Resist composition and method for forming resist pattern

Abstract

To provide a resist composition which achieves both higher sensitivity and roughness reduction when forming a resist pattern and can form a pattern having a good shape with increased rectangularity, a resist pattern forming method, and a compound useful as a basic component for the resist composition.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 (d0). In the formula (d0), Rf represents a hydrocarbon group which may have a fluorine atom; L2 represents an optionally substituted divalent cyclic group; L1 and L3 each independently represent a divalent linking group; x represents an integer of 1-4; Rd0 represents an iodine atom or a bromine atom; y represents an integer of 1-4; z represents an integer of 0-3, provided that 2≤x+y+z≤5; (Mm+)1 / m represents a counter 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 method of forming a resist pattern, a compound, and an acid diffusion controller. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid progress in miniaturization of patterns in the manufacture of semiconductor devices and liquid crystal display devices. A common method of miniaturization is to use shorter wavelengths (higher energy) exposure light sources. Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.

[0003] In forming a resist pattern, the behavior of the acid generated from an acid generator component upon exposure is considered to be one factor that greatly influences the lithography properties. A wide variety of acid generators have been proposed for use in chemically amplified resist compositions, including, for example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators. In general, an alkylsulfonate ion or a fluorinated alkylsulfonate ion in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is used in the anion portion of an onium salt acid generator. In the cation portion of an onium salt acid generator, an onium ion such as triphenylsulfonium is mainly used.

[0004] Further, as a resist material, a chemically amplified resist composition has been proposed which uses, together with an acid generator component, an acid diffusion controller that controls the diffusion of the acid generated from the acid generator component upon exposure. For example, Patent Document 1 discloses a resist composition in which a carboxylate having a specific structure in the anion moiety is selected as an acid diffusion controller. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2022-14782 Summary of the Invention [Problem to be solved by the invention]

[0006] With the further progress of lithography technology and the expansion of application fields, patterns are rapidly becoming finer. Accordingly, when manufacturing semiconductor devices, etc., technology that can form fine patterns with good shapes is required. For example, in lithography using EUV (extreme ultraviolet) or EB (electron beam), the goal is to form fine patterns of several tens of nm. As the pattern dimensions become smaller, it is required to further improve lithography characteristics such as sensitivity, pattern shape, and roughness reduction without making a trade-off between them.

[0007] The present invention has been made in consideration of the above-mentioned circumstances, and an object of the present invention is to provide a resist composition that is capable of achieving both high sensitivity and reduced roughness when forming a resist pattern, and is capable of forming a pattern with a good shape that has enhanced rectangularity; a method of forming a resist pattern that uses the resist composition; and a compound that is useful as a base component for use 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 due to the action of the acid, the resist composition comprising: a base component (A) whose solubility in a developer changes due to the action of an acid; and a compound (D0) represented by the following general formula (d0):

[0009] [ka] [In the formula, Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 1 and L 3 are each independently a divalent linking group. x is an integer of 1 to 4. When x is an integer of 2 or more, a plurality of -L 1 -L 2 -L 3 -Rf may be the same or different. d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. z is an integer of 0 to 3, provided that 2≦x+y+z≦5. (M m+ ) 1 / m is a counter cation. m is an integer of 1 or more.

[0010] A second aspect of the present invention is a method for forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition related to the first aspect, exposing the resist film, and developing the exposed resist film to form a resist pattern.

[0011] A third aspect of the present invention is a compound represented by the following general formula (d0).

[0012] [ka] [In the formula, Rf is a hydrocarbon group which may have a fluorine atom. 2L is a divalent cyclic group which may have a substituent. 1 and L 3 are each independently a divalent linking group. x is an integer of 1 to 4. When x is an integer of 2 or more, a plurality of -L 1 -L 2 -L 3 -Rf may be the same or different. d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. z is an integer of 0 to 3, provided that 2≦x+y+z≦5. (M m+ ) 1 / m is a counter cation. m is an integer of 1 or more.

