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

Abstract

The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits extremely excellent resolution in the formation of ultra-fine patterns (for example, line-and-space patterns with a line width or space width of 20 nm or less, or hole patterns with a pore diameter of 20 nm or less). [Solution] A photosensitive or radiation-sensitive resin composition comprising (A) a resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates an acid upon irradiation with active light or radiation, wherein the resin (A) and the acid generated from compound (B) form a bond upon the action of active light or radiation or the acid; a photosensitive or radiation-sensitive film formed using the photosensitive or radiation-sensitive resin composition; a pattern forming method using the photosensitive or radiation-sensitive resin composition; and a method for manufacturing an electronic device.

Description

Technical Field

[0001] The present invention relates to a radiation-sensitive resin composition, a radiation-sensitive film, a patterning method, and a method for manufacturing an electronic device, which are sensitive to actinic rays or radiation.

Background Art

[0002] In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large-Scale Integrated Circuits), microfabrication by lithography using a photosensitive composition is performed. As a lithography method, a method of forming a resist film with a photosensitive composition, then exposing the obtained film, and then developing it can be mentioned. In particular, in recent years, in addition to ArF excimer lasers, studies have been made on using EB (Electron Beam) and EUV (Extreme ultraviolet) light during exposure, and radiation-sensitive resin compositions suitable for EUV exposure have been developed.

[0003] In the formation of resist patterns using EUV (wavelength 13.5 nm) or an electron beam for the purpose of forming fine patterns, the requirements for various performances are more stringent than when using conventional ArF (wavelength 193 nm) light or the like.

[0004] For example, Patent Document 1 discloses a resist composition containing an acid generator containing a salt represented by a specific structure and a resin having an acid-labile group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

[0006] In recent years, the miniaturization of patterns formed using EUV light or electron beams has progressed, and further improvements in pattern resolution and other performance aspects are required. However, the resolution required today, such as line width or space width of 20 nm or less, is an extremely high degree of miniaturization, and achieving this with conventional resist compositions is extremely difficult.

[0007] Therefore, the object of the present invention is to provide a photosensitive or radiation-sensitive resin composition that exhibits extremely excellent resolution when forming extremely fine patterns (for example, line and space patterns with a line width or space width of 20 nm or less, or hole patterns with a pore diameter of 20 nm or less). 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 problems can be solved by the following configuration.

[0009] [1] (A) A resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: A photosensitive or radiation-sensitive resin composition in which the above-mentioned resin (A) and the acid generated from the above-mentioned compound (B) form a bond upon the action of active light, radiation, or the acid.

[0010] [2] The above resin (A) is a resin having a reactive site (1), and the above compound (B) is an ionic compound having a reactive site (2) in the anionic part. The photosensitive or radiation-sensitive resin composition according to [1], wherein a reactive species generated from one of the reactive sites (1) and (2) reacts with the other of the reactive sites (1) and (2) upon the action of active light or radiation or acid to form the bond.

[0011] [3] The photosensitive or radiation-sensitive resin composition according to [2], wherein the compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) as the reactive site (2) in the anionic portion.

[0012] [ka]

[0013] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In general formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0014] [4] The photosensitive or radiation-sensitive resin composition according to [3], wherein the above-mentioned substructure is a substructure represented by the above-mentioned general formula (1) or the above-mentioned general formula (3). [5] The photosensitive or radiation-sensitive resin composition according to [3], wherein the above substructure is selected from the following substructures.

[0015] [ka] * indicates the connection position.

[0016] [6] The photosensitive or radiation-sensitive resin composition according to [5], wherein the above substructure is a substructure selected from the following.

[0017] [Chemical formula] * represents the bonding position.

[0018] [7] (A) A resin that decomposes under the action of an acid and has an increased polarity, and (B) a compound that generates an acid upon irradiation with actinic rays or radiation A photosensitive or radiation-sensitive resin composition comprising: The resin (A) is a resin having an acid group, an alcoholic hydroxyl group, or an acid-decomposable group. The photosensitive or radiation-sensitive resin composition, wherein the compound (B) is an ionic compound having a partial structure represented by any of the following general formulas (1) to (3) in the anion moiety.

[0019] [Chemical formula]

[0020] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents the bonding position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * represents the bonding position. In general formula (3), R7 represents a hydrogen atom or a substituent. * represents the bonding position.

[0021] [8] The photosensitive or radiation-sensitive resin composition according to [7], wherein the partial structure is a partial structure represented by the general formula (1) or the general formula (3). [9] The photosensitive or radiation-sensitive resin composition according to [7], wherein the partial structure is a partial structure selected from the following.

[0022] [Chemical formula]

[0023] * indicates the connection position.

[0024]

[10] The photosensitive or radiation-sensitive resin composition according to [9], wherein the above substructure is a substructure selected from the following.

[0025] [ka]

[0026] * indicates the connection position.

[0027]

[11] The above compound (B) has no substructure represented by any one of the following general formulas (11) to (14) in the anionic portion, and is a photosensitive or radiation-sensitive resin composition according to any one of items [2] to

[10] .

[0028] [ka]

[0029] In general formula (11), R 11 ~R 13 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (12), R 14 ~R 18 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (13), R 19 ~R 23 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (14), R 24 ~R 26 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position.

[0030]

[12] The above resin (A) has dissociable hydrogen atoms, and is a photosensitive or radiation-sensitive resin composition according to any one of [1] to

[11] .

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

[12] , wherein the resin (A) has phenolic hydroxyl groups.

[0031]

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

[13] , wherein the acid generated from the above compound (B) contains an aromatic ring.

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

[14] .

[0032]

[16] A step of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of items [1] to

[14] , A step of exposing the above-mentioned photosensitive or radiation-sensitive film, A pattern forming method comprising the steps of developing the exposed photosensitive or radiation-sensitive film using a developing solution to form a pattern.

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

[16] . [Effects of the Invention]

[0033] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that exhibits extremely excellent resolution when forming extremely fine patterns (for example, line-and-space patterns with a line width or space width of 20 nm or less, or hole patterns with a pore diameter of 20 nm or less). Furthermore, according to the present invention, it is possible to provide a photosensitive or radiation-sensitive film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. [Modes for carrying out the invention]

[0034] 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. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred.

[0035] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure with emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits.

[0036] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "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".

[0037] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-equivalent values obtained by GPC (Gel Permeation Chromatography) measurement using a GPC apparatus (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 velocity: 1.0 mL / min, detector: refractive index detector).

[0038] In this specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. Specifically, it is a value obtained by calculation based on Hammett substituent constants and a database of known literature values using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0039] Also, pKa can be determined by a molecular orbital calculation method. As a specific method, there is a method of calculating by calculating the dissociation free energy in an aqueous solution based on a thermodynamic cycle. + Regarding the calculation method of the dissociation free energy, for example, it can be calculated by DFT (density functional theory), but various other methods have been reported in the literature and the like, and it is not limited to this. Although there are multiple software that can perform DFT, for example, Gaussian16 can be mentioned. +

[0040] ​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. Furthermore, in this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used. "Solid content" refers to components that form photosensitive or radiation-sensitive films, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered solid content, even if its state is liquid.

[0041] Furthermore, in this specification, there are no particular limitations on the type of substituent, the position of the substituent, or the number of substituents 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 groups excluding hydrogen atoms, and for example, substituents T can be selected from the following:

[0042] (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; and acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl. Examples include alkylsulfanil groups such as methylsulfanil and tert-butylsulfanil; arylsulfanil groups such as phenylsulfanil and p-tolylsulfanil; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[0043] [Actinic ray-sensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin composition of the present invention comprises (A) a resin that decomposes and becomes more polar upon the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: This is a photosensitive or radiation-sensitive resin composition in which the above-mentioned resin (A) and the acid generated from the above-mentioned compound (B) form a bond through the action of active light, radiation, or the acid.

