Resist composition, resist pattern formation method, compound, and acid generator

Abstract

To provide a resist composition which can achieve higher sensitivity when forming a resist pattern and enhance lithographic characteristics such as in-plane uniformity of pattern dimensions and fine resolution.SOLUTION: The present invention employs the resist composition containing: a base component whose solubility in a developer changes by the action of an acid; and a compound represented by general formula (b0). In the formula (b0), Rb represents a base-decomposable group; L03 represents a divalent linking group; Rl0 represents a cyclic organic group; L02 represents a divalent linking group; Rm1 represents a substituent; L01 represents a divalent linking group or a single bond; Vb0 represents an alkylene group, a fluorinated alkylene group or a single bond; R0 represents a fluorinated alkyl group, a fluorine atom or a hydrogen atom; nb1 represents an integer of 1-4; nb2 represents an integer of 1-4; nb3 represents an integer of 0-3; 2≤nb1+nb2+nb3≤5; Mm+ represents an m-valent organic cation; and m represents an integer of 1 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a resist pattern formation method, a compound, and an acid generator. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display elements. Generally, miniaturization is achieved by using shorter wavelengths (higher energy) exposure light sources.

[0003] Resist materials are required to possess lithography characteristics such as sensitivity to these exposure light sources and resolution that can reproduce patterns of fine dimensions. Conventionally, chemically amplified resist compositions have been used as resist materials that satisfy these requirements. These compositions contain a base component whose solubility in a developer changes due to the action of an acid, and an acid generator component that generates acid upon exposure.

[0004] In the formation of resist patterns, the behavior of acids generated from acid-generating agent components upon exposure is considered a significant factor influencing lithography characteristics. A wide variety of acid generators have been proposed for use in chemically amplified resist compositions. For example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators are known. Generally, onium salt-based acid generators use alkyl sulfonate ions or fluorinated alkyl sulfonate ions, in which some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, as the anionic portion. The cation portion of onium salt-based acid generators mainly uses those containing onium ions, such as triphenylsulfonium. For example, Patent Document 1 discloses a resist composition containing a salt of an anion having a polycyclic structure including a bicyclooctane skeleton and an organic cation as an acid generator. This resist composition is said to provide high sensitivity to exposure light sources and improved lithography characteristics. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-92159 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Further advancements in lithography technology and the expansion of its application fields are leading to rapid miniaturization of patterns. Consequently, when manufacturing semiconductor devices and other components, there is a demand for technologies that can form fine patterns with good shape. For example, in EUV (extreme ultraviolet) or EB (electron beam) lithography, the goal is to form fine patterns of several tens of nanometers. As pattern dimensions become smaller, it is necessary to improve lithographic characteristics such as sensitivity and resolution without any trade-offs. However, with the conventional resist compositions described above, when attempting to increase sensitivity, problems such as in-plane uniformity of pattern dimensions (CDU) and fine resolution may arise.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a resist composition that can be made highly sensitive when forming a resist pattern and can improve lithography characteristics such as CDU and fine resolution, a method for forming a resist pattern using the resist composition, and a compound useful as an acid generator component used in the resist composition. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a resist composition that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid, the resist composition being characterized by containing a base material component (A) whose solubility in a developer changes by the action of the acid and a compound (B0) represented by the following general formula (b0).

[0009] [Chemical formula] [In the formula, R b is a base-decomposable group. L 03 is a divalent linking group. Rl 0 is a cyclic organic group that may have a substituent. L 02 is a divalent linking group. I is an iodine atom. R m1 is a substituent other than an iodine atom. L 01 is a divalent linking group or a single bond. Vb 0 is an alkylene group, a fluorinated alkylene group or a single bond. However, L 01 and Vb 0 do not simultaneously become a single bond. R 0 is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom. nb1 is an integer of 1 to 4, nb2 is an integer of 1 to 4, and nb3 is an integer of 0 to 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. M m+ represents an m-valent organic cation. m is an integer of 1 or more.]

[0010] A second aspect of the present invention is a resist pattern forming method characterized by including a step of forming a resist film using the resist composition according to the first aspect on a support, a step of exposing the resist film, and a step of developing the resist film after the exposure to form a resist pattern.

[0011] A third aspect of the present invention is a compound characterized by being represented by the following general formula (b0).

[0012] [ka] [In the formula, R b L is a base-degradable group. 03 Rl is a divalent linking group. 0 L is a cyclic organic group which may have substituents. 02 is a divalent linking group. I is an iodine atom. R m1 L is a substituent other than the iodine atom. 01 This is a divalent linking group or a single bond. Vb 0 is an alkylene group, a fluorinated alkylene group, or a single bond. However, L 01 and Vb 0 It is impossible for them to be single bonds at the same time. 0 nb1 is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. nb1 is an integer from 1 to 4, nb2 is an integer from 1 to 4, and nb3 is an integer from 0 to 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. m+ This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

[0013] A fourth aspect of the present invention is an acid generator characterized by containing a compound according to the third aspect. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a resist composition that can be made highly sensitive when forming a resist pattern and can improve lithography characteristics such as CDU and fine resolution, a method for forming a resist pattern using the resist composition, and a compound useful as an acid generator component used in the resist composition. [Modes for carrying out the invention]

[0015] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that a group "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0016] An "acid-degradable group" is a group that has acid-degradability, meaning that at least some of the bonds in its structure can be cleaved by the action of an acid. Examples of acid-degradable groups whose polarity increases upon the action of an acid include groups that decompose upon the action of an acid to produce polar groups. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfo groups (-SO3H). More specifically, examples of acid-degradable groups include groups in which the aforementioned polar group is protected by an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0017] The term "acid-dissociable group" refers to both (i) a group that has acid-dissociability, in which the bond between the acid-dissociable group and an adjacent atom can be cleaved by the action of an acid, and (ii) a group in which, after some of the bonds are cleaved by the action of an acid, a decarboxylation reaction occurs, further causing the bond between the acid-dissociable group and an adjacent atom to be cleaved. The acid-dissociable group constituting the acid-degradable group must be less polar than the polar group generated by its dissociation. This means that when the acid-dissociable group dissociates due to the action of acid, a polar group with higher polarity is generated, increasing the polarity. As a result, the overall polarity of component (A1) increases. This increase in polarity relatively changes the solubility in the developer; solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.

[0018] "Base material components" are organic compounds that have film-forming ability. Organic compounds used as base material components are broadly classified into nonpolymers and polymers. Nonpolymers typically have a molecular weight of 500 or more and less than 4000 (hereinafter referred to as "low molecular weight compounds"). Hereinafter, when "resins," "high molecular weight compounds," or "polymers" are used, polymers with a molecular weight of 1000 or more are referred to. For polymers, the weight-average molecular weight in terms of polystyrene obtained by GPC (gel permeation chromatography) shall be used as the molecular weight.

[0019] "Induced structural units" refer to structural units formed by the cleavage of multiple bonds between carbon atoms, such as ethylenic double bonds. "Acrylic acid ester" may have a substituent that replaces the hydrogen atom bonded to the α-carbon atom. αx ) is an atom or group other than a hydrogen atom. Also, substituents (R αx Itaconic acid diesters in which ) are substituted with substituents containing an ester bond, or substituents (R αx This also includes α-hydroxyacrylic esters in which the α group is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group thereof. Unless otherwise specified, the α-carbon atom of the acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereafter, acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom is replaced by a substituent are sometimes called α-substituted acrylic acid esters.

[0020] The term "derivative" refers to a compound in which the α-position hydrogen atom of the target compound is substituted with another substituent such as an alkyl group or alkyl halide, as well as derivatives thereof. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound (which may have the α-position hydrogen atom substituted with a substituent) is substituted with an organic group; and those in which a substituent other than a hydroxyl group is bonded to the target compound (which may have the α-position hydrogen atom substituted with a substituent). Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. As substituents that substitute the hydrogen atom at the α-position of hydroxystyrene, R αx Similar examples include the above.

[0021] In this specification and in the claims, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and enantioisomers or diastereomers may exist. In such cases, a single chemical formula will represent all of these isomers. These isomers may be used individually or as a mixture.

[0022] (Resist composition) The resist composition of this embodiment generates acid upon exposure, and its solubility in the developer changes due to the action of the acid. The resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer solution changes due to the action of an acid, and an acid-generating agent component (B) (hereinafter also referred to as "component (B)") that generates acid upon exposure. Component (B) includes a compound (B0) represented by general formula (b0).

[0023] When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, acid is generated from component (B) in the exposed areas of the resist film. The solubility of component (A) in the developer changes due to the action of this acid, while the solubility of component (A) in the developer does not change in the unexposed areas of the resist film. As a result, a difference in solubility in the developer occurs between the exposed and unexposed areas of the resist film. Therefore, when the resist film is developed, if the resist composition is positive type, the exposed areas of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is negative type, the unexposed areas of the resist film are dissolved and removed to form a negative type resist pattern.

[0024] The resist composition of this embodiment may be a positive-type resist composition or a negative-type resist composition. Furthermore, the resist composition of this embodiment may be for an alkaline development process that uses an alkaline developer for the development process during resist pattern formation, or for a solvent development process that uses a developer containing an organic solvent (organic developer) for the development process.

[0025] <Base material component (A)> In the resist composition of this embodiment, component (A) includes a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in the developer solution changes due to the action of an acid. By using component (A1), the polarity of the substrate component changes before and after exposure, so good development contrast can be obtained not only in the alkaline development process but also in the solvent development process. (A) Component (A1) may be used in combination with other high-molecular-weight compounds and / or low-molecular-weight compounds.

[0026] In the resist composition of this embodiment, component (A) may be used alone or in combination of two or more types.

[0027] (A1) About the ingredients Component (A1) is a resin component whose solubility in the developer changes due to the action of acid. (A1) Component is preferably one that has a constituent unit (a1) containing an acid-degradable group whose polarity increases due to the action of an acid. Component (A1) may have other constituent units in addition to the constituent unit (a1) as needed.

[0028] ≪Component Unit (a1)≫ The constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid.

[0029] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Specifically, the following types of acid-dissociable groups have been proposed for base resins used in chemically amplified resist compositions: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," "tertiary alkyloxycarbonyl acid-dissociable groups," and "secondary alkyloxycarbonyl acid-dissociable groups."

[0030] Acetal type acid dissociable group: Examples of acid-dissociable groups that protect a carboxyl group or a hydroxyl group among the aforementioned polar groups include the acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0031] [ka] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. 3 Ra' is a hydrocarbon group. 3 Ra' 1 , Ra' 2 It may combine with any of the following to form a ring.

[0032] In formula (a1-r-1), Ra' 1 and Ra' 2 Preferably, at least one of them is a hydrogen atom, and more preferably, both are hydrogen atoms. Ra' 1 Or Ra' 2 If the alkyl group is an alkyl group, the alkyl group can be the same as those listed in the description of the α-substituted acrylic acid ester above as substituents that may be bonded to the carbon atom at the α position, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc., with methyl group or ethyl group being more preferred, and methyl group being particularly preferred.

[0033] In formula (a1-r-1), Ra' 3 Examples of hydrocarbon groups include linear or branched alkyl groups, or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0034] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0035] Ra' 3 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a polycycloalkane from which one hydrogen atom has been removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically including adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0036] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Ra' 3Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0037] Ra' 3 The cyclic hydrocarbon group in may have substituents. Examples of substituents include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN or -R P2 -COOH (These substituents are collectively referred to as "Ra") x5 It is also called "[...]." Examples include [...]. Here, R P1 This is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 R is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, R P1 and R P2Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the substituents individually, or it may have one or more of each of the substituents. Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0038] Ra' 3 However, Ra' 1 , Ra' 2 When the cyclic group is bonded to any of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

[0039] Tertiary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-2). Furthermore, among the acid-dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may, for convenience, be referred to below as "tertiary alkyl ester type acid-dissociable groups."

[0040] [ka] [In the formula, Ra' 4 ~Ra' 6 Each of these is a hydrocarbon group, Ra' 5 , Ra' 6 They may be joined to each other to form a ring.

[0041] Ra' 4 Examples of hydrocarbon groups include linear or branched alkyl groups, linear or cyclic alkenyl groups, or cyclic hydrocarbon groups. Ra' 4 In the above, linear or branched alkyl groups, cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) are defined as Ra' 3 Similar examples include the above. Ra' 4 The linear or cyclic alkenyl group in this is preferably an alkenyl group having 2 to 10 carbon atoms. Ra' 5 , Ra' 6 The hydrocarbon group is the aforementioned Ra' 3 Similar examples include the above.