[0013] A fourth aspect of the present invention is an acid diffusion controller comprising the compound according to the third aspect. Effect of the Invention

[0014] According to the present invention, it is possible to provide a resist composition that can achieve both high sensitivity and reduced roughness when forming a resist pattern, and that is capable of forming a pattern with a good shape that has improved rectangularity; a method of forming a resist pattern that uses the resist composition; and a compound that is useful as a base component for use in the resist composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this specification and claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group, compound, etc. that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "may have a substituent" includes both the case where a hydrogen atom (-H) is replaced with a monovalent group and the case where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is intended to include any concept including irradiation with radiation.

[0016] The term "acid-decomposable group" refers to a group having acid decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of acid-decomposable groups whose polarity increases under the action of an acid include groups that are decomposed by the action of an acid to generate a polar group. Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO3H). More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).

[0017] The term "acid dissociable group" refers to both (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, and (ii) a group in which a portion of the bond is cleaved by the action of an acid and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group. The acid dissociable group constituting the acid decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid dissociable group, and thus, when the acid dissociable group is dissociated by the action of an acid, a polar group with higher polarity than the acid dissociable group is generated, increasing the polarity. As a result, the polarity of the entire base material component increases. By increasing the polarity, the solubility in the developer changes relatively, and when the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.

[0018] The "base material component" is an organic compound having a film-forming ability. Organic compounds used as base material components are broadly classified into non-polymers and polymers. As non-polymers, those having a molecular weight of 500 or more and less than 4000 are usually used (hereinafter referred to as "low molecular weight compounds"). Hereinafter, when "resin", "polymeric compound" or "polymer" is mentioned, it refers to a polymer having a molecular weight of 1000 or more. As the molecular weight of a polymer, the weight average molecular weight calculated in terms of polystyrene by GPC (gel permeation chromatography) is used.

[0019] The term "derived structural unit" refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. αx ) is an atom or group other than a hydrogen atom. αx Itaconic acid diesters in which the substituent (R αx It also includes α-hydroxyacrylic esters in which the α-position carbon atom of an acrylic ester is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group of the acrylic ester. Unless otherwise specified, the carbon atom at the α-position of an acrylic ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, an acrylic ester in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent will sometimes be referred to as an α-substituted acrylic ester.

[0020] The term "derivative" refers to a concept that includes compounds in which the hydrogen atom at the α-position of the target compound is replaced with other substituents such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include compounds in which the hydrogen atom of the hydroxyl group of a target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is replaced with an organic group; compounds in which the hydrogen atom at the α-position of a target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is bonded with a substituent other than a hydroxyl group, and the like. The α-position refers to the first carbon atom adjacent to the functional group, unless otherwise specified. The substituent that replaces the hydrogen atom at the α-position of hydroxystyrene is R αx Examples of the alkyl group include an alkyl group and a halogenated alkyl group.

[0021] In the present specification and claims, some structures represented by chemical formulas may have asymmetric carbons, and may have enantiomers or diastereomers. In such cases, a single chemical formula represents all of the isomers. These isomers may be used alone or as a mixture.

[0022] (Resist composition) The resist composition related to the first aspect of the present invention generates an acid upon exposure, and the solubility in a developer changes due to the action of the acid. One embodiment of such a resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer changes under the action of an acid, and a base component (hereinafter also referred to as "component (D)") that traps the acid generated by exposure (i.e., controls the diffusion of the acid). In the resist composition of this embodiment, a compound (D0) represented by general formula (d0) is used as the component (D).

[0023] In the resist composition of this embodiment, the component (A) may generate an acid upon exposure, or a component that is blended separately from the component (A) may generate an acid upon exposure. Specifically, the resist composition of this embodiment may be one that further contains (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) the component (A) may be a component that generates an acid upon exposure; or (3) the component (A) may be a component that generates an acid upon exposure, and may further contain component (B). That is, in the above cases of (2) and (3), the component (A) is a "base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid." When the component (A) is a base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid, the component (A1) described below is preferably a resin that generates an acid upon exposure and changes its solubility in a developer by the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, a known one can be used.