[0044] Furthermore, the photosensitive or radiation-sensitive resin composition of the present invention comprises (A) a resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates an acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: The above resin (A) is a resin having an acidic group, an alcoholic hydroxyl group, or an acid-degradable group. The above compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) in the anionic portion, and is a photosensitive or radiation-sensitive resin composition.

[0045] [ka]

[0046] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In general formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0047] The mechanism by which the problems of the present invention are solved with this configuration is not entirely clear, but the inventors believe it to be as follows. As described above, the composition according to the present invention contains a resin (A) and a compound (B) as a photoacid generator, and in the exposed area, the acid generated from the resin (A) and the compound (B) forms a bond due to the action of active light or radiation or acid. Furthermore, as described above, the composition according to the present invention contains a resin (A) and a compound (B) as a photoacid generator, wherein the resin (A) is a resin having an acid group, an alcoholic hydroxyl group, or an acid-degradable group, and the compound (B) is an ionic compound having a substructure represented by any of the above general formulas (1) to (3) in the anionic portion. With such a configuration, as described above, it is considered that in the exposed area, the acid generated from the compound (B) reacts with the resin (A) due to the action of active light or radiation or acid, and forms a bond with the resin (A). As a result, particularly in the formation of the extremely fine patterns described above, more precise reaction control is required in each region. In the resist film of the present invention, it is thought that the unintended movement of acid generated from compound (B) in the exposed area after exposure is suppressed with high precision, allowing the desired reaction to proceed only in the desired region, and thus enabling the acquisition of extremely fine patterns. Based on the above, it is believed that extremely fine patterns (for example, line-and-space patterns with a line width or space width of 20 nm or less, or hole patterns with a pore diameter of 20 nm or less) can be formed, resulting in patterns with extremely high resolution.

[0048] [Components of photosensitive or radiation-sensitive resin compositions] The components that may be included in the photosensitive or radiation-sensitive resin composition (hereinafter also referred to as the composition of the present invention) will be described in detail below. The photosensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. 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 typically a chemically amplified resist composition.

[0049] As described above, the resin (A) and the acid generated from the compound (B) form a bond upon the action of active light or radiation or an acid. The acid referred to in "by the action of active light or radiation or an acid" is not particularly limited as long as it can form the above bond, but is typically an acid generated from compound (B). Furthermore, examples of such bonds include covalent bonds. These bonds are formed in the exposure area.

[0050] The above resin (A) is a resin having a reactive site (1), and the above compound (B) is an ionic compound having a reactive site (2) in the anionic part. It is preferable that a reactive species generated from one of the reactive sites (1) and (2) reacts with the other of the reactive sites (1) and (2) by the action of active light or radiation or acid to form the bond described above.

[0051] The above-mentioned reactive site (1) is not particularly limited, but examples include an acidic group, an alcoholic hydroxyl group, or an acid-degradable group. Details of each unit will be described later. The reactive site (2) is not particularly limited, but examples include substructures represented by any of the following general formulas (1) to (3).

[0052] [ka]

[0053] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In general formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0054] Details of each unit will be described later. It is preferable that the above compound (B) has the above substructure as the reactive site (2) in the anionic portion.

[0055] The reactive species generated by the action of active light or radiation or acid typically originate from either the reactive site (1) or the reactive site (2) described above. The above-mentioned reactive species is not particularly limited as long as it can react with the other of the reactive sites (1) and (2) to form a bond.

[0056] The reactive species generated from the reactive site (2) are not particularly limited, but examples include a site where a substructure of compound (B) of another molecule is attacked by an acid generated from compound (B), resulting in a carbocation. Furthermore, even if the reactive species does not become a carbocation, δ + A carbon atom with a positive charge can also be cited. Examples of how the reactive species generated from the reactive site (2) reacts with the reactive site (1) to form a bond include the following: As mentioned above, if the acid generated from compound (B) is involved in the reaction, then the carbocation or δ described above will be involved. + An acidic group, an alcoholic hydroxyl group, or an acid-degradable group, acting as the reactive site (1) of resin (A), performs a nucleophilic attack on the charged carbon atom, causing resin (A) and compound (B) to bond.

[0057] The reactive species generated from the above-mentioned reactive site (1) are not particularly limited, but for example, when a resin containing a phenolic hydroxyl group as an acid group is used, examples include radicals of oxygen atoms obtained by the removal of a hydrogen atom from the hydroxyl group by active light or radiation, and radicals generated by the removal of a hydrogen atom on the aromatic ring that is in the ortho position relative to the hydroxyl group. Examples of how the reactive species generated from the reactive site (1) reacts with the substructure represented by any of the general formulas (1) to (3) above, which is the reactive site (2), to form a bond include the following: As described above, when active light or radiation is involved in the reaction, the radical site in resin (A) attacks the substructure represented by any of the general formulas (1) to (3) above, which is the reactive site (2) of compound (B), and the resin (A) and compound (B) bond together.

[0058] The reactive site (1) and the reactive site (2) may each consist of one or multiple sites.

[0059] <(A) Resin> A photosensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition") contains a resin (A) (hereinafter also referred to as "resin (A)") that decomposes upon the action of an acid and increases in polarity. Resin (A) is typically an acid-degradable resin and usually contains groups that decompose and increase in polarity due to the action of acid (hereinafter also referred to as "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. Therefore, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic-based developer is used as the developer, a negative-type pattern is suitably formed. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are also preferred as repeating units having acid-degradable groups.

[0060] In a preferred embodiment, the resin (A) has a reactive site (1). The above-mentioned reactive site (1) is not particularly limited, but examples include an acidic group, an alcoholic hydroxyl group, or an acid-degradable group.

[0061] The acid group is not particularly limited, but an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorine alcohol groups, sulfonic acid groups, or sulfonamide groups, with phenolic hydroxyl groups or fluorine alcohol groups being more preferred. A phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic ring. A hexafluoroisopropanol group is preferred as the fluorine alcohol group. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. 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-.

[0062] An alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, excluding hydroxyl groups directly bonded to an aromatic ring (phenolic hydroxyl groups). It excludes aliphatic alcohols (e.g., hexafluoroisopropanol groups) in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom. Preferably, the alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0063] An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group that is released upon the action of an acid. In other words, resin (A) has repeating units that decompose upon the action of an acid to produce a polar group. Resins having these repeating units become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents. Preferred polar groups are 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 (typically groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), as well as alcoholic hydroxyl groups.

[0064] Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0065] 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)

[0066] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). 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 Rx1 to Rx3 may combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably 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. The cycloalkyl groups Rx1 to Rx3 are preferably 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. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. 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 cycloalkyl groups formed by the bonding of two Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with 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.

[0067] If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0068] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include groups containing heteroatoms such as oxygen atoms and / or 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 groups containing heteroatoms such as oxygen atoms and / or 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. If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0069] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0070] [ka]

[0071] 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 containing 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 formed by 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, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0072] If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom (that is, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group). Furthermore, if the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and the group which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom which may contain a heteroatom.

[0073] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. If the composition of the present invention is, for example, a composition for EUV lithography, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0074] 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.

[0075] Other leaving groups that are removed by the action of an acid may include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0076] As mentioned above, acid-degradable groups can be reactive sites (1), specifically as follows: In the exposed area, the acid causes the leaving group to detach from the acid-degradable group, generating a polar group. This polar group can become a reactive site (1). The above acid is typically an acid generated from compound (B).

[0077] The reactive species generated from the above-mentioned reactive site (1) are not particularly limited, but for example, when a resin containing a phenolic hydroxyl group as an acid group is used, examples include radicals of oxygen atoms obtained by the removal of a hydrogen atom from the hydroxyl group by active light or radiation, and radicals generated by the removal of a hydrogen atom on the aromatic ring that is in the ortho position relative to the hydroxyl group.

[0078] In a preferred embodiment, the resin (A) has an acidic group, an alcoholic hydroxyl group, or an acid-degradable group. Acidic groups, alcoholic hydroxyl groups, or acid-degradable groups are as described above. Acidic groups, alcoholic hydroxyl groups, or acid-degradable groups can each be reactive sites (1). Reactive sites (1) may also be sites that generate reactive species upon the action of active light or radiation or acid.