[0042] Ra' 5 and Ra' 6 When these groups bond to each other to form a ring, the following groups are preferred: the group represented by the general formula (a1-r2-1), the group represented by the general formula (a1-r2-2), and the group represented by the general formula (a1-r2-3). Meanwhile, Ra' 4 ~Ra' 6 When these are independent hydrocarbon groups that are not bonded to each other, the groups represented by the following general formula (a1-r2-4) are preferred.

[0043] [ka] [In formula (a1-r2-1), Ra' 10 This represents a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups. 11 Ra' 10 This indicates a group that forms an aliphatic cyclic group with a bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. 101 ~Ra 103 Each of these is independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in these linear saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. 101 ~Ra 103 Two or more of these may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra 104 is an aromatic hydrocarbon group which may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. 14 is a hydrocarbon group that may have substituents. * indicates a bond (the same applies hereafter).

[0044] In the above equation (a1-r2-1), Ra' 10 This is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups.

[0045] Ra' 10In the case of a linear alkyl group, the number of carbon atoms is 1 to 12, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra’ 10 In the case of a branched alkyl group, examples of the branched alkyl group include those similar to the above Ra’ 3 and the like.

[0046] Ra’ 10 The alkyl group in may be partially substituted with a halogen atom or a heteroatom-containing group. For example, a part of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Further, a part of the carbon atoms (such as a methylene group) constituting the alkyl group may be substituted with a heteroatom-containing group. Examples of the heteroatom mentioned here include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O- and the like.

[0047] In formula (a1-r2-1), Ra’ 11 (The aliphatic cyclic group formed together with the carbon atom to which Ra’ 10 is attached) is preferably a group exemplified as the monocyclic group or polycyclic group of Ra’ 3 in formula (a1-r-1), which is an aliphatic hydrocarbon group (alicyclic hydrocarbon group). Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable. <​​​​​​​Examples include substituents similar to those that may be present on the cyclic hydrocarbon group in the above. In formula (a1-r2-2), Ra 101 ~Ra 103 Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Ra 101 ~Ra 103 Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Ra 101 ~Ra 103 Of these, from the viewpoint of ease of synthesis, hydrogen atoms and monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred, and among these, hydrogen atoms, methyl groups, and ethyl groups are more preferred, with hydrogen atoms being particularly preferred.

[0049] The above Ra 101 ~Ra 103 Examples of substituents on a chain-like saturated hydrocarbon group or an aliphatic cyclic saturated hydrocarbon group represented by the above-mentioned Ra x5 Similar bases can be cited.

[0050] Ra 101 ~Ra 103Groups containing a carbon-carbon double bond formed by two or more of these groups bonding to each other to form a cyclic structure include, for example, cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylideneethenyl group, and cyclohexyllideneethenyl group. Among these, cyclopentenyl group, cyclohexenyl group, and cyclopentylideneethenyl group are preferred from the viewpoint of ease of synthesis.

[0051] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). 3 The aliphatic hydrocarbon groups listed above, which are monocyclic or polycyclic groups, are preferred. In formula (a1-r2-3), Ra 104 Aromatic hydrocarbon groups in this context include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring with 5 to 30 carbon atoms. Among them, Ra 104 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from benzene or naphthalene with one or more hydrogen atoms removed; and most preferably a group from benzene with one or more hydrogen atoms removed.

[0052] Ra in equation (a1-r2-3) 104 Examples of substituents that may be present include methyl groups, ethyl groups, propyl groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and alkyloxycarbonyl groups.

[0053] In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. 12 and Ra' 13In this context, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above-mentioned Ra 101 ~Ra 103 Examples include monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 Among these, alkyl groups having 1 to 5 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. The above Ra' 12 and Ra' 13 When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Ra x5 Similar bases can be cited.

[0054] In formula (a1-r2-4), Ra' 14 Ra' is a hydrocarbon group that may have substituents. 14 Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0055] Ra' 14 The linear alkyl group in this compound preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0056] Ra' 14 The branched alkyl group in this compound preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0057] Ra'14 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a polycycloalkane from which one hydrogen atom has been removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically including adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0058] Ra' 14 As for aromatic hydrocarbon groups in this context, Ra 104 Examples include those similar to aromatic hydrocarbon groups in [the text]. Among them, Ra' 14 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from naphthalene or anthracene with one or more hydrogen atoms removed; and most preferably a group from naphthalene with one or more hydrogen atoms removed. Ra' 14 A substituent that may be present is Ra 104 Examples of substituents that may be present include those similar to those that the molecule may have.

[0059] Ra' in equation (a1-r2-4) 14 If is a naphthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in equation (a1-r2-4) 14When it is an antryl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be any of the 1-position, 2-position or 9-position of the antryl group.

[0060] Specific examples of the group represented by the formula (a1-r2-1) are listed below.

[0061]

Chemical formula

[0062]

Chemical formula

[0063]

Chemical formula

[0064] Specific examples of the group represented by the formula (a1-r2-2) are listed below.

[0065]

Chemical formula

[0066]

Chemical formula

[0067]

Chemical formula

[0068] Specific examples of the group represented by the formula (a1-r2-3) are listed below.

[0069]

Chemical formula

[0070] Specific examples of the group represented by the formula (a1-r2-4) are given below.

[0071]

Chemical formula

[0072] Tertiary alkyloxycarbonyl acid dissociable group: Among the above polar groups, examples of the acid dissociable group that protects the hydroxyl group include the acid dissociable group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as "tertiary alkyloxycarbonyl acid dissociable group" for convenience).

[0073]

Chemical formula

[0074] In the formula (a1-r-3), Ra’ 7 ~Ra’ 9 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Also, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0075] Secondary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group that protects the carboxy group include the acid dissociable group represented by the following general formula (a1-r-4).

[0076]

Chemical formula

[0077] In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in this is the Ra' 3 Similar examples include the above. In the formula, Ra' 11a and Ra' 11b The alkyl group in is the aforementioned Ra' 1 Examples include alkyl groups similar to those in the above. In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in, and Ra' 11a and Ra' 11b The alkyl group in may have substituents. For example, the above-mentioned Ra is an example of such substituent. x5 These are some examples.

[0078] Ra' 10 and Ra' 11a Or Ra' 11b These elements may be bonded to each other to form a ring. This ring may be polycyclic or monocyclic, and may be an alicyclic or aromatic ring. The alicyclic and aromatic rings may also contain heteroatoms.

[0079] Ra' 10 and Ra' 11a Or Ra' 11b The rings formed by the bonding of these elements are preferably monocycloalkenes, rings in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), monocycloalkadienes, cycloalkenes having 3 to 6 carbon atoms, and cyclopentene or cyclohexene.

[0080] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may be a fused ring. Specific examples of such fused rings include indane.

[0081] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may have substituents. For example, the above-mentioned Ra x5 These are some examples.

[0082] Ra' 11a Or Ra' 11b And, Ra' 12 These elements may be bonded together to form a ring, and the ring may be Ra' 10 and Ra' 11a Or Ra' 11b Examples include rings formed by the bonding of these elements together.

[0083] Specific examples of the group represented by the formula (a1-r-4) are given below.

[0084] [ka]

[0085] Examples of constituent units (a1) include constituent units derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent, constituent units derived from acrylamide, constituent units derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group of a constituent unit is protected by a substituent containing the acid-degradable group, and constituent units derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group is protected by a substituent containing the acid-degradable group.

[0086] As for the constituent unit (a1), among the above, a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent is preferred. A preferred example of such a constituent unit (a1) is a constituent unit represented by the following general formulas (a1-1), (a1-2), or (a1-3).

[0087] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va 1 n is a divalent hydrocarbon group which may have an ether bond. a1 is an integer between 0 and 2. 1 This is an acid-dissociable group represented by the general formula (a1-r-1), (a1-r-2), or (a1-r-4) above. 1 is n a2 It is a +1 valent hydrocarbon group, n a2 is an integer between 1 and 3, and Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above. 001 It is a single bond or a divalent linking group. 01 It is a single bond or a divalent linking group. Rax 01 is an acid-dissociable group represented by the general formula (a1-r-1), (a1-r-2), or (a1-r-4) above. q is an integer between 0 and 3. n is an integer greater than or equal to 1, where n ≤ q × 2 + 4.

[0088] In formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. A halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

[0089] In the above formula (a1-1), Va 1 The divalent hydrocarbon group in this expression may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0090] Va 1 The aliphatic hydrocarbon group as a divalent hydrocarbon group in this compound may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0091] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0092] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear or branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a monocycloalkane with two hydrogen atoms removed. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a polycycloalkane with two hydrogen atoms removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0093] Va 1 In this context, an aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings in aromatic hydrocarbon groups include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0094] In the above formula (a1-1), Ra 1 This is an acid-dissociable group represented by the above formula (a1-r-1), (a1-r-2), or (a1-r-4).

[0095] In the above formula (a1-2), Wa 1 n in a2 The +1 valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group that is a combination of a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure. The aforementioned n a2 The +1 valent is preferably 2 to 4 valent, and more preferably 2 or 3 valent.

[0096] In the above formula (a1-2), Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above.

[0097] In the above formula (a1-3), Ya 001 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Ya 001 The alkylene group is preferably an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Among these, Ya 001The combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0098] In the above formula (a1-3), Ya 01 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Ya 01 Among the above, it is preferable that the ester bond [-C(=O)-O-, -OC(=O)-], ether bond (-O-), linear or branched alkylene group, aromatic hydrocarbon group or a combination thereof, or single bond. Among these, Ya 01 The combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0099] In the above formula (a1-3), Rax 01 The acid-dissociable group is preferably represented by the general formula (a1-r-2) or (a1-r-4) described above, and among these, the acid-dissociable group represented by the general formula (a1-r-2) is more preferred, and the group represented by the general formula (a1-r2-1) is even more preferred.

[0100] In the above formula (a1-3), q is an integer between 0 and 3. When q is 0, it is a benzene structure; when q is 1, it is a naphthalene structure; when q is 2, it is an anthracene structure; and when q is 3, it is a tetracene structure. In the above formula (a1-3), n is an integer of 1 or more, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. In the above formula (a1-3), n ≤ q × 2 + 4. For example, if q is 1 and the structure is naphthalene, then all six hydrogen atoms in the naphthalene may be substituted with hydroxyl groups. Also, in the naphthalene, Ya 001 、-Ya 01 -C(=O)-O-Ra01 The substitution positions of the group and the hydroxyl group are not particularly limited.

[0101] The following are specific examples of constituent units (a1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] The constituent units (a1) of component (A1) may be one type or two or more types. As for the constituent unit (a1), the constituent unit represented by formula (a1-1) or the constituent unit represented by formula (a1-3) is more preferable because it is easier to improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography. In particular, it is suitable for EB or EUV applications as it can enhance reactivity, and therefore has an acid-dissociating group (Ra 1 Rax 01 Preferably, each of these groups is an acid-dissociable group represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4), and among these, it is particularly preferable to select a cyclic group.

[0117] The proportion of constituent units (a1) in component (A1) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 70 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of the constituent unit (a1) to be above the lower limit of the preferred range described above, lithography characteristics such as sensitivity, in-plane uniformity of pattern dimensions (CDU), and fine resolution are improved. On the other hand, if it is below the upper limit of the preferred range described above, a balance can be achieved with other constituent units, resulting in good lithography characteristics in various aspects.

[0118] <<Other constituent units>> Component (A1) may have other constituent units in addition to the constituent unit (a1) described above, as needed. Other constituent units include, for example, the constituent unit represented by the following general formula (a10-1), the constituent unit containing a lactone-containing cyclic group (a2), and the constituent unit derived from the compound represented by the following general formula (a8-1).

[0119] Unit of composition (a10): The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0120] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. x1 Wa is a single bond or a divalent linking group. x1 n is an aromatic hydrocarbon group which may have substituents. ax1 [ is an integer greater than or equal to 1.]