[0024] Among the above, the resist composition of this embodiment is preferably the above-mentioned case (1). That is, the resist composition of this embodiment preferably contains the component (A), the compound (D0), and the component (B).

[0025] When a resist film is formed using the resist composition of this embodiment and the resist film is selectively exposed, an acid is generated from the component (B) in the exposed portion of the resist film, for example, and the solubility of the component (A) in the developer changes due to the action of the acid, while the solubility of the component (A) in the developer does not change in the unexposed portion of the resist film, so that a difference in solubility in the developer occurs between the exposed portion and the unexposed portion of the resist film. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the unexposed portion of the resist film is dissolved and removed to form a negative type resist pattern.

[0026] The resist composition of the present embodiment may be a positive resist composition or a negative resist composition. The resist composition of the present embodiment may be for an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or may be for a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.

[0027] <(A) component: base material component> In the resist composition of this embodiment, the component (A) preferably contains a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in a developer changes under the action of an acid. By using the component (A1), the polarity of the base component changes before and after exposure, so that good development contrast can be obtained not only in an alkaline development process but also in a solvent development process. As the component (A), at least one other polymeric compound and low molecular weight compound may be used in combination with the component (A1).

[0028] In the resist composition of this embodiment, the component (A) may use either a single type, or a combination of two or more types.

[0029] Regarding component (A1) The component (A1) is a resin component whose solubility in a developer changes under the action of an acid. The component (A1) preferably has a structural unit (a1) that contains an acid-decomposable group whose polarity increases under the action of an acid. The component (A1) may contain other structural units in addition to the structural unit (a1), as necessary. Examples of other structural units include the structural unit (a10) represented by the general formula (a10-1) described below; the structural unit (a2) containing a lactone-containing cyclic group; and the structural unit (a8) derived from a compound represented by the general formula (a8-1) described below.

[0030] Regarding the structural unit (a1): The structural unit (a1) is a structural unit that contains an acid-decomposable group whose polarity increases when acted upon by an acid.

[0031] Examples of the acid-decomposable group include a group in which a polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group). Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups in base resins for chemically amplified resist compositions. Specific examples of the acid dissociable group that have been proposed for the base resin of the chemically amplified resist composition include the “acetal type acid dissociable group,” “tertiary alkyl ester type acid dissociable group,” “tertiary alkyloxycarbonyl acid dissociable group,” and “secondary alkyl ester type acid dissociable group,” which are explained below.

[0032] Acetal type acid dissociable group: Among the polar groups, examples of the acid-dissociable group that protects a carboxy group or a hydroxyl group include an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0033] [ka] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. 3 is a hydrocarbon group, and Ra' 3 Is, Ra' 1 , Ra' 2 may be bonded to any one of the following to form a ring.

[0034] In formula (a1-r-1), Ra' 1 and Ra' 2 At least one of these is preferably a hydrogen atom, and both are more preferably hydrogen atoms. Ra' 1 Or Ra' 2 When is an alkyl group, the alkyl group may be the same as the alkyl group exemplified as the substituent that may be bonded to the carbon atom at the α-position in the explanation of the α-substituted acrylic acid ester above, and an alkyl group having 1 to 5 carbon atoms is preferable. Specifically, a linear or branched alkyl group is preferable. More specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like are preferable, and a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

[0035] In formula (a1-r-1), Ra' 3 Examples of the hydrocarbon group include a linear or branched alkyl group, and a cyclic hydrocarbon group. 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. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0036] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.

[0037] Ra' 3 When is a cyclic hydrocarbon group, the hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The alicyclic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0038] Ra' 3 When the cyclic hydrocarbon group is 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 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Ra' 3 Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The number of carbon atoms of 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.

[0039] Ra' 3 The cyclic hydrocarbon group in may have a substituent. Examples of the substituent 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 (hereinafter, these substituents are collectively referred to as "Rax5 " Also known as ".) Here, R P1 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. P2 is a single bond, a divalent linear 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. P1 and R P2 Some or all of the hydrogen atoms in the chain saturated hydrocarbon group, the alicyclic saturated hydrocarbon group and the aromatic hydrocarbon group may be substituted with fluorine atoms. The alicyclic hydrocarbon group may have one or more of the above-mentioned substituents or may have one or more of each of the above-mentioned substituents. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, or phenanthrene.