[0079] The resin (A) described above preferably has dissociable hydrogen atoms. Examples of dissociable hydrogen atoms include hydrogen atoms in the OH group of the acid group and hydrogen atoms in the alcoholic hydroxyl group. In a preferred embodiment, the site having a dissociable hydrogen atom may be a phenolic hydroxyl group. In other words, it is preferable that the resin (A) has phenolic hydroxyl groups. Furthermore, it is preferable that the resin (A) has repeating units having phenolic hydroxyl groups.

[0080] Resin (A) may have an acidic group, an alcoholic hydroxyl group, or an acid-degradable group, or it may have two of the acidic group, alcoholic hydroxyl group, or acid-degradable group, or it may have all of the acidic group, alcoholic hydroxyl group, and acid-degradable group.

[0081] (Repeating unit having an acid-degradable group (a2)) Resin (A) may contain repeating units having acid-degradable groups (also referred to as "repeating units (a2)"). The acid-degradable groups are as described above.

[0082] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0083] [ka]

[0084] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, L1 is preferably -CO-, an arylene group, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO-, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0085] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0086] R2 represents a leaving group that is eliminated by the action of an acid and may contain a fluorine atom or an iodine atom. Examples of leaving groups that may contain a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that contain a fluorine atom or an iodine atom.

[0087] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0088] [ka]

[0089] In equation (AI), Xa1 represents a hydrogen atom or an alkyl group which may have substituents. T represents a single bond or a divalent linking group. Each of Rx1 to Rx3 independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, if 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. Two of Rx1 to Rx3 may bond together to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0090] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0091] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0092] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 14 carbon atoms, and more preferably aryl groups having 6 to 10 carbon atoms. Examples include phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups 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. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. 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 containing 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 repeating unit represented by formula (AI) preferably has, for example, Rx1 being a methyl group or an ethyl group, and Rx2 and Rx3 being bonded to form the cycloalkyl group described above.

[0093] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less. In one preferred embodiment, it is preferable that two of Rx1 to Rx3 are bonded together to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, etc.).

[0094] The repeating unit represented by formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0095] Specific examples of repeating units having acid-degradable groups are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] Resin (A) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0102] [ka]

[0103] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0104] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0105] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic group is preferred.

[0106] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. An ethynyl group is preferred as the alkynyl group for Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 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. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Ry3 are bonded together to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0107] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0108] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenylene group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0109] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0110] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''':R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, or monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or -SO3- group, a vinylidene group, or a combination thereof, and n and m represent integers of 0 or more.

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0116] The resin (A) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of the following repeating units (20) to (29). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom, a bromine atom, or an iodine atom, which are described later and do not have either an acid-degradable group or an acid group. (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having photoacid generators, as described later (24) Repeating units represented by formula (V-1) or formula (V-2) below, as described later. (25) Repeating units represented by formula (A), as described later (26) Repeating units represented by formula (B), which will be described later (27) Repeating units represented by formula (C), as described later (28) Repeating units represented by formula (D), which will be described later (29) Repeating units represented by formula (E), which will be described later Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0117] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from the photoacid generator is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0118] When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group A. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that resin (A) contains at least one of a fluorine atom and an iodine atom. If resin (A) contains both a fluorine atom and an iodine atom, resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or resin (A) may contain two types of repeating units: one containing a fluorine atom and another containing an iodine atom. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is also preferable that the resin (A) has repeating units having aromatic groups. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. Furthermore, when the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have aromatic groups.

[0119] (Repeating units containing acidic groups) The resin (A) may have repeating units having acidic groups. The acid group is as described above. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, the resulting pattern shape is excellent, and the resolution is also excellent. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0120] Examples of repeating units having an acidic group include the following:

[0121] [ka]

[0122] As a repeating unit having an acid group, the repeating unit represented by the following formula (1) is preferred.

[0123] [ka]

[0124] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. If there are multiple Rs, they may cooperate to form a ring. A hydrogen atom is preferred as R. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0125] The following are examples of repeating units containing an acid group. In the formulas, 'a' represents an integer from 1 to 3.

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] Of the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer from 1 to 3.

[0131] [ka]

[0132] [ka]

[0133] The content of repeating units having acid groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0134] (A repeating unit that does not possess either an acid-degradable group or an acidic group, but has a fluorine atom, a bromine atom, or an iodine atom.) Resin (A) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. Furthermore, it is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0135] The repeating unit X is preferably represented by formula (C).

[0136] [ka]

[0137] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom. 10 This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof.

[0138] Examples of repeating units having fluorine or iodine atoms are shown below.

[0139] [ka]

[0140] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A).

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

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

[0143] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more 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 formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following 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).

[0144] [ka]

[0145] The above 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, 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.

[0146] Examples of repeating units having a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3), include the repeating unit represented by the following formula (AI).

[0147] [ka]

[0148] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among these, a single bond or a linking group represented as -Ab1-CO2- is preferred for Ab. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

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

[0150] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by the following formula (A-1) is preferred.

[0151] [ka]

[0152] In formula (A-1), R A 1 R represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0153] The unit Y is exemplified below.

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] The content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0158] (Repeating unit with photoacid-generating group) The resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (hereinafter also referred to as a "photoacid generating group"). An example of a repeating unit having a photoacid-generating group is the repeating unit represented by formula (4).

[0159] [ka]

[0160] R 41 L represents a hydrogen atom or a methyl group. 41 L represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.

[0161] [ka]

[0162] Other examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

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

[0163] The content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0164] (The repeating unit is represented by formula (V-1) or formula (V-2) below) The resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). It is preferable that the repeating units represented by the following formulas (V-1) and (V-2) are different from the repeating units described above.

[0165] [ka]

[0166] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. Linear or branched alkyl groups having 1 to 10 carbon atoms are preferred as alkyl groups. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and the number of carbon atoms is preferably 3 to 15, more preferably 3 to 10, and even more preferably 3 to 6. n3 represents an integer between 0 and 6. n4 represents an integer between 0 and 4. X 4 This is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

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

[0167] (A repeating unit that reduces the mobility of the main chain) Resin (A) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). Furthermore, the calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0168] To increase the Tg of resin (A) (preferably to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking of annular structures to the main chain Furthermore, it is preferable that resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher. Furthermore, there are no particular restrictions on the type of repeating units in which the homopolymer Tg is 130°C or higher; any repeating unit in which the homopolymer Tg calculated by the Bicerano method is 130°C or higher is acceptable. Note that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described later, some repeating units may be considered to have a homopolymer Tg of 130°C or higher.

[0169] One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into resin (A).

[0170] [ka]

[0171] Formula (A), R A R represents a group containing a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, which may or may not be condensed. Specific examples of repeating units represented by formula (A) are those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0172] One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into resin (A).

[0173] [ka]

[0174] In formula (B), R b1 ~R b4 Each of these independently represents a hydrogen atom or an organic group, and R b1 ~R b4 At least two of these represent organic groups. Furthermore, if at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited. Furthermore, if none of the organic groups are directly linked to the main chain in the repeating unit, then at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Specific examples of repeating units represented by formula (B) are those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0175] One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A).

[0176] [ka]

[0177] In formula (C), R c1 ~R c4 Each of these independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. In particular, it is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of resin (A). Specific examples of repeating units represented by formula (C) are those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0178] One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A).

[0179] [ka]

[0180] In formula (D), "cylic" represents a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Specific examples of repeating units represented by formula (D) are those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0181] One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A).

[0182] [ka]

[0183] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substitution mechanisms. A "cylic" is a cyclic group that contains carbon atoms in the main chain. There are no particular restrictions on the number of atoms that can be included in a cyclic group. Specific examples of repeating units represented by formula (E) are those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0184] (A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0185] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating units having a hydroxyl group or a cyano group do not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921. In one preferred embodiment, the hydroxyl group is an alcoholic hydroxyl group. Furthermore, if the resin (A) has repeating units having alcoholic hydroxyl groups, the content of repeating units having alcoholic hydroxyl groups is preferably 5 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to the total repeating units in resin (A).