[0121] In formula (a10-1), R is the same as R in general formula (a1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0122] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0123] • Divalent hydrocarbon groups which may have substituents: The divalent hydrocarbon group, which may have substituents, may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0124] Aliphatic hydrocarbon groups An aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferable to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0125] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0126] The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0127] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0128] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred. A fluorine atom is preferred as the halogen atom used as the substituent. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0129] Aromatic hydrocarbon groups The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0130] The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halides that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0131] • Divalent linking groups containing heteroatoms: Examples of divalent linking groups containing heteroatoms include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 0 to 3. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each of these is independently a divalent hydrocarbon group which may have substituents. Examples of such divalent hydrocarbon groups are the same as those described above. Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 Preferably, the group is a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y 21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0132] Ya x1 Preferred members include single bonds, ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), linear or branched alkylene groups, or combinations thereof, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0133] In the above formula (a10-1), Wa x1 This is an aromatic hydrocarbon group which may have substituents. Wa x1 The aromatic hydrocarbon group in this context may be an aromatic ring that may have substituents (n ax1 A group with 1+1 hydrogen atoms removed is an example. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Also, Wa x1 The aromatic hydrocarbon group in this context is an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.) (n ax1 Another example is a group with (+1) hydrogen atoms removed. Among the above, Wa x1 Examples include benzene, naphthalene, anthracene, or biphenyl (nax1 A group with (+1) hydrogen atoms removed is preferred, and (n ax1 A group with (+1) hydrogen atoms removed is more preferable, and from benzene (n ax1 A group with (+1) hydrogen atoms removed is even more preferable.

[0134] Wa x1 The aromatic hydrocarbon group in may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents include Ya x1 Examples of substituents for cyclic aliphatic hydrocarbon groups in are similar to those listed above. The substituents are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably linear or branched alkyl groups having 1 to 3 carbon atoms, even more preferably ethyl or methyl groups, and particularly preferably methyl groups. x1 In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0135] In the above formula (a10-1), n ax1 is an integer greater than or equal to 1, preferably an integer between 1 and 10, more preferably an integer between 1 and 5, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0136] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In each of the following equations, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] The constituent units (a10) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a10), but it is preferable that it has constituent units (a10). If component (A1) has constituent units (a10), the proportion of constituent units (a10) in component (A1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of constituent unit (a10) above the lower limit, sensitivity can be more easily increased. On the other hand, by setting it below the upper limit, it becomes easier to balance it with other constituent units.

[0141] Unit of composition (a2): Component (A1) may have a constituent unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to constituent unit (a1)). The lactone-containing cyclic group of component (a2) is effective in improving the adhesion of the resist film to the substrate when component (A1) is used to form a resist film. Furthermore, the presence of component (a2) improves lithography characteristics, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0142] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Any lactone-containing cyclic group can be used in the constituent unit (a2) without any particular limitations. Specifically, this includes the groups represented by the general formulas (a2-r-1) to (a2-r-8) described below.

[0143] Among the constituent units (a2), those derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent are preferred. The constituent unit (a2) is preferably a constituent unit represented by the following general formula (a2-1).

[0144] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. 21 It is a single bond or a divalent linking group. 21 The R' is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La 21 If -O-, Ya 21 It does not become -CO-. 21 It is a lactone-containing cyclic group.

[0145] In formula (a2-1) above, R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0146] In the above formula (a2-1), Ya 21 The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. 21 The divalent linking group in the above general formula (a10-1) is Ya x1 Examples include divalent linking groups similar to those in [the relevant context].

[0147] Ya 21 Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0148] In the above formula (a2-1), Ya 21 It is a single bond, La 21 It is preferable that it be -COO- or -OCO-.

[0149] In the above formula (a2-1), Ra 21 It is a lactone-containing cyclic group. Ra 21 Suitable lactone-containing cyclic groups in this compound include those represented by the general formulas (a2-r-1) to (a2-r-8), as described below.

[0150] The constituent units (a2) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a2). If component (A1) has constituent units (a2), the proportion of constituent units (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 1 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is set above a preferred lower limit, the effects of including constituent unit (a2) are fully obtained due to the effects described above, and if it is below the upper limit, a balance can be achieved with other constituent units, resulting in good lithography characteristics.

[0151] Unit of composition (a8): The constituent unit (a8) is a constituent unit derived from the compound represented by the following general formula (a8-1).

[0152] [ka] [In the formula, W 2This is a polymerizable group-containing group. x2 is a single bond or (n ax2 It is a linking group with a +1 valence. x2 and W 2 It may form a fused ring with R. 1 R is a fluorinated alkyl group having 1 to 12 carbon atoms. 2 R is an organic group having 1 to 12 carbon atoms, which may contain a fluorine atom, or a hydrogen atom. 2 and Ya x2 These may be bonded to each other to form a ring structure. ax2 [This is an integer between 1 and 3.]

[0153] W 2 In the context of polymerizable group-containing groups, "polymerizable group" refers to a group that enables a compound containing a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond.

[0154] The polymerizable group-containing group may be a group composed solely of a polymerizable group, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of other groups other than the polymerizable group include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Examples of polymerizable groups include those with the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 The group represented by - is preferably mentioned. In this chemical formula, R X11 , R X12 and R X13 These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 It is a single bond or a divalent linking group.

[0155] Ya x2 and W 2 The condensed ring formed by these is W 2 Polymerizable groups of the site and Ya x2 The condensed ring formed by and W 2Other groups besides the polymerizable group of the site and Ya x2 A condensed ring formed by these is one example. Ya x2 and W 2 The fused ring formed by these two components may have substituents.

[0156] The following are specific examples of constituent units (a8). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0157] [ka]

[0158] Among the examples above, the constituent unit (a8) is preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0159] The constituent units (a8) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a8). The proportion of constituent units (a8) in component (A1) is preferably 0 to 50 mol%, and more preferably 0 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0160] The (A1) component contained in the resist composition may be used alone or in combination of two or more types.

[0161] (A1) Examples of components include polymer compounds containing a repeating structure of constituent units (a1) and (a10). A preferred (A1) component is a polymer compound consisting of a repeating structure of constituent units (a1) and constituent units (a10). The proportion of constituent units (a1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 40 to 60 mol%, based on the total amount (100 mol%) of all constituent units that make up the (A1) component. The proportion of constituent units (a10) is preferably 20 to 80 mol%, more preferably 30 to 75 mol%, even more preferably 40 to 70 mol%, and particularly preferably 40 to 60 mol%, based on the total amount (100 mol%) of all constituent units that make up the (A1) component.

[0162] Such component (A1) can be produced by dissolving monomers that induce each constituent unit in a polymerization solvent and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the mixture and polymerizing it. Alternatively, such component (A1) can be produced by dissolving a monomer that induces a constituent unit (a1) and a monomer that induces an arbitrary constituent unit (for example, a monomer that induces a constituent unit (a10), etc.) in a polymerization solvent, adding a radical polymerization initiator as described above to carry out polymerization, and then performing a deprotection reaction. Furthermore, during polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group at the terminal. Copolymers in which a hydroxyalkyl group, in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, are introduced are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0163] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, even more preferably 4,000 to 30,000, and particularly preferably 5,000 to 10,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance and a good cross-sectional shape of the resist pattern. (A1) The degree of dispersion of component (Mw / Mn) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0164] (A2) About the ingredients The resist composition of this embodiment may also include, as component (A), a base component (hereinafter referred to as "component (A2)") that does not correspond to component (A1) and whose solubility in the developer changes due to the action of an acid. (A2) The component is not particularly limited and can be arbitrarily selected from a large number of components that have been conventionally known as base components for chemically amplified resist compositions. (A2) Component may be a single high-molecular-weight compound or a low-molecular-weight compound, or two or more may be used in combination.

[0165] The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, it becomes easier to form a resist pattern with excellent lithography characteristics such as high sensitivity, in-plane uniformity of pattern dimensions (CDU), and fine resolution.

[0166] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0167] <Acid generating agent component (B)> The resist composition of this embodiment further contains an acid-generating agent component (component (B)) that generates acid upon exposure, in addition to component (A). Component (B) includes a compound (B0) represented by the following general formula (b0) (hereinafter also referred to as "component (B0)").

[0168] • About component (B0) Component (B0) is a compound represented by the following general formula (b0).

[0169] [ka] [In the formula, R b L is a base-degradable group. 03 Rl is a divalent linking group. 0 L is a cyclic organic group which may have substituents. 02 is a divalent linking group. I is an iodine atom. R m1 L is a substituent other than the iodine atom. 01 This is a divalent linking group or a single bond. Vb 0 is an alkylene group, a fluorinated alkylene group, or a single bond. However, L 01 and Vb 0 It is impossible for them to be single bonds at the same time. 0 nb1 is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. nb1 is an integer from 1 to 4, nb2 is an integer from 1 to 4, and nb3 is an integer from 0 to 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. m+ This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

[0170] {(B0) component anion part} In the above equation (b0), R b It is a basic-degradable group. In this context, a "basic-degradable group" refers to a group that is degradable in which at least some of the bonds in its structure can be cleaved by the action of an alkaline developer. "Degradability that allows the bond to be cleaved by the action of an alkaline developer" means that the material decomposes upon the action of an alkaline developer of 0.1 to 30% by mass (preferably, decomposition upon the action of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C), and its solubility in the alkaline developer increases. This is due, for example, to the decomposition (hydrolysis) of the ester bond by the action of the alkaline developer (base), which generates a hydrophilic group. Examples of such hydrophilic groups include carboxyl groups and hydroxyl groups.

[0171] R b The base-degradable group in this product is not particularly limited as long as it decomposes with a base and changes the (B0) component to be soluble in an alkaline developer. Any base-degradable group that has been proposed in components incorporated into chemically amplified resist compositions can be used, for example, a structure containing an ester bond. In particular, R in equation (b0) b It is preferable that the group includes a lactone-containing cyclic group.

[0172] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Such lactone-containing cyclic groups are not particularly limited and any group can be used. Specifically, examples include the groups represented by the following general formulas (a2-r-1) to (a2-r-8).

[0173] [ka] [In the formula, Ra' 21Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom, where n' is an integer from 0 to 2 and m' is 0 or 1. * indicates a bond.

[0174] In the above formulas (a2-r-1) to (a2-r-8), Ra' 21 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. Among these, the methyl group or ethyl group is preferred, and the methyl group is particularly preferred. Ra' 21 The alkoxy group in is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' 21 Examples of alkyl groups in this context include groups formed by linking an alkyl group with an oxygen atom (-O-). Ra' 21 In this mixture, a fluorine atom is preferred as the halogen atom. Ra' 21 The halogenated alkyl group in is the Ra' 21 Examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. Fluorinated alkyl groups are preferred as the halogenated alkyl group, and perfluoroalkyl groups are particularly preferred.

[0175] Ra' 21 In -COOR'' and -OC(=O)R'', R'' is either a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' can be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R'' is a linear or branched alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When R'' is a cyclic alkyl group, it is preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of lactone-containing cyclic groups in R'' include those similar to those represented by the general formulas (a2-r-1) to (a2-r-8) mentioned above. Ra' 21 The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, specifically the Ra' 21 Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0176] Ra' 21 Among the above, it is preferable that each is independently either a hydrogen atom or a cyano group.

[0177] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5) above, the alkylene group having 1 to 5 carbon atoms in A'' is preferably a linear or branched alkylene group, such as a methylene group, ethylene group, n-propylene group, isopropylene group, etc. If the alkylene group contains an oxygen atom or a sulfur atom, specific examples include a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A'', an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0178] The following are specific examples of groups represented by the general formulas (a²-r-1) to (a²-r-8).

[0179] [ka]

[0180] [ka]

[0181] In the above equation (b0), R b The group is preferably a lactone-containing cyclic group, more preferably a group represented by the general formulas (a2-r-1) to (a2-r-8), even more preferably a group represented by the general formulas (a2-r-1) to (a2-r-2), and particularly preferably a group represented by the general formula (a2-r-1).

[0182] In the above formula (b0), Rl 0 In this context, the cyclic organic group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0183] Rl 0In this context, the aliphatic hydrocarbon group of the monocyclic group is preferably a group obtained by removing two or more hydrogen atoms from a monocycloalkane or monocycloalkene. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The monocycloalkene is preferably one having 3 to 6 carbon atoms, specifically cyclopentene, cyclohexene, etc. Rl 0 In this context, the polycyclic aliphatic hydrocarbon group is preferably a polycycloalkane or polycycloalkene from which two or more hydrogen atoms have been removed. The polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. The polycycloalkene is preferably one having 7 to 12 carbon atoms, specifically adamantene, norbornene, isobornene, tricyclodecene, tetracyclododecene, etc.

[0184] Rl 0 In this context, the aromatic hydrocarbon group is preferably a group obtained by removing two or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene, more preferably a group obtained by removing two or more hydrogen atoms from benzene, naphthalene, or anthracene, and even more preferably a group obtained by removing two or more hydrogen atoms from benzene.