[0040] Ra' 3 But Ra' 1 , Ra' 2When it is bonded to any one of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, etc.

[0041] Tertiary alkyl ester type acid-labile group: Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-2). Among the acid-dissociable groups represented by the following formula (a1-r-2), those constituted by an alkyl group may be referred to as "tertiary alkyl ester-type acid-dissociable groups" hereinafter for the sake of convenience.

[0042] [ka] [In the formula, Ra' 4 ~Ra' 6 are each a hydrocarbon group, and Ra' 5 , Ra' 6 may be bonded to each other to form a ring.

[0043] Ra' 4 Examples of the hydrocarbon group include a linear or branched alkyl group, a linear or cyclic alkenyl group, a linear alkynyl group, or a cyclic hydrocarbon group. Ra' 4 The linear or branched alkyl group and the cyclic hydrocarbon group (the alicyclic hydrocarbon group which is a monocyclic group, the alicyclic hydrocarbon group which is a polycyclic group, and the aromatic hydrocarbon group) in the formula Ra' 3 The same can be mentioned. Ra' 4 The chain or cyclic alkenyl group in is preferably an alkenyl group having 2 to 10 carbon atoms. Ra' 5 , Ra' 6 As the hydrocarbon group of Ra' 3 The same can be mentioned.

[0044] Ra' 5 and Ra'6 and (a1-r2-3) are preferably used. On the other hand, Ra' 4 ~Ra' 6 When are not bonded to each other and are independent hydrocarbon groups, preferred examples include groups represented by the following general formula (a1-r2-4).

[0045] [ka] [In formula (a1-r2-1), Ra' 10 Ra' represents a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group. 11 Is Ra' 10 In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in the linear saturated hydrocarbon group and the cyclic aliphatic saturated hydrocarbon group may be substituted. 101 ~Ra 103 Two or more of 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 which forms an aliphatic cyclic group together with Yaa. Ra 104 In formula (a1-r2-4), Ra' is an aromatic hydrocarbon group which may have a substituent. 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted. 14is a hydrocarbon group which may have a substituent. * indicates a bond (hereinafter the same).

[0046] In the above formula (a1-r2-1), Ra' 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be partially substituted with a halogen atom or a heteroatom-containing group.

[0047] Ra' 10 In the formula, the linear alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra' 10 As the branched alkyl group in the formula (I), 3 The same can be mentioned.

[0048] Ra' 10 The alkyl group in may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. In addition, some of the carbon atoms (e.g., methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group. The heteroatom includes an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0049] In formula (a1-r2-1), Ra' 11 (Ra' 10 The aliphatic cyclic group formed together with the carbon atom to which is bonded) is Ra' in formula (a1-r-1). 3 Among them, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl and cyclohexyl groups are more preferred.

[0050] In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya includes Ra' in the formula (a1-r-1). 3 Examples of such groups include groups in which one or more hydrogen atoms have been further removed from the cyclic monovalent hydrocarbon group (alicyclic hydrocarbon group) in the above formula. The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of the substituent include the above-mentioned Ra' 3 Examples of the substituents include those similar to those that the cyclic hydrocarbon group in the above may have. In formula (a1-r2-2), Ra 101 ~Ra 103 In the above formula, examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. Ra 101 ~Ra 103 In the above formula, examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group. Ra 101 ~Ra 103 Among these, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among these, a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.

[0051] The above Ra 101 ~Ra 103 Examples of the substituents of the chain saturated hydrocarbon group or the cyclic saturated aliphatic hydrocarbon group represented by the formula x5 The same groups as those shown below can be mentioned.

[0052] Ra101 ~Ra 103 Examples of groups containing a carbon-carbon double bond formed by two or more of the above being bonded to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.

[0053] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is represented by Ra' in formula (a1-r-1). 3 The groups mentioned above as the alicyclic hydrocarbon group are preferably monocyclic or polycyclic groups of the above formula. In formula (a1-r2-3), Ra 104 Examples of the aromatic hydrocarbon group in the formula include a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. 104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.