[0186] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bisulfonylimide groups, and aliphatic alcohols (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

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

[0187] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion solution during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0188] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0189] [ka]

[0190] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

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

[0191] (Other repeating units) Furthermore, resin (A) may have repeating units other than those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. Examples of such repeating units are shown below.

[0192] [ka]

[0193] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0194] As for resin (A), (especially when the composition is used as an active photosensitive or radiation-sensitive resin composition for ArF) it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. In this case, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0195] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0196] In the composition of the present invention, the content of resin (A) is preferably 30.0 to 99.9% by mass, more preferably 60.0 to 90.0% by mass, and even more preferably 60.0 to 85.0% by mass, based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of multiple types.

[0197] The composition of the present invention may contain, in addition to resin (A), a resin different from resin (A) (also called resin (A')), as long as the effects of the present invention are not impaired. Resin (A') is not particularly limited as long as it is a different resin from resin (A), but examples include resins that do not have acidic groups, alcoholic hydroxyl groups, or acid-degradable groups in resin (A). If the composition of the present invention contains resin (A'), the ratio of the content of resin (A) to the content of resin (A') in the composition of the present invention is preferably 9:1 to 8:2 by mass.

[0198] <(B) Compounds that generate acid upon irradiation with active light or radiation> The composition of the present invention contains a compound (also referred to as compound (B), photoacid generator, or photoacid generator (B)) that generates acid upon irradiation with active light or radiation. The photoacid generator is a compound that generates acid upon exposure. The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer (for example, resin (A) described later). Alternatively, both the form of a low molecular weight compound and the form incorporated into a polymer (for example, resin (A) described later) may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). In the present invention, the photoacid generator (B) is preferably in the form of a low molecular weight compound. The photoacid generator (B) may be an ionic compound having both a cation and anion.

[0199] In a preferred embodiment, the compound (B) is preferably an ionic compound having a reactive site (2) in the anionic portion. The reactive site (2) is not particularly limited, but examples include substructures represented by any of the following general formulas (1) to (3).

[0200] [ka]

[0201] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In general formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0202] The substituents R1 to R3 are not particularly limited, but examples include alkyl groups. The alkyl group is not particularly limited, but examples include linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred.

[0203] Examples of divalent linking groups for L include -COO-, -CO-, -O-, alkylene groups, cycloalkylene groups, arylene groups, and linking groups formed by linking multiple of these groups. The alkylene group is not particularly limited and may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The cycloalkylene group is not particularly limited, but may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 6. The arylene group is not particularly limited, but an arylene group having 6 to 14 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is more preferred. The alkylene group, cycloalkylene group, and arylene group may have substituents. In a preferred embodiment, the substituent is not particularly limited, but examples include alkyl groups and halogen atoms. Examples of alkyl groups are linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0204] For L, a single bond, -COO-, or -O- is preferred. R2 and R3 preferably represent hydrogen atoms.

[0205] The substituents R4 to R6 are not particularly limited, but examples include alkyl groups. The alkyl group is not particularly limited, but examples include linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred. R6 preferably represents a hydrogen atom.

[0206] The substituent for R7 is not particularly limited, but examples include alkyl groups. The alkyl group is not particularly limited, but examples include linear or branched alkyl groups having 1 to 12 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 3 carbon atoms being more preferred.

[0207] The above substructure is preferably represented by the above general formula (1) or the above general formula (3).

[0208] The above substructure is preferably a substructure selected from the following.

[0209] [ka]

[0210] * indicates the connection position.

[0211] The above substructure is preferably a substructure selected from the following.

[0212] [ka]

[0213] * indicates the connection position.

[0214] The reactive species generated from the reactive site (2) are not particularly limited, but examples include a site where a substructure of compound (B) of another molecule is attacked by an acid generated from compound (B), resulting in a carbocation. Furthermore, even if the reactive species does not become a carbocation, δ + A carbon atom with a positive charge can also be cited.

[0215] In a preferred embodiment, compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) in the anionic portion.

[0216] [ka]

[0217] In formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0218] Each of the groups in the above general formulas (1) to (3) is as described above. Each of the substructures represented by the above general formulas (1) to (3) can be a reactive site (2). The reactive site (2) may also be a site that generates reactive species upon the action of active light, radiation, or acid.

[0219] The above substructure is preferably represented by the above general formula (1) or the above general formula (3).

[0220] The above substructure is preferably a substructure selected from the following.

[0221] [ka]

[0222] * indicates the connection position.

[0223] The above substructure is preferably a substructure selected from the following.

[0224] [ka]

[0225] * indicates the connection position.

[0226] The above compound (B) may or may not have a substructure represented by any of the following general formulas (11) to (14) in the anionic portion. However, since the polymerization reaction of the above compound (B) tends to proceed, it is preferable that the anionic portion does not have a substructure represented by any of the following general formulas (11) to (14).

[0227] [ka]

[0228] In general formula (11), R 11 ~R 13 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (12), R 14 ~R 18 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (13), R 19 ~R 23 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (14), R 24 ~R 26 Each of these independently represents a hydrogen atom or a substituent. * represents a bond position.

[0229] R 11 ~R 13 The substituent is not particularly limited as long as it is a monovalent substituent, but an example is the substituent T mentioned above. R 14 ~R 18 The substituent is not particularly limited as long as it is a monovalent substituent, but an example is the substituent T mentioned above. R 19 ~R 23 The substituent is not particularly limited as long as it is a monovalent substituent, but an example is the substituent T mentioned above. R 24 ~R 26 The substituent is not particularly limited as long as it is a monovalent substituent, but an example is the substituent T mentioned above.

[0230] The acid generated from compound (B) above preferably contains an aromatic ring. The aromatic ring is not particularly limited, but may be monocyclic or polycyclic. Examples of aromatic rings include benzene rings, naphthalene rings, and anthracene rings.

[0231] For example, the photoacid generator (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.

[0232] "M + X - In the compound represented by ", M + This represents an organic cation. The organic cation is not particularly limited. Furthermore, the valency of the organic cation may be 1 or 2 or higher. In particular, among the above organic cations, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0233] [ka]

[0234] In the above equation (ZaI), R 201 , R 202 , and R 203 Each of these independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. 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-.

[0235] Preferable embodiments of the organic cation in formula (ZaI) include the cations (ZaI-1), (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.

[0236] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 ~R 203 is an aryl group. For the arylsulfonium cation, all of R 201 ~R 203 may be aryl groups, or a part of R 201 ~R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups. Also, one of R 201 ~R 203 is an aryl group, and the remaining two of R 201 ~R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R 201 ~R 203 include an alkylene group (e.g., a butylene group, a 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 the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0237] As the aryl group contained in the arylsulfonium cation, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation may have as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0238] R 201 ~R 203 Preferred examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R~R may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom (for example, fluorine and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. When possible, the above substituents may further have substituents, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. Further, it is also preferable that the above substituents form an acid-decomposable group by any combination. The acid-decomposable group is intended to be a group that decomposes by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a leaving group that leaves by the action of an acid. The above polar group and leaving group are as described above.

[0239] 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 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0240] 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 a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. Also, R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0241] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0242] [ka]

[0243] 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 R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0244] 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.

[0245] 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.

[0246] R 1c ~R 5c , R 6c , R 7c , R x , R y , and 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.

[0247] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0248] [ka]

[0249] 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 containing a cycloalkyl group as part). 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.

[0250] 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 preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. Also, R 13 ~R 15 , and R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0251] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents 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 the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. 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).

[0252] 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.

[0253] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0254] [ka]

[0255] [ka]

[0256] [ka]

[0257] "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. Organic anions have a substructure represented by any of the above general formulas (1) to (3).