[0185] Rl 0 Examples of substituents that the cyclic organic group may have include the above-mentioned Ra x5 Similar bases can be cited. Furthermore, the organic group may have some of its constituent carbon atoms (such as a methylene group) replaced by a heteroatom-containing group. Examples of heteroatoms used here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc. In other words, Rl0 The cyclic organic group which may have substituents may be a group obtained by removing two or more hydrogen atoms from an aromatic heterocycle such as a pyridine ring or a thiophene ring; or a group obtained by removing two or more hydrogen atoms from an aliphatic heterocycle such as tetrahydrofuran, tetrahydropyran, or tetrahydrothiophene.

[0186] Rl 0 The cyclic organic group in may be a fused ring group containing a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridging ring system with one or more aromatic rings fused to it. Specific examples of the bridging ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to a bicycloalkane.

[0187] In the above general formula (b0), Rl 0 Among the above, from the viewpoint of improving the uniformity of the dispersion of component (B0) within the resist film, it is preferable that the (B0) is an aromatic hydrocarbon group which may have substituents, or a polycyclic alicyclic hydrocarbon group which may have substituents, and more preferably an aromatic hydrocarbon group which is a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon group, a polycycloalkane or polycycloalkene, or a fused ring which includes a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring.

[0188] Rl 0 Specifically, it is preferable that the group be represented by any of the following chemical formulas (Rl0-1) to (Rl0-4), more preferably by the following chemical formulas (Rl0-1), (Rl0-2), or (Rl0-4), and even more preferably by the following chemical formula (Rl0-4). Furthermore, the hydrogen atoms in the groups represented by the following chemical formulas (Rl0-1) to (Rl0-4) may each be independently substituted with substituents. The substituents include the above-mentioned Ra x5 Similar examples include the above.

[0189] [ka]

[0190] In the above formula (b0), L 01 L is a divalent linking group or a single bond. 02 L is a divalent linking group. 03 It is a divalent linking group. L 01 , L 02 and L 03 In this context, a divalent linking group containing an oxygen atom is preferred. L 01 , L 02 and L 03 However, if it is a divalent linking group containing an oxygen atom, L 01 , L 02 and L 03 It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of divalent linking groups containing an oxygen atom include non-hydrocarbon oxygen-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-OC(=O)-O-); and combinations of such non-hydrocarbon oxygen-containing linking groups with alkylene groups. A sulfonyl group (-SO2-) may be further linked to this combination.

[0191] L 01 , L 02 and L 03 More specifically, the divalent linking groups in are -O-, -CO-, -OCO-, -COO-, -SO2-, -N(R a )-C(=O)-,-N(R a )-,-C(R a )(R a )-N(R a )-,-C(R a )(N(R a)(R a ))-, or -C(=O)-N(R a )-, or a combination of the aforementioned non-hydrocarbon oxygen atom-containing linking group and alkylene group, etc. a Each of these is independently either a hydrogen atom or an alkyl group.

[0192] In the above formula (b0), L 01 Among the above, it is preferably a divalent linking group, and more preferably a divalent linking group containing an oxygen atom, such as -OCO-, -COO-, or -C(=O)-N(R a It is more preferable that the combination is -OCO-, -COO-, or the combination is the combination of the non-hydrocarbon oxygen atom-containing linking group and an alkylene group.

[0193] In the above formula (b0), L 02 Among the above, it is preferable that the linking group is a divalent group containing an oxygen atom, such as -OCO-, -COO-, or -C(=O)-N(R a It is more preferable that it is -OCO-, -COO-, or -C(=O)-NH-.

[0194] In the above formula (b0), L 03 Among the above, it is preferable that the linking group is a divalent group containing an oxygen atom, such as -OCO-, -COO-, or -C(=O)-N(R a It is more preferable that it be -OCO- or -COO-, and particularly preferable that it be -OCO- or -COO-.

[0195] In the above equation (b0), R m1 Examples of substituents other than the iodine atom in this compound include hydroxyl groups, alkyl groups, fluorinated alkyl groups, fluorine atoms, and chlorine atoms. The alkyl group and the alkyl group in the fluorinated alkyl group are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably methyl or ethyl groups.

[0196] In the above formula (b0), Vb 0 The alkylene group and the fluorinated alkylene group in each are preferably having 1 to 4 carbon atoms, and more preferably having 1 to 3 carbon atoms. Vb 0 Examples of fluorinated alkylene groups include groups in which some or all of the hydrogen atoms of an alkylene group are replaced with fluorine atoms. Vb 0 Among the above, it is preferably an alkylene group or a fluorinated alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms or a fluorinated alkylene group having 1 to 4 carbon atoms, and even more preferably a methylene group (-CH2-), -CH(CF3)-, -CH2CH2CF2-, or -CH2CH2CHF-.

[0197] For example, -L in the general formula (b0) 01 -Vb 0 -Examples of linking groups include those represented by any of the following general formulas (b0-r-1) to (b0-r-7).

[0198] [ka] [In the formula, L 011 L is an alkylene group or single bond with 1 to 5 carbon atoms. 012 This is a divalent saturated hydrocarbon group or single bond having 1 to 30 carbon atoms. Vb 01 This is a fluorinated alkylene group or single bond having 1 to 4 carbon atoms. However, L 012 and Vb 01 They cannot be single bonds at the same time.

[0199] In the above formulas (b0-r-1), (b0-r-2), and (b0-r-5) to (b0-r-7), L 012 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms. -L in the above general formula (b0) 01-Vb 0 -Among these, a linking group represented by any of the general formulas (b0-r-1) to (b0-r-2) is particularly preferred.

[0200] In the above equation (b0), R 0 This is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. R 0 The fluorinated alkyl group having 1 to 5 carbon atoms is preferably a fluorine atom, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferably a fluorine atom, and even more preferably a fluorine atom.

[0201] In formula (b0), nb1 represents the number of iodine atoms (I), and is an integer from 1 to 4, preferably from 1 to 3, and more preferably 2 or 3. nb2 is an integer between 1 and 4, preferably 1 or 2, and more preferably 1. nb3 is a substituent other than the iodine atom (R m1 This indicates the number of ), which is an integer between 0 and 3, preferably 0 or 1, and more preferably 0.

[0202] The following are some preferred specific examples of the anion portion of component (B0). The anions represented by the following chemical formulas (b0-an-101) to (b0-an-129) are Rl in formula (b0) 0 This is an example of the anionic part when the ring is a benzene ring. The anions represented by the following chemical formulas (b0-an-201) to (b0-an-223) are Rl in formula (b0) above. 0 This is an example of the anion part when it is a norbornene ring. The anions represented by the following chemical formulas (b0-an-301) to (b0-an-322) are Rl in formula (b0) above. 0 This is an example of the anionic part when it is a bicyclooctane ring.

[0203] [ka]

[0204]

change

[0205]

change

[0206]

change

[0207]

change

[0208]

change

[0209]

change

[0210]

change

[0211]

change

[0212]

change

[0213]

change

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] The anion portion of component (B0) is preferably selected from the group consisting of anions represented by the above chemical formulas (b0-an-101) to (b0-an-129), selected from the group consisting of anions represented by the above chemical formulas (b0-an-201) to (b0-an-223), or selected from the group consisting of anions represented by the above chemical formulas (b0-an-301) to (b0-an-322). Among these, the anionic portion of component (B0) is more preferably selected from the group consisting of anions represented by the chemical formulas (b0-an-301) to (b0-an-322) above, as this makes it easier to obtain the effects of the present invention.

[0220] {(B0) component cation} In the above formula (b0), M m+ This is an m-valent organic cation, where m is an integer greater than or equal to 1. M m+As the organic cation in this, onium cations are preferred, and among these, sulfonium cations and iodonium cations are more preferred.

[0221] M m+ Examples of organic cations in this context include the organic cations represented by the following general formulas (ca-1) to (ca-3).

[0222] [ka] [In the formula, R 201 ~R 207 Each of these independently represents an aryl group, alkyl group, or alkenyl group, which may have substituents. 201 ~R 203 , R 206 ~R 207 These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-.

[0223] In the above equations (ca-1) to (ca-3), R 201 ~R 207 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0224] [ka] [In the formula, R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0225] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0226] R' 201 The aromatic hydrocarbon group in this context is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: e.g., phenyl group, naphthyl group, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0227] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0228] Among them, R' 201The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0229] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0230] Also, R' 201The cyclic hydrocarbon group in this formula may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8), the -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4) described below, and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16) below.

[0231] [ka]

[0232] R' 201 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As alkyl groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. As the halogen atom used as a substituent, a fluorine atom is preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0233] Chain-like alkyl groups that may have substituents: R' 201 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0234] A chain-like alkenyl group which may have substituents: R' 201 The linear alkenyl group may be linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0235] R' 201 Substituents in the chain-like alkyl or alkenyl group include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R' 201 Examples include cyclic groups in this context.

[0236] R' 201In addition to those mentioned above, the optionally substituted cyclic groups, optionally substituted linear alkyl groups, or optionally substituted linear alkenyl groups may also include those similar to the acid-dissociable group represented by formula (a1-r-2) above, as optionally substituted cyclic groups or optionally substituted linear alkyl groups.

[0237] Among them, R' 201 The cyclic group is preferably a cyclic group which may have substituents, and more preferably a cyclic hydrocarbon group which may have substituents. More specifically, preferred groups include, for example, a phenyl group, a naphthyl group, a polycycloalkane from which one or more hydrogen atoms have been removed; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8) mentioned above; and -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4) mentioned below.

[0238] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring preferably has 3 to 10 members, and particularly preferably 5 to 7 members, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0239] R 208 ~R 209Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond with other elements to form a ring.

[0240] R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 210 In this context, any -SO2-containing cyclic group can be used without particular limitations. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) are examples, with "-SO2-containing polycyclic groups" being preferred, and the group represented by general formula (b5-r-1) being more preferred.

[0241] [ka] [In the formula, Rb' 51 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or a -SO2--containing cyclic group; B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n' is an integer from 0 to 2. * indicates a bond.

[0242] In the above general formulas (b5-r-1) to (b5-r-2), B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, or an oxygen atom or a sulfur atom. B'' is preferably an alkylene group or -O- having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0243] In the above general formulas (b5-r-1) to (b5-r-4), Rb' 51 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group, and among these, each is preferably independently a hydrogen atom or a cyano group.

[0244] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group.

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas.

[0249] [ka]

[0250] [ka]

[0251] [ka] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0252] [ka]

[0253] [ka]

[0254] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the aforementioned R 201 ~R 207 , and R 210 ~R 212 These are the same as those listed as substituents that may be present.

[0255] [ka]

[0256] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0257] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0258] [ka]

[0259] M m+ The organic cation is preferably at least one selected from the group consisting of cations represented by the general formulas (ca-1) to (ca-3), and among these, the cation represented by the general formula (ca-1) is more preferred. In particular, from the viewpoint of increasing sensitivity, preferred cations represented by the above formula (ca-1) are those having electron-withdrawing groups such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as substituents. For example, cations selected from the group consisting of cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferred.

[0260] The following are specific examples of component (B0), but are not limited to these.

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] [ka]

[0265] [ka]

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] Component (B0) is preferably selected from the group consisting of compounds represented by the chemical formulas (B0-1) to (B0-29) above. Alternatively, component (B0) is preferably selected from the group consisting of compounds represented by the above chemical formulas (B0-1) to (B0-12), the group consisting of compounds represented by the above chemical formulas (B0-13) to (B0-18), or the group consisting of compounds represented by the above chemical formulas (B0-19) to (B0-29). Among these, component (B0) is more preferably selected from the group consisting of compounds represented by the above chemical formulas (B0-19) to (B0-29).

[0271] In the resist composition of this embodiment, component (B0) may be used alone or in combination of two or more types. In the resist composition of this embodiment, the content of component (B0) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 20 to 35 parts by mass, per 100 parts by mass of component (A). If the content of component (B0) is above the lower limit of the preferred range described above, high sensitivity can be achieved in resist pattern formation, and lithography characteristics such as CDU and fine resolution can be easily improved. On the other hand, if it is below the upper limit of the preferred range described above, sensitivity can be maintained more effectively. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability of the resist composition is good, which is preferable.

[0272] The proportion of component (B0) in the total of component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of component (B0) in the total of component (B) may be 100% by mass.

[0273] • About ingredient (B1) The resist composition of this embodiment may contain an acid generating agent component other than the above-described component (B0) (hereinafter also referred to as "component (B1)"). The (B1) component is not particularly limited, and any acid generators previously proposed for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts; oximesulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators, among many others.

