may combine to form a ring. 【Chemistry 2】 In general formula (FA3), j represents either 0 or 1. Q3 represents a nitro group. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m6 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA3). 【Transformation 3】 In the general formula (FA4), j represents either 0 or 1. Q4 represents a nitro group. m4 represents an integer between 1 and 5. m5 represents an integer between 1 and (6 + 2j - m4), inclusive. m7 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m4 - m5). *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (FA4).

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has repeating units represented by the following general formula (A2). 【Chemistry 4】 In general formula (A2), R １０１ , R １０２ and R １０３ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L Ａ This represents a single bond or a divalent linking group. Ar Ａ This represents an aromatic group. k represents an integer between 1 and 5. However, R １０２ Ar Ａ It may also be combined with R １０２ and Ar Ａ When they combine, R １０２ represents a single bond or an alkylene group.

3. The photosensitive or radiation-sensitive resin composition according to claim 1, comprising a compound that generates acid upon irradiation with active light or radiation.

4. A photosensitive or radiation-sensitive film formed using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 3.

5. A step of forming a resist film using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 3, The steps include: exposing the resist film, The process involves developing the exposed resist film using a developer solution, A pattern forming method having the following characteristics.

6. A method for manufacturing an electronic device, comprising the pattern formation method described in claim 5.

Images