[0258] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0259] 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).

[0260] 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.

[0261] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0262] 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.

[0263] An example of a sulfonylimid anion is the saccharin anion.

[0264] 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.

[0265] 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.

[0266] 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.

[0267] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0268] [ka]

[0269] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Furthermore, preferred non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0270] 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.

[0271] 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-, -SO2-O-, or -COO-alkylene group-.

[0272] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0273] In formula (AN1-1), * a R in equation (AN1) 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 (AN1) 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 (AN1-1) is 1 or greater, and R in equation (AN1-1) 2a and R 2bIf 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 (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0274] In formula (AN1), R 3 This represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0275] 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 (AN1). 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.

[0276] The above formula (AN1) has a substructure represented by any of the above general formulas (1) to (3).

[0277] 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.

[0278] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0279] [ka]

[0280] In equation (AN2), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0281] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, 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, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0282] R 4 and R 5 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred for R4 and R5.

[0283] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0284] 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.

[0285] 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.

[0286] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0287] The anion represented by formula (AN2) 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 (AN2). q' represents an integer from 0 to 10. The above formula (AN2) has a substructure represented by any of the above general formulas (1) to (3).

[0288] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0289] [ka]

[0290] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0291] 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.

[0292] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group). B may have substituents. The above formula (AN3) has a substructure represented by any of the above general formulas (1) to (3).

[0293] As a non-nucleophilic anion, the methido anion represented by the following formula (AN4) is also preferred.

[0294] [ka]

[0295] In the above formula (AN4), R 11 , R 12 , R 13 Each of these independently represents an organic group. A1 to A3 each independently represents -C(=O)- or -S(=O)2-. 11 , R 12 , R 13 At least two of these may be joined together to form a ring.

[0296] In formula (AN4), R 11 , R 12 , R 13 Each of these independently represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0297] In particular, the above organic group is preferably an organic group having a cyclic structure. The above cyclic structure may be monocyclic or polycyclic, and may have substituents. 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, or an aryl 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 aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. 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. The organic group having the above cyclic structure may have substituents. The above formula (AN4) has a substructure represented by any of the above general formulas (1) to (3).

[0298] 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, R q 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. R q It has a substructure represented by any of the above general formulas (1) to (3).

[0299] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0300] [ka]

[0301] [ka]

[0302] 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).

[0303] 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 represented by the above formulas (AN1) to (AN3) is different from the anion. 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.

[0304] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0305] In formula (d1-4), R 53 and R 54 Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). 53 and R 54 They may be joined to each other to form a ring. The anions represented by formulas (d1-1) to (d1-4) have a substructure represented by any of the above general formulas (1) to (3).

[0306] Organic anions may be used individually or in combination of two or more.

[0307] The photoacid generator is preferably at least one selected from the group consisting of compounds (I) to (II).

[0308] (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. Furthermore, the above compound (I) satisfies the following condition I.

[0309] 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.

[0310] 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.

[0311] 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 it becomes a "compound having one HA2" corresponds to the above acid dissociation constant a1. Also, "two A1" - The acid dissociation constant when the "compound having one HA2" becomes "two A1" - and A2 - The acid dissociation constant when it becomes a "compound having" corresponds to the acid dissociation constant a2. That is, in the case of such a compound PI, when there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 obtained by replacing the cationic site M1 in the above structural site X with H + the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. In addition, when the acid dissociation constant when the compound PI becomes a "compound having one A1" + one HA1 and one HA2 is aa, and when the "compound having one A1" - one HA1 and one HA2 becomes a "compound having two A1" - one HA1 and one HA2 and the acid dissociation constant at this time is ab, the relationship between aa and ab satisfies aa < ab. - and one HA2

[0312] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-described method for measuring the acid dissociation constant. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - and two or more of the above M1 + may be the same or different from each other. Also, in the compound (I), the above A1 - and the above A2 - as well as the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0313] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or greater, more preferably 0.5 or greater, and even more preferably 1.0 or greater. There is no particular upper limit to the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are multiple acid dissociation constants a1) and the acid dissociation constant a2, but for example, it is 16 or less.

[0314] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0315] 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.

[0316] 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 one specified above, 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. In formula (AA-2), R A R represents a monovalent organic group. AThe monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0317] [ka]

[0318] Also, cation site M1 + and cation site M2 + This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. + Examples of organic cations represented by the following are given.

[0319] Compound (I) has a substructure in its anionic portion that is represented by any of the above general formulas (1) to (3). The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later.

[0320] - Compound represented by formula (Ia-1) - In the following, we will first discuss the compound represented by formula (Ia-1).

[0321] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0322] 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.

[0323] 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 11 It 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.

[0324] In formula (Ia-1), M 11 + and M 12 + The organic cations represented by the above M are as follows: +Examples of organic cations represented by the following are given.

[0325] 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). A 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). Also, A 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.

[0326] [ka]

[0327] 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. R A1The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0328] R A2 The monovalent organic group represented is preferably a linear or branched alkyl group, cycloalkyl group, or 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. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and the number of carbon atoms is preferably 3 to 15, more preferably 3 to 10, and even more preferably 3 to 6. The above cycloalkyl group may have substituents. Preferably, the substituent is a fluorine atom or a cyano group, and more preferably a fluorine atom.

[0329] 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, or perfluoroalkyl groups being more preferred.

[0330] In equations (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented is preferably a linear or branched alkyl group, cycloalkyl group, or 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.

[0331] The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and the number of carbon atoms is preferably 3 to 15, more preferably 3 to 10, and even more preferably 3 to 6. The above cycloalkyl group may have substituents. Preferably, the substituent is a fluorine atom or a cyano group, and more preferably a fluorine atom. In a cycloalkyl group, the carbon atom that becomes the bond position (for example, in the cases of formulas (BX-1) and (BX-4), the carbon atom directly bonded to the -CO- explicitly stated in the formula of the cycloalkyl group; in the cases of formulas (BX-2) and (BX-3), the carbon atom directly bonded to the -SO2- explicitly stated in the formula of the cycloalkyl group; and in the case of formula (BX-6), the carbon atom that becomes the bond position in the cycloalkyl 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 above cycloalkyl group may have carbon atoms substituted with carbonyl carbons.

[0332] 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.

[0333] 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).

[0334] In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1).

[0335] [ka]

[0336] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111 The 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.

[0337] The anion portion in formula (Ia-1) has a substructure represented by any of the above general formulas (1) to (3).

[0338] - Compounds represented by formulas (Ia-2) to (Ia-4) - Next, we will explain the compounds represented by formulas (Ia-2) to (Ia-4).

[0339] [ka]

[0340] 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).

[0341] [ka]

[0342] 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 M is 11 + 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.

[0343] 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.

[0344] 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).

[0345] [ka]

[0346] 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 M is 11 + 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.

[0347] 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 A32 - 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.

[0348] In equation (Ia-4), A 41a - , A 41b - , and A 42 - 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. 41a + M 41b + , and M 42 +The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 41 This represents a trivalent organic group.

[0349] 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.

[0350] 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).

[0351] 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).

[0352] [ka]

[0353] 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.

[0354] 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).

[0355] 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. Each anion portion in equations (Ia-2) to (Ia-4) independently has a substructure represented by any of the above general equations (1) to (3).

[0356] - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5).

[0357] [ka]

[0358] 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.

[0359] 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 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 51 and L 53 Each of these independently represents a divalent organic group. 51 and L 53 As a divalent organic group represented by the above formula (Ia-2), L 21 and L 22 This is synonymous with the same thing, and the preferred embodiment is also the same. L 52 L represents a trivalent organic group.52 As a trivalent organic group represented by the above formula (Ia-4), L 41 This is synonymous with the same thing, and the preferred embodiment is also the same.