[0274] In the resist composition of this embodiment, component (B1) may be used alone or in combination of two or more types. If the resist composition of this embodiment contains component (B1), the proportion of component (B1) to the total amount of component (B) is preferably less than 50% by mass, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably less than 20% by mass.

[0275] <Other ingredients> The resist composition of this embodiment may further contain other components in addition to the above-described components (A) and (B). Examples of other components include components (D), (E), (F), and (S) shown below. ≪Basic component (D)≫ The resist composition of this embodiment may also contain, in addition to components (A) and (B), a basic component (component (D)) that traps (i.e., controls the diffusion of) the acid generated by exposure. Component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. Examples of component (D) include a photo-disintegrating base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure and loses its ability to control acid diffusion, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under component (D1). Among these, a photo-disintegrating base (component (D1)) is preferred because it is easier to improve the characteristics of high sensitivity, roughness reduction, and suppression of coating defects.

[0276] • About the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), the compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Components (d1-1) to (d1-3) decompose in the exposed areas of the resist film and lose their acid diffusion control properties (basicity), so they do not act as quenchers, but they act as quenchers in the unexposed areas of the resist film.

[0277] [ka] [In the formula, Rd 1 ~Rd 4Rd in formula (d1-2) is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 2 In this example, assume that no fluorine atoms are bonded to the carbon atoms adjacent to the sulfur atoms. 1 is a single bond or a divalent linking group. m is an integer greater than or equal to M m+ These are each independently m-valent organic cations.

[0278] {(d1-1) component} ··Anion Club In formula (d1-1), Rd 1 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of the above R' is... 201 Similar examples include the above. Among these, Rd 1 Preferred substituents are optionally substituted aromatic hydrocarbon groups, optionally substituted aliphatic cyclic groups, or optionally substituted linear alkyl groups. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8), ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and in this case, preferred substituents are the linking groups represented by the general formulas (y-al-1) to (y-al-5). Note that Rd 1 If the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in has a linking group represented by the general formulas (y-al-1) to (y-al-7) as a substituent, then in the general formulas (y-al-1) to (y-al-7), Rd in formula (d3-1) 1 The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in the above general formula (y-al-1) to (y-al-7) is V'. 101 That is the case. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably one with 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0279] When the chain-like alkyl group is a fluorinated alkyl group having a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.

[0280] The following are some preferred specific examples of the anionic portion of component (d1-1).

[0281] [ka]

[0282] ··Cation section In formula (d1-1), M m+ This is an m-valent organic cation. M m+Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-3), respectively, with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the formulas (ca-1-1) to (ca-1-84) being even more preferred. (d1-1) Component may be used alone or in combination of two or more types.

[0283] {(d1-2) component} ··Anion Club In formula (d1-2), Rd 2 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. However, Rd 2 In this mixture, we assume that the carbon atom adjacent to the S atom is not bonded to a fluorine atom (i.e., not fluorine-substituted). This results in the anions of components (d1-2) becoming appropriately weak acid anions, improving the quenching ability of component (D). Rd 2 Preferably, the group is a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents, and more preferably an aliphatic cyclic group which may have substituents.

[0284] The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (it may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0285] Rd 2 The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). 1Examples include substituents similar to those that may be present on hydrocarbon groups (aromatic hydrocarbon groups, aliphatic cyclic groups, and linear alkyl groups) in the above.

[0286] The following are preferred specific examples of the anionic portion of component (d1-2).

[0287] [ka]

[0288] ··Cation section In formula (d1-2), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-2) Components may be used individually or in combination of two or more.

[0289] {(d1-3) components} ··Anion Club In formula (d1-3), Rd 3 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and the R' 201 Similar groups are mentioned, and it is preferable that they are cyclic groups containing a fluorine atom, linear alkyl groups, or linear alkenyl groups. Among these, fluorinated alkyl groups are preferred, and the aforementioned Rd 1 A fluorinated alkyl group similar to the one shown is more preferable.

[0290] In formula (d1-3), Rd 4 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. In particular, alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups, which may have substituents, are preferred. Rd 4The alkyl group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. 4 Some of the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups, cyano groups, etc. Rd 4 The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specifically, examples of alkoxy groups having 1 to 5 carbon atoms include the methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group. Among these, the methoxy group and ethoxy group are preferred.

[0291] Rd 4 The alkenyl group in R' 201 Examples of alkenyl groups similar to those in the above include vinyl groups, propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups, which are preferred. These groups may further have substituents of an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0292] Rd 4 The cyclic group in is the R' 201 Examples of cyclic groups similar to those in the above include alicyclic groups obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, or aromatic groups such as phenyl groups and naphthyl groups. 4 When Rd is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in good lithography properties. 4 When the group is an aromatic group, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithographic characteristics in lithography using EUV or the like as the exposure light source.

[0293] In formula (d1-3), Yd 1 It is a single bond or a divalent linking group. Yd 1 The divalent linking group in formula (a2-1) is not particularly limited, but may include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) which may have substituents, and divalent linking groups containing heteroatoms. 21 Examples include divalent hydrocarbon groups that may have substituents, and divalent linking groups containing heteroatoms, as mentioned in the explanation of divalent linking groups in [the relevant section]. Yd 1 The preferred members are carbonyl groups, ester bonds, amide bonds, alkylene groups, or combinations thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0294] The following are preferred specific examples of the anionic parts of components (d1-3).

[0295] [ka]

[0296] [ka]

[0297] ··Cation section In formula (d1-3), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-3) Components may be used individually or in combination of two or more.

[0298] Component (D1) may consist of only one of the above components (d1-1) to (d1-3), or it may consist of a combination of two or more components. If the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of component (A).

[0299] Component (D1) preferably contains the above-mentioned component (d1-1). The content of component (d1-1) in the total amount of component (D1) is preferably 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more, and component (D1) may consist only of compound (d1-1).

[0300] (D1) Method for producing component: The methods for producing the aforementioned components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Furthermore, the method for producing components (d1-3) is not particularly limited and may be, for example, similar to the method described in US2012-0149916.

[0301] • About the (D2) component Component (D) may include nitrogen-containing organic compounds that do not fall under component (D1) above (hereinafter referred to as "component (D2)"). Component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and it is preferable that the aliphatic group has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0302] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0303] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0304] Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tripenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, and 2,6-di-tert-butylpyridine.

[0305] (D2) Component may be used alone or in combination of two or more types. When the resist composition contains component (D2), the content of component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of component (A). By using this range, the resist pattern shape, aging stability, etc., are improved.

[0306] <<At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and their derivatives>> The resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and their derivatives (hereinafter referred to as "component (E)"). Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, among which salicylic acid is preferred. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred among these.

[0307] In the resist composition of this embodiment, component (E) may be used alone or in combination of two or more types. If the resist composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A). By setting the content within the above range, the lithography characteristics are further improved.

[0308] ≪Fluorine additive component (F)≫ The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water repellency to the resist film and, when used as a resin separate from component (A), can improve lithography properties. As component (F), for example, fluorine-containing polymer compounds described in Japanese Patent Publication No. 2010-002870, Japanese Patent Publication No. 2010-032994, Japanese Patent Publication No. 2010-277043, Japanese Patent Publication No. 2011-13569, and Japanese Patent Publication No. 2011-128226 can be used. More specifically, component (F) includes polymers having a constituent unit (f1) represented by the following general formula (f1-1). This polymer is preferably a polymer (homopolymer) consisting only of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the constituent unit (a1); and more preferably a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid and the constituent unit (a1). Here, the constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, and more preferably a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0309] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 They may be the same or different. 1 Rf is an integer between 0 and 5. 101 It is an organic group containing a fluorine atom.

[0310] In formula (f1-1), R bonded to the α-carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf 102 and Rf 103 A fluorine atom is preferred as the halogen atom. Rf 102 and Rf 103 Examples of alkyl groups having 1 to 5 carbon atoms in R include those similar to the alkyl groups having 1 to 5 carbon atoms in R above, with methyl or ethyl groups being preferred. 102 and Rf103 Specifically, examples of halogenated alkyl groups having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are preferred as the halogen atoms, particularly Rf. 102 and Rf 103 Preferably, the element is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; more preferably, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group; and even more preferably, a hydrogen atom. In formula (f1-1), nf 1 is an integer between 0 and 5, preferably between 0 and 3, and more preferably 1 or 2.

[0311] In formula (f1-1), Rf 101 This is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing fluorine atoms may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Furthermore, in hydrocarbon groups containing fluorine atoms, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and particularly preferable that 60% or more are fluorinated, as this increases the hydrophobicity of the resist film during immersion exposure. Among them, Rf 101 More preferably, fluorinated hydrocarbon groups having 1 to 6 carbon atoms are used, with trifluoromethyl groups, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3 being particularly preferred.

[0312] The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in resist solvents for use as a resist, and if it is above the lower limit of this range, the water repellency of the resist film is good. The degree of dispersion of component (F) (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0313] In the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. If the resist composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A).

[0314] ≪Organic solvent component (S)≫ The resist composition of this embodiment can be manufactured by dissolving a resist material in an organic solvent component (hereinafter referred to as "component (S)"). In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0315] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred as component (S). The mixing ratio (mass ratio) can be appropriately determined considering the compatibility between PGMEA and the polar solvent. As component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited and is set appropriately according to the coating thickness, at a concentration that can be applied to a substrate or the like. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0316] The resist composition of this embodiment may be subjected to removal of impurities after dissolving the resist material in component (S), using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include those described in Japanese Patent Application Publication No. 2016-155121.

[0317] The resist composition of this embodiment described above contains a substrate component (A) and a compound (B0) represented by general formula (b0). Compound (B0) has an iodine atom, and therefore has high absorption of EUV (extreme ultraviolet) and EB (electron beam). On the other hand, the presence of an iodine atom tends to increase the hydrophobicity of the material itself, and decrease its solubility in alkaline developers. Compound (B0) used in this embodiment has a base-degradable group (R) in its structure. b Because it has ), the solubility of the resist film in an alkaline developer can be improved by hydrolysis through the action of an alkaline developer (base). In other words, by including a compound (B0) having both an iodine atom and a base-degradable group in the resist composition, sensitivity and fine resolution can be enhanced. Furthermore, compound (B0) has a cyclic organic group (Rl 0 Because it has a relatively bulky structure, the diffusion length of the acid is moderately suppressed, and it is also adjusted to have a high affinity with the base material components. This improves the in-plane uniformity (CDU) of the pattern dimensions. Therefore, it is presumed that the resist composition of this embodiment containing compound (B0) can achieve high sensitivity when forming a resist pattern and improve lithography characteristics such as CDU and fine resolution.

[0318] (Method for forming resist patterns) A resist pattern formation method according to a second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of such a resist pattern formation method is, for example, a resist pattern formation method carried out as follows.

[0319] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-application bake (PAB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus, either through exposure via a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without going through a mask pattern. After this, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C. Next, the resist film is subjected to a developing process. In the case of an alkaline developing process, an alkaline developer is used, and in the case of a solvent developing process, a developer containing an organic solvent (organic developer) is used.

[0320] After the developing process, a rinsing process is preferably performed. In the case of an alkaline developing process, a water rinse using pure water is preferred, and in the case of a solvent developing process, a rinsing solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing process, a process may be performed to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After development or rinsing, the film is dried. In some cases, a bake (post-bake) process may be performed after the development process.

[0321] The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. As for the wiring pattern material, for example, copper, aluminum, nickel, and gold can be used.

[0322] The wavelength used for exposure is not particularly limited, and can be used with radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays.

[0323] The method for exposing the resist film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography. Immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is first filled with a solvent (immersion medium) that has a refractive index greater than that of air, and then exposure (immersion exposure) is performed in that state. As the immersion medium, a solvent having a refractive index greater than that of air and less than that of the resist film being exposed is preferred. Examples include water, fluorinated inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is preferably used as the immersion medium.

[0324] Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. The organic solvent contained in the organic developer solution used in the solvent development process can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0325] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0326] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0327] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

[0328] The development process can be carried out by known development methods, such as immersing the support in a developer solution for a certain period of time (dip method), piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time (paddle method), spraying the developer solution onto the surface of the support (spray method), or continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method).

[0329] In the solvent-based development process, the rinsing solution used for rinsing after development can contain an organic solvent that is less likely to dissolve the resist pattern, selected from among the organic solvents listed above for use in the organic developer. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used individually or in combination of two or more. They may also be used in mixtures with other organic solvents or water.

[0330] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method).

[0331] As described above, the resist pattern formation method of this embodiment uses the above-mentioned resist composition, which enables high sensitivity when forming the resist pattern and allows for the formation of a resist pattern with enhanced lithography characteristics such as CDU and fine resolution.

[0332] The resist compositions of the embodiments described above, and the various materials used in the pattern forming methods of the embodiments described above (for example, resist solvents, developers, rinse solutions, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of metal atom-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The impurity content in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).

[0333] (Compound represented by general formula (b0)) The compound according to the third aspect of the present invention is a compound represented by the following general formula (b0) (compound (B0)).

[0334] [ka] [In the formula, R b L is a base-degradable group. 03 Rl is a divalent linking group. 0 L is a cyclic organic group which may have substituents. 02 is a divalent linking group. I is an iodine atom. R m1 L is a substituent other than the iodine atom. 01 This is a divalent linking group or a single bond. Vb 0 is an alkylene group, a fluorinated alkylene group, or a single bond. However, L 01 and Vb 0 It is impossible for them to be single bonds at the same time. 0 nb1 is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. nb1 is an integer from 1 to 4, nb2 is an integer from 1 to 4, and nb3 is an integer from 0 to 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. m+This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

[0335] The compound represented by the above general formula (b0) is the same as component (B0) in the resist composition according to the first aspect of the present invention described above. In the above equation (b0), R b , L 03 , Rl 0 , L 02 , R m1 , L 01 Vb 0 , R 0 nb1, nb2, nb3, M m+ The explanation for and m is the same as the explanation above. In the compound of this embodiment, R in the above general formula (b0) b However, groups containing a lactone-containing cyclic group are preferred, groups represented by the general formulas (a2-r-1) to (a2-r-8) are more preferred, groups represented by the general formulas (a2-r-1) to (a2-r-2) are even more preferred, and the group represented by the general formula (a2-r-1) is particularly preferred. In the compound of this embodiment, -L in the above general formula (b0) 01 -Vb 0 - Preferably, the linking group is represented by one of the following general formulas (b0-r-1) to (b0-r-7). In formulas (b0-r-1), (b0-r-2), and (b0-r-5) to (b0-r-7), L 012 The explanation for this is the same as the explanation above. -L in the general formula (b0) above 01 -Vb 0 -Among these, a linking group represented by any of the general formulas (b0-r-1) to (b0-r-2) is particularly preferred.

[0336] [ka] [In the formula, L 011 L is an alkylene group or single bond with 1 to 5 carbon atoms. 012 This is a divalent saturated hydrocarbon group or single bond having 1 to 30 carbon atoms. Vb 01This is a fluorinated alkylene group or single bond having 1 to 4 carbon atoms. However, L 012 and Vb 01 They cannot be single bonds at the same time.

[0337] Specific examples of the compounds of this embodiment include compounds in which the anion portion is represented by the above-mentioned chemical formulas (b0-an-101) to (b0-an-129) respectively (Rl in formula (b0) above). 0 If the compound is a benzene ring, the anion part is represented by the above chemical formulas (b0-an-201) to (b0-an-223), respectively (Rl in formula (b0) above). 0 (When is a norbornene ring), the compound is one in which the anion part is represented by the above chemical formulas (b0-an-301) to (b0-an-322) respectively (Rl in formula (b0) above). 0 Examples include cases where it is a bicyclooctane ring. Specific examples of the compounds of this embodiment include, but are not limited to, the compounds represented by the chemical formulas (B0-1) to (B0-29) described above.

[0338] [Method for producing compounds represented by general formula (b0)] Component (B0) can be produced using known manufacturing methods. For example, component (B0) can be obtained by carrying out a salt exchange reaction between a precursor Bpre represented by the following general formula (Bpre) and a compound S0 represented by the following general formula (S-0).

[0339] [ka] [In the formula, R b L is a base-degradable group. 03 Rl is a divalent linking group. 0 L is a cyclic organic group which may have substituents. 02 is a divalent linking group. I is an iodine atom. R m1 L is a substituent other than the iodine atom. 01 This is a divalent linking group or a single bond. Vb0 is an alkylene group, a fluorinated alkylene group, or a single bond. However, L 01 and Vb 0 It is impossible for them to be single bonds at the same time. 0 This is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. nb1 is an integer from 1 to 4, nb2 is an integer from 1 to 4, and nb3 is an integer from 0 to 3. (M1” m+ ) 1 / m This is an ammonium cation. - M is a non-nucleophilic ion. m+ This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

[0340] More specifically, the above salt exchange reaction is a process of reacting the precursor Bpre with the salt exchange compound S0 in a solvent such as water, dichloromethane, acetonitrile, or chloroform to exchange the cations of the precursor Bpre with the cations of the compound S0, thereby obtaining component (B0).

[0341] In the above formula, (M1” m+ ) 1 / m This is an ammonium cation, which may be an ammonium cation derived from an aliphatic amine or an ammonium cation derived from an aromatic amine.

[0342] In the above formula, Z - Examples include ions that can become acids with lower acidity than the precursor Bpre, specifically halogen ions such as bromide ions and chloride ions; BF4 - AsF6 - SbF6 - PF6 - ClO4 - These are some examples.

[0343] The reaction temperature is, for example, 0 to 100°C, and the reaction time is, for example, between 10 minutes and 24 hours.

[0344] After the salt exchange reaction is complete, compound (B0) in the reaction solution may be isolated and purified. Conventional methods can be used for isolation and purification, and for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc., can be used in appropriate combinations. The structure of the compound obtained as described above is, 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19 It can be identified by common organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.

[0345] Examples of methods for producing precursor Bpre include the following method 1 for producing precursor Bpre.

[0346] Method 1 for producing precursor Bpre: Method 1 for producing precursor Bpre comprises: Step A, a step of reacting a compound represented by the following general formula (CA-00) (hereinafter referred to as "compound (CA00)") with a compound represented by the following general formula (X-00) (hereinafter referred to as "compound (X00)") to obtain a compound represented by the following general formula (Y-00) (hereinafter referred to as "compound (Y00)"); and Step B, a step of reacting compound (Y00) with a compound represented by the following general formula (Al-00) (hereinafter referred to as "compound (Al00)") to obtain precursor Bpre' represented by the following general formula (Bpre'). Precursor Bpre' is a compound used to obtain compound (B0), and is L in general formula (b0). 01 and L 02 These are compounds where the ester bond is (-C(=O)-O-).

[0347] [ka] [In the formula, R m1 nb1 is an integer between 1 and 4, nb2 is an integer between 1 and 4, and nb3 is an integer between 0 and 3, where 2 ≤ nb1 + nb2 + nb3 ≤ 5. 0R is an alkylene group, a fluorinated alkylene group, or a single bond. 0 This is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. (M1” m+ ) 1 / m is an ammonium cation. m is an integer greater than or equal to 1. b L is a base-degradable group. 03 Rl is a divalent linking group. 0 This is a cyclic organic group which may have substituents.

[0348] Process A: Step A is a step in which, for example, compound (CA00) and compound (X00) are reacted in an organic solvent (acetonitrile, tetrahydrofuran, hexane, etc.) to obtain compound (Y00).

[0349] In the reaction in step A, a condensing agent, a basic catalyst, etc., may be used. Examples of specific condensing agents include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyldiimidazole (CDI). Examples of basic catalysts include tertiary amines such as trimethylamine, triethylamine, and tributylamine; aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine; and diazabicyclononene (DBN) and diazabicycloundecene (DBU).

[0350] The reaction temperature is, for example, 0 to 80°C, and the reaction time is, for example, between 10 minutes and 24 hours.

[0351] Process B: Step B is a step in which, for example, compound (Y00) and compound (Al00) are reacted in an organic solvent (such as dichloromethane) to obtain a precursor Bpre'.

[0352] In step B, a condensing agent, a basic catalyst, etc., may be used, similar to step A. The reaction temperature in step B is, for example, 0 to 50°C, and the reaction time is, for example, 10 minutes to 24 hours.

[0353] Compound (Al00) contains a cyclic organic group (Rl 0 A compound obtained by alkylating (e.g., tert-butyl esterification) acetic anhydride containing the same structure as ) and a basic degradable group (R b It can be obtained by reaction with an alcohol containing the same structure as (for example, a lactone alcohol).

[0354] The compounds of this embodiment described above are suitable as acid generators for resist compositions according to the first aspect of the present invention. Furthermore, the compounds of this embodiment can be used as acid generators according to the fourth aspect, which will be described later.

[0355] (Acid generator) The acid generator according to the fourth aspect of the present invention includes the compound according to the third aspect (compound (B0)). The acid generator of this embodiment is particularly suitable as an acid generator component for the resist composition according to the first embodiment described above. [Examples]

[0356] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0357] <Manufacturing of compounds> [Example of intermediate synthesis (1): Synthesis of intermediates H1~H4] Synthesis of intermediate -H1: In a 300 mL three-necked flask, 1,1'-carbonyldiimidazole (CDI) (4.60 g, 28.4 mmol) and acetonitrile (20 g) were added. Then, a solution of 3-hydroxy-4-iodobenzoic acid (CA1) (6.74 g, 25.5 mmol) dissolved in acetonitrile (20 g) was added dropwise over 30 minutes, and the mixture was allowed to react for 1 hour. Subsequently, compound (I-1) (9.5 g, 30.6 mmol) was added and the mixture was reacted at 65°C for 3 hours. After cooling, ultrapure water (250 g) was added, and after stirring for 30 minutes, the precipitated solid was filtered. The filtrate was again dissolved in methanol (100 g) and added dropwise to methyl tert-butyl ether (MTBE) (500 g), and the precipitated solid was filtered. The filtrate was dried under reduced pressure to obtain intermediate-H1 (9.5 g, yield 67.0%).

[0358] [ka]

[0359] Synthesis of intermediates -H2~H4: 3-hydroxy-4-iodobenzoic acid (CA1) was replaced in equimolar amounts with the following carboxylic acids (CA2) to (CA4), and the synthesis was carried out in the same manner as the synthesis of intermediate-H1, yielding intermediate-H2 (12.0 g, yield 69.0%), intermediate-H3 (11.9 g, yield 68.5%), and intermediate-H4 (15.2 g, yield 73.5%).

[0360] [ka]

[0361] [ka]

[0362] [ka]

[0363] [Example of intermediate synthesis (2): Synthesis of intermediates H5~H7] Synthesis of intermediate H5: The synthesis was carried out in the same manner as the synthesis of intermediate-H1, except that 3-hydroxy-4-iodobenzoic acid (CA1) (6.74 g, 25.5 mmol) was replaced with carboxylic acid (CA2) (10.0 g, 25.5 mmol), and compound (I-1) (9.5 g, 30.6 mmol) was replaced with compound (I-2) (11.6 g, 30.6 mmol), yielding intermediate-H5 (13.8 g, yield 72.0%).

[0364] [ka]

[0365] Synthesis of intermediate H6: The synthesis was carried out in the same manner as the synthesis of intermediate-H1, except that 3-hydroxy-4-iodobenzoic acid (CA1) (6.74 g, 25.5 mmol) was replaced with carboxylic acid (CA2) (10.0 g, 25.5 mmol), and compound (I-1) (9.5 g, 30.6 mmol) was replaced with compound (I-3) (11.0 g, 30.6 mmol), yielding intermediate-H6 (13.0 g, 70.0% yield).

[0366] [ka]

[0367] Synthesis of intermediate H7: The synthesis was carried out in the same manner as the synthesis of intermediate-H1, except that 3-hydroxy-4-iodobenzoic acid (CA1) (6.74 g, 25.5 mmol) was replaced with carboxylic acid (CA2) (10.0 g, 25.5 mmol), and compound (I-1) (9.5 g, 30.6 mmol) was replaced with compound (I-4) (11.5 g, 30.6 mmol), yielding intermediate-H7 (13.6 g, yield 71.0%).