[0360] Furthermore, in the above equation (Ia-5), M 51a + M 51b + M 51c + M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, which is obtained by substituting A, 52a Acid dissociation constants a2-1 and A, which originate from the acidic site represented by H. 52b The acid dissociation constant a2-2, which originates from the acidic site represented by H, is A 51a Acid dissociation constants a1-1 and A derived from H. 51b Acid dissociation constants a1-2 and A originate from the acidic site represented by H. 51c This is greater than the acid dissociation constant a1-3 derived from the acidic site represented by H. Note that acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 mentioned above, and acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 mentioned above. Note A 51a - , A 51b - , and A 51c - They may be the same or different from each other. Also, 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 + M51c + 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. The anion portion in formula (Ia-5) has a substructure represented by any of the above general formulas (1) to (3).

[0361] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids.

[0362] 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.

[0363] 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.

[0364] 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.

[0365] 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.

[0366] [ka]

[0367] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0368] Compound (II) has a substructure in its anionic portion that is represented by any of the above general formulas (1) to (3). Compound (II) is not particularly limited, but examples include compounds represented by the following formulas (IIa-1) and (IIa-2).

[0369] [ka]

[0370] In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) described above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 61a + and M 61b + 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-1), L 61 and L 62 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0371] In formula (IIa-1), R 2X R represents a monovalent organic group. 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).

[0372] 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. The above formula (IIa-1) has a substructure represented by any of the above general formulas (1) to (3) in the anion portion.

[0373] 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.

[0374] 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. The above formula (IIa-2) has a substructure represented by any of the above general formulas (1) to (3) in the anion portion.

[0375] Examples of sites other than cations that the photoacid generator (B) may have are given below.

[0376] [ka]

[0377] [ka]

[0378] The following are specific examples of photoacid generators, but are not limited to these. In the compounds listed below, the anion and cation can be exchanged as desired.

[0379] [ka]

[0380] [ka]

[0381] [ka]

[0382] The photoacid generator (B) preferably has a sulfonamide structure, as this provides superior effects for the present invention. In a preferred embodiment, the photoacid generator (B) preferably has a sulfonamide structure in its anionic portion. Examples of sulfonamide structures include the following structures.

[0383] [ka]

[0384] R 31 represents a hydrogen atom or an organic group. * indicates the connection position. The organic group is not particularly limited, but examples include organic groups having 1 to 20 carbon atoms.

[0385] The content of the photoacid generator (B) in the composition of the present invention is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of the composition. Furthermore, the above content is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 50.0% by mass or less. The photoacid generator (B) may be used alone or in combination of two or more types.

[0386] The composition of the present invention may contain, in addition to the photoacid generator (B), a compound (C) (also referred to as compound (C) or photoacid generator (C)) that generates acid upon irradiation with an active light or radiation different from that of the photoacid generator (B), to the extent that the effects of the present invention are not impaired. Compound (C) is not particularly limited as long as it is a different compound from the photoacid generator (B), but for example, a compound that does not have a substructure represented by any of the above general formulas (1) to (3) in the photoacid generator (B) can be mentioned.

[0387] Examples of non-cationic sites that compounds (I) to (II) above may have if they do not have a substructure represented by any of the general formulas (1) to (3) above are given below. Furthermore, the cation in the above compound is M in the above photoacid generator (B). + The organic cations listed above can be used.

[0388] [ka]

[0389] [ka]

[0390] Furthermore, specific examples of photoacid generators (C) include the following compounds. In the compounds below, the anion and cation can be arbitrarily exchanged.

[0391] [ka]

[0392] [ka]

[0393] In the composition of the present invention, the content of the photoacid generator (C) is preferably 0.1 to 20.0% by mass, more preferably 0.5 to 17.5% by mass, and even more preferably 1.0 to 15.0% by mass, based on the total solid content.

[0394] <Acid diffusion control agent> The composition of the present invention may contain an acid diffusion control agent. The acid diffusion control agent traps the acid generated from photoacid generators during exposure and acts as a quencher to suppress the reaction of acid-degradable resins in unexposed areas due to excess generated acid. The type of acid diffusion control agent is not particularly limited and includes, for example, basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation. Furthermore, for example, specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

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

[0137] to

[0155] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824; and specific examples of basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation include those described in paragraph

[0164] of International Publication No. 2020 / 066824. Furthermore, specific examples of onium salt compounds (CDs) that are relatively weak acids with respect to photoacid generators include those described in paragraphs

[0305] to

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

[0395] In addition to the above, known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[0396] If the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (total if there are multiple types) is preferably 0.1 to 15.0% by mass, and more preferably 0.5 to 15.0% by mass, based on the total solid content of the composition. In the composition of the present invention, one acid diffusion control agent may be used alone, or two or more may be used in combination.

[0397] <Hydrophobic resin> The composition of the present invention may further contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0398] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. Furthermore, the hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

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

[0399] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition.

[0400] <Surfactants> The composition of the present invention may contain a surfactant. The inclusion of a surfactant results in superior adhesion and the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0401] These surfactants may be used individually or in combination of two or more types.

[0402] If the composition of the present invention contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition.

[0403] <Solvent> The composition of the present invention may contain a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0404] The inventors have found that when such solvents are used in combination with the resins described above, the coatability of the composition is improved, and patterns with fewer development defects can be formed. Although the reason for this is not entirely clear, the inventors believe that these solvents have a good balance of solubility, boiling point, and viscosity with the resins described above, which suppresses unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

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

[0405] As described above, the solvent may further contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0406] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the applicability of the composition of the present invention. Furthermore, "solid content" refers to all components other than the solvent, and as mentioned above, it refers to the components that form a photosensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the mass of the components other than the solvent, relative to the total mass of the composition of the present invention. "Total solids" refers to the total mass of the components of the composition of the present invention, excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent, as described above, and may be solid or liquid at 25°C, for example.

[0407] <Other additives> The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0408] The composition of the present invention may further contain a dissolution-inhibiting compound. Here, a "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer.

[0409] The composition of the present invention is suitably used as a composition for EUV light. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0410] When the A value calculated by the following formula (1) is high, the absorption efficiency of EUV light and electron beams of the resist film formed from the composition of the present invention becomes high, which is effective in reducing photon shot noise. The A value represents the absorption efficiency of EUV light and electron beams by mass percentage of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value of 0.120 or higher is preferred. There is no particular upper limit, but if the A value is too high, the EUV light and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result it becomes difficult to obtain a good pattern shape. Therefore, 0.240 or lower is preferred, and 0.220 or lower is more preferred.

[0411] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from the total solids in the photosensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition. For example, if the resist composition contains an acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-degradable resin, the photoacid generator, and the acid diffusion control agent constitute the solid content. In other words, the total atoms of the total solid content refer to the sum of the total atoms derived from the resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the total hydrogen atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent to the sum of the total atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent.

[0412] The A value can be calculated by determining the atomic ratio of the constituent components if the structure and content of the total solid components in the resist composition are known. Even if the constituent components are unknown, the atomic ratio can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.

[0413] Furthermore, the present invention relates to (A) a resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: The above resin (A) is a resin having an acidic group, an alcoholic hydroxyl group, or an acid-degradable group. The present invention also relates to a photosensitive or radiation-sensitive resin composition in which compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) in the anionic portion.

[0414] [ka]

[0415] In general formula (1), R1 to R3 each independently represent a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents a bond position. In general formula (2), R4 to R6 each independently represent a hydrogen atom or a substituent. * indicates a bond position. In general formula (3), R7 represents a hydrogen atom or substituent. * represents a bond position.

[0416] In the above resin (A), the acidic group, alcoholic hydroxyl group, or acid-degradable group are as described above. The resin (A) mentioned above can be the resin (A) described above. Each group in the substructure represented by any of the above general formulas (1) to (3) is as described above. The compound (B) mentioned above is an example of the compound (B) described above.

[0417] The above composition comprises (A) a resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: This is one embodiment for achieving the above-mentioned photosensitive or radiation-sensitive resin composition, wherein the resin (A) and the acid generated from the compound (B) form a bond through the action of active light, radiation, or the acid.