[0368] [ka]

[0369] [Example of intermediate synthesis (3): Synthesis of intermediates AA, BA, and NA] Synthesis of intermediate AA: A 1.06 M lithium diisopropylamide (LDA) tetrahydrofuran (THF) / hexane solution (87 mL, 92.3 mmol) was added to a 500 mL three-necked flask. After cooling to 5°C, a solution of tert-butyl alcohol (8.0 g, 108.6 mmol) dissolved in THF (30 g) was added, and the mixture was reacted at a temperature below 5°C for 2 hours. Subsequently, compound (M-1) (15.0 g, 54.3 mmol) was dissolved in THF (225 g) and added, and the reaction was carried out at 5°C or below for 2 hours. The reaction mixture was added to ultrapure water (205 g) over 30 minutes, then heptane (205 g) was added, and after stirring for 30 minutes, the organic layer was removed. The aqueous layer was washed three times with heptane (100 g), then MTBE (150 g) and 10% citric acid aqueous solution (205 g, 106.1 mmol) were added, and after stirring for 30 minutes, the aqueous layer was removed. The recovered organic layer was washed three times with ultrapure water (150 g), and the organic layer was concentrated using a rotary evaporator. The concentrate was recrystallized with ethyl acetate to obtain intermediate-AA (11.1 g, yield 58.3%).

[0370] [ka]

[0371] Synthesis of intermediates -BA,NA: Compound (M-1) was replaced with compounds (M-2) and (M-3) in equimolar amounts, respectively, and the synthesis was carried out in the same manner as the synthesis of intermediate-AA to obtain intermediates-BA and-NA.

[0372] [ka]

[0373] [Example of intermediate synthesis (4): Synthesis of intermediates LAA, LBA, and LNA] Synthesis of intermediate-LAA1: In a 200 mL three-necked flask, intermediate-AA (11.2, 32.2 mmol), α-hydroxy-γ-butyrolactone (lactone alcohol 1) (3.5 g, 34.0 mmol), and dichloromethane (180 g) were added and stirred at room temperature to dissolve. Next, diisopropylcarbodiimide (DIC) (6.2 g, 48.4 mmol) and dimethylaminopyridine (0.4 g, 3.2 mmol) were added, and the mixture was reacted at room temperature for 5 hours. The reaction mixture was filtered, and the recovered organic layer was transferred to a 300 mL three-necked flask. Subsequently, trifluoroacetic acid (TFA) (22 g, 193.2 mmol) was added, and the mixture was stirred at room temperature for 24 hours. The precipitated solid was filtered. The filtrate was again dissolved in methanol (60 g) and added dropwise to ultrapure water (600 g), and the precipitated solid was filtered. After repeating this procedure twice, the filtrate was dried under reduced pressure to obtain intermediate-LAA1 (9.1 g, yield 75.0%).

[0374] [ka]

[0375] Synthesis of intermediates LAA2 and LAA3: Lactone alcohol 1 was replaced with lactone alcohol 2 and lactone alcohol 3 in equimolar amounts, respectively, and the synthesis was carried out in the same manner as the synthesis of intermediate-LAA1 to obtain intermediate-LAA2 and intermediate-LAA3.

[0376] [ka]

[0377] [ka]

[0378] Synthesis of intermediates LBA1, LBA2, and LBA3: Intermediate AA was replaced with intermediate BA in equimolar amounts, and using lactone alcohols 1 to 3 respectively, the synthesis was carried out in the same manner as the synthesis of intermediate LBA1, yielding intermediates LBA1, LBA2, and LBA3.

[0379] [ka]

[0380] Synthesis of intermediates LNA1 and LNA2: Intermediate AA was replaced with intermediate NA in equimolar amounts, and using lactone alcohol 1 and lactone alcohol 3 respectively, the synthesis was carried out in the same manner as the synthesis of intermediate LAA1 to obtain intermediates LNA1 and LNA2.

[0381] [ka]

[0382] [Example of precursor synthesis (1): Synthesis of precursors (Bpre-01) to (Bpre-09)] Synthesis of the precursor (Bpre-01): Intermediate-LBA1 (4.0, 16.1 mmol), intermediate-H1 (8.1 g, 14.5 mmol), and dichloromethane (180 g) were added to a 200 mL three-necked flask and stirred at room temperature to dissolve. Next, diisopropylcarbodiimide (DIC) (3.1 g, 24.2 mmol) and dimethylaminopyridine (0.2 g, 1.6 mmol) were added and the mixture was reacted at room temperature for 5 hours. The reaction mixture was filtered, and the filtrate was concentrated using a rotary evaporator. The concentrate was dissolved in acetonitrile (40 g), then added dropwise to MTBE (200 g), and the precipitated solid was filtered. The filtrate was again dissolved in acetonitrile (50 g), added dropwise to MTBE (400 g), and the precipitated solid was filtered. After repeating this procedure twice, the filtrate was dried under reduced pressure to obtain the precursor (Bpre-01) (8.6 g, yield 75.5%).

[0383] [ka]

[0384] Synthesis of precursors (Bpre-02) to (Bpre-09): Using the carboxylic acid group of intermediates LBA1 to LBA3 (16.1 mmol) and the phenol type group of intermediates H1 to H7 (14.5 mmol), the synthesis was carried out in the same manner as the synthesis of precursor (Bpre-01), yielding precursors (Bpre-02) to (Bpre-09). The combinations of carboxylic acids and intermediates used to obtain each precursor are shown below. Precursor (Bpre-01): Combination of intermediate-LBA1 and intermediate-H1 Precursor (Bpre-02): Combination of intermediate-LBA1 and intermediate-H2 Precursor (Bpre-03): Combination of intermediate-LBA1 and intermediate-H3 Precursor (Bpre-04): Combination of intermediate-LBA1 and intermediate-H4 Precursor (Bpre-05): Combination of intermediate-LBA3 and intermediate-H2 Precursor (Bpre-06): Combination of intermediate-LBA2 and intermediate-H2 Precursor (Bpre-07): Combination of intermediate-LBA1 and intermediate-H5 Precursor (Bpre-08): Combination of intermediate-LBA1 and intermediate-H6 Precursor (Bpre-09): Combination of intermediate-LBA1 and intermediate-H7

[0385] [ka]

[0386] [ka]

[0387] [Example of precursor synthesis (2): Synthesis of precursors (Bpre-13) to (Bpre-17)] Using the carboxylic acid group of intermediates LNA1 and LNA2 (16.1 mmol) and the phenol type group of intermediates H1, H2, H4, and H5 (14.5 mmol), the synthesis was carried out in the same manner as the synthesis of precursor (Bpre-01), yielding precursors (Bpre-13) to (Bpre-17). The combinations of carboxylic acids and intermediates used to obtain each precursor are shown below. Precursor (Bpre-13): Combination of intermediate-LNA1 and intermediate-H1 Precursor (Bpre-14): Combination of intermediate-LNA1 and intermediate-H2 Precursor (Bpre-15): Combination of intermediate-LNA1 and intermediate-H4 Precursor (Bpre-16): Combination of intermediate-LNA2 and intermediate-H2 Precursor (Bpre-17): Combination of intermediate-LNA1 and intermediate-H5

[0388] [ka]

[0389] [Example of precursor synthesis (3): Synthesis of precursors (Bpre-19) to (Bpre-26)] Using the carboxylic acid group of intermediates LAA1, LAA2, and LAA3 (16.1 mmol) and the phenol type group of intermediates H1, H2, H4, H5, H6, and H7 (14.5 mmol), the synthesis was carried out in the same manner as the synthesis of precursor (Bpre-01), yielding precursors (Bpre-19) to (Bpre-26). The combinations of carboxylic acids and intermediates used to obtain each precursor are shown below. Precursor (Bpre-19): Combination of intermediate-LAA1 and intermediate-H1 Precursor (Bpre-20): Combination of intermediate-LAA1 and intermediate-H2 Precursor (Bpre-21): Combination of intermediate-LAA1 and intermediate-H4 Precursor (Bpre-22): Combination of intermediate-LAA2 and intermediate-H2 Precursor (Bpre-23): Combination of intermediate-LAA3 and intermediate-H2 Precursor (Bpre-24): Combination of intermediate-LAA1 and intermediate-H5 Precursor (Bpre-25): Combination of intermediate-LAA1 and intermediate-H6 Precursor (Bpre-26): Combination of intermediate-LAA1 and intermediate-H7

[0390] [ka]

[0391] [ka]

[0392] [Synthesis example of compound (B0): Synthesis of compounds (B0-1) to (B0-29)] Synthesis of compound (B0-1): The precursor (Bpre-01) (7.9 g, 10.0 mmol) and salt exchange compound A (3.8 g, 11.0 mmol) were dissolved in dichloromethane (120 g), and ultrapure water (120 g) was added. The mixture was reacted at room temperature for 30 minutes. After the reaction was complete, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (120 g). The organic phase was concentrated to dryness using a rotary evaporator to obtain compound (B0-1) (8.7 g, yield 96.5%).

[0393] [ka]

[0394] Synthesis of compounds (B0-2) to (B0-29): Compounds (B0-2) to (B0-29) were synthesized in the same manner as compound (B0-1), except that the combinations of the above precursors (Bpre-02) to (Bpre-09), precursors (Bpre-13) to (Bpre-17), precursors (Bpre-19) to (Bpre-26) and salt exchange compounds A to D below were changed.

[0395] [ka]

[0396] Each of the obtained compounds was subjected to NMR measurement, and its structure was identified based on the following analytical results.

[0397] Compound (B0-1): Combination of precursor (Bpre-01) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.67-7.90 (m, ArH+Ar-I, 17H), 7.53-7.63 (d, ArH, 4H), 6.94 (d, Ar-I, 1H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0398] Compound (B0-2): Combination of precursor (Bpre-02) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0399] Compound (B0-3): Combination of precursor (Bpre-03) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 9.48 (s, NH, 1H), 8.12 (m, Ar-I, 1H), 8.01 (d, Ar-I, 1H), 7.74-7.90 (m, ArH, 15H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0400] Compound (B0-4): Combination of precursor (Bpre-04) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 8.12 (d, Ar-I, 1H), 7.74-7.90 (m, ArH, 15H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2, 1H)

[0401] [ka]

[0402] Compound (B0-5): Combination of precursor (Bpre-05) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 4.51-4.68 (m, CF2CH2+CH (lactone), 4H), 3.31 (m, CH (lactone), 1H), 2.59 (m, CH (lactone), 2H), 1.63-2.10 (m, CH2 (lactone), 4H)

[0403] Compound (B0-6): Combination of precursor (Bpre-06) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.51 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.50 (m, CH2 (lactone), 1H), 4.37 (m, CH2 (lactone), 1H), 2.86 (m, CH2 (lactone), 1H), 2.66 (m, CH2 (lactone), 1H)

[0404] [ka]

[0405] Compound (B0-7): Combination of precursor (Bpre-07) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.90 (m, CF3CH, 1H), 5.39 (m, CH (lactone), 1H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0406] Compound (B0-8): Combination of precursor (Bpre-08) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.91-5.20 (m, CFCH, 1H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.95-4.20 (m, COOCH2CH2, 2H), 2.65 (m, CH2 (lactone), 1H), 2.30-2.45 (m, COOCH2CH2, 1H), 2.25 (m, CH2 (lactone), 1H), 2.05 (m, COOCH2CH2, 1H)

[0407] Compound (B0-9): Combination of precursor (Bpre-09) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.41 (m, CH2 (lactone), 1H), 4.05-4.25 (m, COOCH2CH2+CH2 (lactone), 3H), 2.63-2.73 (m, COOCH2CH2+CH2 (lactone), 3H), 2.25 (m, CH2 (lactone), 1H)

[0408] [ka]

[0409] Compound (B0-10): Combination of precursor (Bpre-02) and salt exchange compound B 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.70-8.22 (m, ArH+Ar-I, 16H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.30-3.45 (m, SO2CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H), 1.09-1.90 (m, cyclohexyl, 10H)

[0410] Compound (B0-11): Combination of precursor (Bpre-02) and salt exchange compound C 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.77-7.99 (m, ArH+Ar-I, 13H), 7.53-7.63 (d, ArH, 4H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0411] Compound (B0-12): Combination of precursor (Bpre-02) and salt exchange compound D 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 8.50 (d, ArH, 2H), 8.37 (d, ArH, 2H), 7.99 (d, Ar-I, 1H), 7.93 (t, ArH, 2H), 7.84 (d, Ar-I, 1H), 7.53-7.75 (d, ArH, 11H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0412] [ka]

[0413] Compound (B0-13): Combination of precursor (Bpre-13) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.74-7.90 (m, ArH+Ar-I, 17H), 6.94 (d, Ar-I, 1H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.38 (m, CH, 1H), 2.25 (m, CH2 (lactone), 1H), 1.30-1.50 (m, CH2, 2H)

[0414] Compound (B0-14): Combination of precursor (Bpre-14) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.38 (m, CH, 1H), 2.25 (m, CH2 (lactone), 1H), 1.30-1.50 (m, CH2, 2H)