[0418] [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.

[0419] [Actinic ray-sensitive or radiation-sensitive film] The present invention also relates to photosensitive or radiation-sensitive films (typically "resist films") formed by the photosensitive or radiation-sensitive composition of the present invention. Such films are formed, for example, by coating the composition of the present invention onto a support such as a substrate. The thickness of the film is preferably 0.01 to 0.15 μm. The coating is applied to the substrate by various methods, including spin coating, roll coating, flow coating, dip coating, spray coating, and doctor coating. Spin coating is preferred, with a preferred rotation speed of 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. The materials constituting the substrate to be processed and its outermost layer can, for example, be silicon wafers in the case of semiconductor wafers. Examples of materials for the outermost layer include Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, and organic anti-reflective coatings.

[0420] [Pattern formation method] The procedure for a pattern-forming method using the above-mentioned photosensitive or radiation-sensitive resin composition is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive or radiation-sensitive resin composition. Step 2: Exposure of a photosensitive or radiation-sensitive film. Step 3: A process of developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern. The following details the steps for each of the above processes.

[0421] <Step 1: Actinic ray- or radiation-sensitive film formation step> Step 1 is a step of forming an activated light-sensitive or radiation-sensitive film on a substrate using an activated light-sensitive or radiation-sensitive resin composition.

[0422] One method for forming a photosensitive or radiation-sensitive film on a substrate using a photosensitive light or a radiation-sensitive resin composition is to apply the photosensitive light or radiation-sensitive resin composition onto the substrate. Furthermore, it is preferable to filter the reactive light or radiation-sensitive resin composition before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0423] The light-sensitive or radiation-sensitive resin composition can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the reactive light or radiation-sensitive resin composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic film, organic film, anti-reflective film) may be formed beneath the resist film.

[0424] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0425] The thickness of the light-sensitive or radiation-sensitive film is not particularly limited, but 10 to 120 nm is preferred because it allows for the formation of more precise fine patterns. In particular, when using EUV exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0426] Furthermore, a topcoat may be formed on the upper layer of the light-sensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition can be applied uniformly to the top layer of the light-sensitive or radiation-sensitive film without being mixed with the light-sensitive or radiation-sensitive film. The topcoat is not particularly limited, and any conventionally known topcoat can be formed by conventionally known methods. For example, a topcoat can be formed based on the description in paragraphs

[0072] to

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

[0427] <Step 2: Exposure Process> Step 2 is the step of exposing the reactive light or radiation-sensitive film. One method of exposure is to irradiate the formed reactive light or radiation-sensitive film with reactive light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with wavelengths of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with wavelengths of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.

[0428] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also called post-exposure baking.

[0429] <Process 3: Development process> Step 3 is the process of developing the exposed light-sensitive or radiation-sensitive film using a developer solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0430] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and leaving it still for a certain period of time for development (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0431] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

[0432] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0433] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, based on the total amount of the developer.

[0434] <Other processes> The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0435] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may also be added to the rinsing solution.

[0436] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0437] The rinsing process is not particularly limited and can be performed by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or spraying rinsing solution onto the substrate surface (spray method). Furthermore, the pattern formation method of the present invention may include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of softening the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0438] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask. Dry etching is preferably performed using oxygen plasma etching.

[0439] The compositions of the present invention and the various materials used in the pattern forming method of the present invention (e.g., solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0440] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

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

[0441] Furthermore, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0442] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred.

[0443] In organic processing solutions such as rinsing solutions, a conductive compound may be added to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. For chemical piping, various types of piping can be used, such as SUS (stainless steel), or piping coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.). Similarly, for filters and O-rings, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) can be used.

[0444] <Method of manufacturing electronic devices> Furthermore, the present invention relates to a method for manufacturing an electronic device, including the pattern formation method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present invention include those mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0445] 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.

[0446] [Various components of photosensitive or radiation-sensitive resin compositions] [Resin (A)] The resins A (resins A-1 to A-25) shown in Table 3 are listed below. Resins A-1 to A-25 were synthesized according to the synthesis method for resin A-1 described later (synthesis Example 1). Table 1 shows the composition ratio (mol% ratio), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit shown below. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resins A-1 to A-25 were measured by GPC (solvent: tetrahydrofuran (THF)). The composition ratio (mol% ratio) of the resins was also determined. 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0447] [Table 1]

[0448] The structures of monomers MA-1 to MA-20 and monomers MB-1 to MB-31, which correspond to each repeating unit constituting resins A-1 to A-25 shown in Table 1, are shown below.

[0449] [ka]

[0450] [ka]

[0451] <Synthesis Example 1: Synthesis of Resin A-1> 61 parts by mass of cyclohexanone was heated to 85°C under a nitrogen stream. To this solution, a mixed solution consisting of 21 parts by mass of monomer represented by structural formula MB-10, 16 parts by mass of monomer represented by structural formula MA-16, 60 parts by mass of cyclohexanone, and 3 parts by mass of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours while stirring to obtain a reaction solution. After the dropwise addition was complete, the reaction solution was stirred at 85°C for a further 2 hours. After the reaction solution was allowed to cool, it was reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the resulting solid was vacuum dried to obtain resin A-1. The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-1, determined from the GPC (carrier: tetrahydrofuran (THF)), was 8500, and the degree of dispersion (Mw / Mn) was 1.6. 13 The composition ratio of repeating units derived from MB-10 and MA-16, as measured by 13C-NMR (nuclear magnetic resonance), was 50 / 50 in molar ratio.

[0452] Other resins were synthesized in the same manner.

[0453] [Photoacid generator] <Photoacid Generator (B)> The structures of the photoacid generator (B) (compounds B-1 to B-12), as shown in Table 3, are shown below. Compounds B-1 to B-12 were synthesized according to the synthesis method for compound B-1 described later (Synthesis Example 2). Although compound B-9 is not a photoacid generator (B), it is listed under photoacid generator (B) in Table 3 for convenience.

[0454] [ka]

[0455] [ka]

[0456] <Synthesis Example 2: Synthesis of Compound B-1> A mixture was obtained by mixing methylene chloride (100 mL) and water (100 mL). B-1-a (10.0 g) and B-1-b (8.9 g) were added to the mixture. After stirring the mixture for 1 hour, the aqueous phase was removed. The remaining organic phase was washed with 1% potassium carbonate aqueous solution (100 mL), 0.01 N hydrochloric acid (100 mL), and water (100 mL). B-1 (15.5 g) was obtained by distilling off the solvent from the organic phase (yield 99%).

[0457] [ka]

[0458] Based on the above synthesis method, other photoacid generators were synthesized.

[0459] <Photoacid Generator (C)> The structures of the photoacid generator (C) (compounds C-1 to C-11), as shown in Table 3, are shown below.

[0460] [ka]

[0461] [ka]

[0462] [Acid diffusion control agent] The structures of the acid diffusion control agents (compounds D-1 to D-12) shown in Table 3 are shown below.

[0463] [ka]

[0464] [Hydrophobic resin] The hydrophobic resins (resins E-1 to E-12) shown in Table 3 are listed below. Resins E-1 to E-12 were synthesized according to the synthesis method for resin A-1 described above (synthesis Example 1). Table 2 shows the composition ratio (mol% ratio), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit shown below. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resins E-1 to E-12 were measured by GPC (solvent carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The composition ratio (mol% ratio) of the resins was also determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0465] [Table 2]

[0466] The structures of monomers ME-1 to ME-21, which correspond to each repeating unit constituting resins E-1 to E-12 shown in Table 2, are shown below.