[0415] Compound (B0-15): Combination of precursor (Bpre-15) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 8.12 (d, Ar-I, 1H), 7.74-7.90 (m, ArH, 15H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 5.39 (m, CH (lactone), 1H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.38 (m, CH, 1H), 2.25 (m, CH2 (lactone), 1H), 1.30-1.50 (m, CH2, 2H)

[0416] Compound (B0-16): Combination of precursor (Bpre-16) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 4.51-4.68 (m, CF2CH2+CH (lactone), 4H), 3.31 (m, CH (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.59 (m, CH (lactone), 2H), 2.38 (m, CH, 1H), 1.63-2.10 (m, CH2 (norbornene)+CH2 (lactone), 6H)

[0417] [ka]

[0418] Compound (B0-17): Combination of precursor (Bpre-17) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 5.90 (m, CF3CH, 1H), 5.39 (m, CH (lactone), 1H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.38 (m, CH, 1H), 2.25 (m, CH2 (lactone), 1H), 1.30-1.50 (m, CH2, 2H)

[0419] Compound (B0-18): Combination of precursor (Bpre-17) and salt exchange compound C 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.77-7.99 (m, ArH, 13H), 6.30 (d, CH, 1H), 6.10 (d, CH, 1H), 5.90 (m, CF3CH, 1H), 5.39 (m, CH (lactone), 1H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15 (m, CH, 2H), 3.00 (m, CH, 1H), 2.65 (m, CH2 (lactone), 1H), 2.38 (m, CH, 1H), 2.25 (m, CH2 (lactone), 1H), 1.30-1.50 (m, CH2, 2H)

[0420] [ka]

[0421] Compound (B0-19): Combination of precursor (Bpre-19) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.74-7.90 (m, ArH+Ar-I, 17H), 7.01-7.47 (m, ArH, 8H), 6.94 (d, Ar-I, 1H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0422] Compound (B0-20): Combination of precursor (Bpre-20) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (m, Ar-I, 1H), 7.74-7.90 (m, ArH+ Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0423] Compound (B0-21): Combination of precursor (Bpre-21) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 8.12 (m, Ar-I, 1H), 7.74-7.90 (m, ArH, 15H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0424] Compound (B0-22): Combination of precursor (Bpre-22) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (m, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.51 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.50 (m, CH2 (lactone), 1H), 4.37 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.86 (m, CH2 (lactone), 1H), 2.66 (m, CH2 (lactone), 1H)

[0425] Compound (B0-23): Combination of precursor (Bpre-23) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (m, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2+CH (lactone), 4H), 3.15-3.40 (m, CH, 3H), 2.59 (m, CH (lactone), 2H), 1.63-2.10 (m, CH2 (lactone), 4H)

[0426] [ka]

[0427] Compound (B0-24): Combination of precursor (Bpre-24) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (m, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.90 (m, CF3CH, 1H), 5.51 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.50 (m, CH2 (lactone), 1H), 4.37 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.86 (m, CH2 (lactone), 1H), 2.66 (m, CH2 (lactone), 1H)

[0428] Compound (B0-25): Combination of precursor (Bpre-25) and salt exchange compound A 1¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.91-5.20 (m, CFCH, 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 3.95-4.20 (m, COOCH2CH2, 2H), 2.65 (m, CH2 (lactone), 1H), 2.30-2.45 (m, COOCH2CH2, 1H), 2.25 (m, CH2 (lactone), 1H), 2.05 (m, COOCH2CH2, 1H)

[0429] Compound (B0-26): Combination of precursor (Bpre-26) and salt exchange compound A 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.99 (d, Ar-I, 1H), 7.74-7.90 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.41 (m, CH2 (lactone), 1H), 4.05-4.25 (m, COOCH2CH2+CH2 (lactone), 3H), 3.15-3.40 (m, CH, 2H), 2.63-2.73 (m, COOCH2CH2+CH2 (lactone), 3H), 2.25 (m, CH2 (lactone), 1H)

[0430] [ka]

[0431] Compound (B0-27): Combination of precursor (Bpre-20) and salt exchange compound B 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.70-8.22 (m, ArH+Ar-I, 16H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.45 (m, SO2CH+CH, 3H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H), 1.09-1.90 (m, cyclohexyl, 10H)

[0432] Compound (B0-28): Combination of precursor (Bpre-20) and salt exchange compound C 1 ¹H-NMR (DMSO, 400MHz): δ(ppm) = 7.77-7.99 (m, ArH+Ar-I, 13H), 7.01-7.47 (m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0433] Compound (B0-29): Combination of precursor (Bpre-20) and salt exchange compound D 1H-NMR(DMSO,400MHz):δ(ppm)=8.50 (d, ArH, 2H), 8.37 (d, ArH, 2H), 7.99 (m, Ar-I, 1H), 7.93 (t, ArH, 2H), 7.84 (d, Ar-I, 1H), 7.55-7.75 (m, ArH, 7H), 7.01-7.47(m, ArH, 8H), 5.39 (m, CH (lactone), 1H), 4.70-4.85 (m, -OCO-CH-CH-COO-, 2H), 4.51-4.68 (m, CF2CH2, 2H), 4.41 (m, CH2 (lactone), 1H), 4.25 (m, CH2 (lactone), 1H), 3.15-3.40 (m, CH, 2H), 2.65 (m, CH2 (lactone), 1H), 2.25 (m, CH2 (lactone), 1H)

[0434] [ka]

[0435] <Preparation of the resist composition> (Examples 1-33, Comparative Examples 1-4) Each of the components shown in Tables 1-5 was mixed and dissolved to prepare the resist compositions for each example.

[0436] [Table 1]

[0437] [Table 2]

[0438] [Table 3]

[0439] [Table 4]

[0440] [Table 5]

[0441] In Tables 1-5, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients. (A)-1: A polymer compound represented by the following chemical formula (A1-1). For this polymer compound (A1-1), the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 5800, and the molecular weight dispersion (Mw / Mn) is 1.54. 13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 50 / 50. (A)-2: A polymer compound represented by the following chemical formula (A1-2). For this polymer compound (A1-2), the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 6000, and the molecular weight dispersion (Mw / Mn) is 1.55. 13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 50 / 50. (A)-3: A polymer compound represented by the following chemical formula (A1-3). For this polymer compound (A1-3), the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 5900, and the molecular weight dispersion (Mw / Mn) is 1.54. 13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 50 / 50.

[0442] [ka]

[0443] (B)-31: An acid generator consisting of the following compound (B1-1). (B)-32: An acid generator consisting of the following compounds (B1-2). (B)-33: An acid generator consisting of the following compounds (B1-3). (B)-34: An acid generator consisting of the following compounds (B1-4). (B)-1 to (B)-29: Compounds (B0-1) to (B0-29) listed above.

[0444] [ka]

[0445] (D)-1: An acid diffusion control agent consisting of the following compound (D1-1).

[0446] [ka]

[0447] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0448] <Resist pattern formation> Each example of the resist composition was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and a 50 nm thick resist film was formed by pre-baking (PAB) on a hot plate at 110°C for 60 seconds and drying. Next, the resist film was subjected to a JEOL-JBX-9300FS electron beam lithography system (manufactured by JEOL Ltd.) at an acceleration voltage of 100kV to create a contact hole pattern (hereinafter referred to as the "CH pattern") in which holes with a diameter of 32nm were arranged at equal intervals (pitch of 64nm). Subsequently, post-exposure heating (PEB) treatment was performed at 100°C for 60 seconds. Next, alkaline development was performed at 23°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterward, a 15-second rinse was performed using pure water. As a result, a CH pattern was formed in which holes with a diameter of 32 nm were arranged at equal intervals (pitch of 64 nm).

[0449] [Sensitivity evaluation] The optimal exposure amount Eop(μC / cm²) for forming a CH pattern of the target size through the above <resist pattern formation> method is to form a CH pattern of the target size. 2 The result was calculated as "Eop(μC / cm²)". 2 )" is shown in Tables 6-7.

[0450] [Evaluation of in-plane uniformity (CDU) of pattern dimensions] The CH pattern formed by the above <Resist Pattern Formation> was observed from above using a measuring SEM (Scanning Electron Microscope, accelerating voltage 500V, product name: CG5000, Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. Then, the value of three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. The results are shown in Tables 6-7 as "CDU (nm)". The smaller the 3σ value obtained in this way, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film.

[0451] [Evaluation of limiting resolution] The critical resolution at the optimal exposure dose (Eop) for forming the CH pattern as described above (<Resist Pattern Formation>) was determined using a scanning electron microscope (product name: S-9380, Hitachi High-Technologies Corporation). Specifically, the hole diameter (nm) of the pattern resolved when gradually decreasing the exposure dose from the optimal exposure dose (Eop) to form the CH pattern was determined. The results are shown in Tables 6-7 as "Critical Resolution (nm)".

[0452] [Table 6]

[0453] [Table 7]

[0454] From the results shown in Tables 6-7, a comparison of Examples 1-33 with Comparative Examples 1-4 confirms that the resist compositions of Examples 1-33 to which the present invention is applied achieve both high sensitivity and in-plane uniformity of pattern dimensions (CDU) and fine resolution. In addition, it can be confirmed that the resist compositions of Examples 1 to 33 have improved CDU and fine resolution compared to the resist compositions of Comparative Examples 1 to 4.

Claims

1. A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, A base component (A) whose solubility in the developer changes due to the action of acid, Compound (B0) represented by the following general formula (b0), A resist composition containing the following: 【Chemistry 1】 [In the formula, R ｂ is a base-labile group. L ０３ is a divalent linking group. Rl ０ is a cyclic organic group which may have a substituent. L ０２ is a divalent linking group. I is an iodine atom. R ｍ１ is a substituent other than an iodine atom. L ０１ is a divalent linking group or a single bond. Vb ０ is an alkylene group, a fluorinated alkylene group or a single bond. However, L ０１ and Vb ０ do not simultaneously become a single bond. R ０ is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom. nb1 is an integer between 1 and 4, nb2 is an integer between 1 and 4, and nb3 is an integer between 0 and 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. M ｍ＋ This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

2. R in the above general formula (b0) ｂ The resist composition according to claim 1, wherein the group includes a lactone-containing cyclic group.

3. -L in the above general formula (b0) ０１ -Vb ０ The resist composition according to claim 1 or 2, wherein - is a linking group represented by any of the following general formulas (b0-r-1) to (b0-r-7). 【Chemistry 2】 [In the formula, L ０１１ L is an alkylene group or single bond having 1 to 5 carbon atoms. ０１２ Vb is a divalent saturated hydrocarbon group or single bond having 1 to 30 carbon atoms. ０１ This is a fluorinated alkylene group or single bond having 1 to 4 carbon atoms. However, L ０１２ and Vb ０１ They cannot be single bonds at the same time.

4. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition described in claim 1 or 2; exposing the resist film; and developing the exposed resist film to form a resist pattern.

5. A compound represented by the following general formula (b0). 【Transformation 3】 [In the formula, R ｂ L is a basic-degradable group. ０３ Rl is a divalent linking group. ０ L is a cyclic organic group which may have substituents. ０２ R is a divalent linking group. I is an iodine atom. ｍ１ L is a substituent other than the iodine atom. ０１ Vb is a divalent linking group or a single bond. ０ is an alkylene group, a fluorinated alkylene group, or a single bond. However, L ０１ and Vb ０ It is impossible for them to be single bonds at the same time. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom. nb1 is an integer between 1 and 4, nb2 is an integer between 1 and 4, and nb3 is an integer between 0 and 3. However, 2 ≤ nb1 + nb2 + nb3 ≤ 5. M ｍ＋ This represents an m-valent organic cation, where m is an integer greater than or equal to 1.

6. R in the above general formula (b0) ｂ The compound according to claim 5, wherein the group includes a lactone-containing cyclic group.

7. -L in the above general formula (b0) ０１ -Vb ０ The compound according to claim 5 or 6, wherein - is a linking group represented by any of the following general formulas (b0-r-1) to (b0-r-7). 【Chemistry 4】 [In the formula, L ０１１ L is an alkylene group or single bond having 1 to 5 carbon atoms. ０１２ Vb is a divalent saturated hydrocarbon group or single bond having 1 to 30 carbon atoms. ０１ This is a fluorinated alkylene group or single bond having 1 to 4 carbon atoms. However, L ０１２ and Vb ０１ They cannot be single bonds at the same time.

8. An acid generator comprising the compound described in claim 5 or 6.

Images