[0467] [ka]

[0468] [Surfactants] The surfactants shown in Table 3 are listed below. H-1: Megafuck F176 (manufactured by DIC Corporation, fluorine-based surfactant) H-2: Megafuck R08 (manufactured by DIC Corporation, containing fluorine and silicone-based surfactants) H-3: PF656 (manufactured by OMNOVA, a fluorine-based surfactant)

[0469] 〔solvent〕 The solvents shown in Table 3 are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene Carbonate F-10: Diacetone alcohol

[0470] (Examples 1-29 and Comparative Example 1) <Preparation of resist composition> (EB exposure) (Examples 1-20, 23-29, Comparative Example 1) The components shown in Table 3 were dissolved in the solvents shown in Table 3 to prepare a solution with a solid content of 2.3%, which was then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare a resist composition. Note that "solid content" refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. In the table, the "Quantity" column indicates the content (mass %) of each component relative to the total solids in the resist composition. The table also shows the amount (parts by mass) of the solvent used.

[0471] <Pattern formation method (1): EB exposure, alkaline development (positive)> (Examples 1-19, 23-29, Comparative Example 1) The above resist composition was applied to a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 40 nm. Here, 1 inch is equal to 0.0254 m. Furthermore, similar results can be obtained by changing the Si wafer to a chromium substrate.

[0472] The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam lithography system (HL750, Hitachi, Ltd., accelerating voltage 50KeV). During this process, the pattern was drawn to form a 1:1 line-and-space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm.

[0473] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure dose exhibiting the above sensitivity was defined as the L / S resolution (nm).

[0474] <Pattern formation method (2): EB exposure, organic solvent development (negative)> (Example 20) The above resist composition was applied to a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater, and dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 40 nm.

[0475] The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam lithography system (Hitachi HL750, accelerating voltage 50KeV). During this process, the pattern was drawn to form a 1:1 line-and-space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with n-butyl acetate for 30 seconds, spin-dried, and heated at 95°C for 60 seconds to obtain a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm.

[0476] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure dose exhibiting the above sensitivity was defined as the L / S resolution (nm).

[0477] <Preparation of Resist Composition> (EUV Exposure) (Examples 21-22) The components shown in Table 3 were dissolved in the solvents shown in Table 3 to prepare a solution with a solid content of 2.3%, which was then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare a resist composition. Note that "solid content" refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. In the table, the "Quantity" column indicates the content (mass %) of each component relative to the total solids in the resist composition. The table also shows the amount (parts by mass) of the solvent used.

[0478] <Pattern formation method (3): EUV exposure, alkaline development (positive)> (Example 21) A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base layer. On top of that, the resist composition shown in the table was applied and baked at 100°C for 60 seconds to form a 40 nm thick resist film. A silicon wafer with the obtained resist film was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the rectilation mask. The resist film after exposure was baked at 90°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. Afterward, it was spin-dried to obtain a positive-type pattern.

[0479] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 20 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure dose exhibiting the above sensitivity was defined as the L / S resolution (nm).

[0480] <Pattern formation method (4): EUV exposure, organic solvent development (negative)> (Example 22) A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base layer. On top of that, the resist composition shown in the table was applied and baked at 100°C for 60 seconds to form a 40 nm thick resist film. A silicon wafer with the obtained resist film was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the rectilation mask. After exposure, the resist film was baked at 90°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative-type pattern.

[0481] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (Hitachi S-4300). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line-and-space resist pattern with a line width of 20 nm was defined as the sensitivity (Eop). The limiting resolution (the smallest line width at which lines and spaces (line:space = 1:1) are separated and resolved) at the exposure dose exhibiting the above sensitivity was defined as the L / S resolution (nm).

[0482] The evaluation results obtained are shown in Table 4.

[0483] [Table 3]

[0484] [Table 4]

[0485] As shown in Table 4 above, the resist composition of the present invention was confirmed to exhibit excellent resolution when forming extremely fine patterns of 20 nm or less by alkaline development or organic solvent development. On the other hand, the resist composition of the comparative example showed insufficient performance in this regard. [Industrial applicability]

[0486] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that exhibits extremely excellent resolution when forming extremely fine patterns (for example, line-and-space patterns with a line width or space width of 20 nm or less, or hole patterns with a pore diameter of 20 nm or less). Furthermore, according to the present invention, it is possible to provide a photosensitive or radiation-sensitive film using the above-mentioned photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[0487] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-47795 filed on March 22, 2021, and Japanese Patent Application No. 2021-126332 filed on July 30, 2021, the contents of which are incorporated herein by reference.

Claims

1. (A) A resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: A photosensitive or radiation-sensitive resin composition in which the resin (A) and the acid generated from the compound (B) form a bond upon the action of active light, radiation, or the acid.

2. The resin (A) is a resin having a reactive site (1), and the compound (B) is an ionic compound having a reactive site (2) in the anionic part. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein a reactive species generated from one of the reactive sites (1) and (2) reacts with the other of the reactive sites (1) and (2) upon the action of active light or radiation or an acid to form the bond.

3. The photosensitive or radiation-sensitive resin composition according to claim 2, wherein the compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) as the reactive site (2) in the anionic portion. 【Chemistry 1】 In general formula (1), R １ ~R ３ Each of these independently represents a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents the bond position. In general formula (2), R ４ ~R ６ Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (3), R ７ * represents a hydrogen atom or substituent. * represents a bond position.

4. The photosensitive or radiation-sensitive resin composition according to claim 3, wherein the substructure is a substructure represented by the general formula (1) or the general formula (3).

5. The photosensitive or radiation-sensitive resin composition according to claim 3, wherein the aforementioned substructure is a substructure selected from the following. 【Chemistry 2】 * indicates the joining position.

6. The photosensitive or radiation-sensitive resin composition according to claim 5, wherein the aforementioned substructure is a substructure selected from the following. 【Transformation 3】 * indicates the joining position.

7. (A) A resin that decomposes and becomes more polar due to the action of an acid, and (B) a compound that generates acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition comprising: The resin (A) is a resin having an acidic group, an alcoholic hydroxyl group, or an acid-degradable group. A photosensitive or radiation-sensitive resin composition in which the compound (B) is an ionic compound having a substructure represented by any of the following general formulas (1) to (3) in the anionic portion. 【Chemistry 4】 In general formula (1), R １ ~R ３ Each of these independently represents a hydrogen atom or a substituent. L represents a single bond or a divalent linking group. * represents the bond position. In the general formula (2), R ４ to R ６ each independently represents a hydrogen atom or a substituent. * represents the bonding position. In general formula (3), R ７ * represents a hydrogen atom or substituent. * represents a bond position.

8. The photosensitive or radiation-sensitive resin composition according to claim 7, wherein the substructure is a substructure represented by the general formula (1) or the general formula (3).

9. The photosensitive or radiation-sensitive resin composition according to claim 7, wherein the aforementioned substructure is a substructure selected from the following. 【Transformation 5】 * indicates the joining position.

10. The photosensitive or radiation-sensitive resin composition according to claim 9, wherein the aforementioned substructure is a substructure selected from the following. 【Transformation 6】 * indicates the joining position.

11. The photosensitive or radiation-sensitive resin composition according to any one of claims 2 to 10, wherein the compound (B) does not have a substructure represented by any of the following general formulas (11) to (14) in the anionic portion. 【Transformation 7】 In general formula (11), R １１ ~R １３ Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (12), R １４ ~R １８ Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (13), R １９ ~R ２３ Each of these independently represents a hydrogen atom or a substituent. * represents a bond position. In general formula (14), R ２４ ~R ２６ Each of these independently represents a hydrogen atom or a substituent. * represents a bond position.

12. The photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, wherein the resin (A) has dissociable hydrogen atoms.

13. The photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 12, wherein the resin (A) has phenolic hydroxyl groups.

14. The photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 13, wherein the acid generated from the compound (B) contains an aromatic ring.

15. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 14.

16. A step of forming a photosensitive or radiation-sensitive film on a substrate using the photosensitive or radiation-sensitive resin composition described in any one of claims 1 to 14, A step of exposing the aforementioned photosensitive or radiation-sensitive film, A pattern forming method comprising the steps of developing the exposed photosensitive or radiation-sensitive film using a developing solution to form a pattern.

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

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