[0054] Ra in formula (a1-r2-3) 104 Examples of the substituent that may be possessed by the group include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), and an alkyloxycarbonyl group.

[0055] In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of Ra' is independently a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. 12 and Ra' 13In the above, the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms is 101 ~Ra 103 Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in the above formula (1) include those in which some or all of the hydrogen atoms in the chain saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 Among these, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group or an ethyl group is further preferable, and a methyl group is particularly preferable. The above Ra' 12 and Ra' 13 In the case where the chain saturated hydrocarbon group represented by the formula (I) is substituted, examples of the substituent include the above-mentioned Ra x5 The same groups as those shown below can be mentioned.

[0056] In formula (a1-r2-4), Ra' 14 Ra' is a hydrocarbon group which may have a substituent. 14 The hydrocarbon group in the formula (I) includes a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0057] Ra' 14 The linear alkyl group in the formula (I) preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0058] Ra' 14 The branched alkyl group in the above formula (I) preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.

[0059] Ra'14 When is a cyclic hydrocarbon group, the hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The alicyclic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0060] Ra' 14 As the aromatic hydrocarbon group in 104 Among them, the aromatic hydrocarbon group Ra' is the same as that in 14 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene. Ra' 14 Examples of the substituent that may be possessed by Ra include 104 The substituents may be the same as those which may be possessed by the group.

[0061] Ra' in formula (a1-r2-4) 14 When is a naphthyl group, the position at which it is bonded to the tertiary carbon atom in the above formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group. Ra' in formula (a1-r2-4) 14When is an anthryl group, the position at which it is bonded to the tertiary carbon atom in the above formula (a1-r2-4) may be any one of the 1-position, 2-position, or 9-position of the anthryl group.

[0062] Specific examples of the group represented by formula (a1-r2-1) are shown below.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] Specific examples of the group represented by formula (a1-r2-2) are shown below.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] Specific examples of the group represented by formula (a1-r2-3) are shown below.

[0071] [ka]

[0072] Specific examples of the group represented by formula (a1-r2-4) are shown below.

[0073] [ka]

[0074] Tertiary alkyloxycarbonyl acid dissociating group: Among the polar groups, examples of the acid dissociable group that protects the hydroxyl group include acid dissociable groups represented by the following general formula (a1-r-3) (hereinafter, for convenience, may be referred to as "tertiary alkyloxycarbonyl acid dissociable group").

[0075] [ka] [In the formula, Ra' 7 ~Ra' 9 are each an alkyl group.

[0076] In formula (a1-r-3), Ra' 7 ~Ra' 9 Each of the groups is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0077] Secondary alkyl ester type acid-labile group: Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-4).

[0078] [ka] [In the formula, Ra' 10 is a hydrocarbon group. 11a and Ra' 11b Each of Ra' independently represents a hydrogen atom, a halogen atom, or an alkyl group. 12is a hydrogen atom or a hydrocarbon group. 10 and Ra' 11a Or Ra' 11b and may be bonded to each other to form a ring. 11a Or Ra' 11b And, Ra' 12 may be bonded to each other to form a ring.

[0079] In the formula, Ra' 10 and Ra' 12 As the hydrocarbon group in Ra', 3 The same can be mentioned. In the formula, Ra' 11a and Ra' 11b As the alkyl group in the above, Ra' 1 The alkyl groups in the above formula (I) are the same as those in the above formula (I). In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in 11a and Ra' 11b The alkyl group in may have a substituent. Examples of the substituent include the above-mentioned Ra x5 etc.

[0080] Ra' 10 and Ra' 11a Or Ra' 11b may be bonded to each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, an alicyclic ring, or an aromatic ring. The alicyclic and aromatic rings may contain heteroatoms.

[0081] Ra' 10 and Ra' 11a Or Ra' 11b and are bonded to each other to form a ring. Among the above, preferred are monocycloalkenes, rings in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), and monocycloalkadiene, more preferred are cycloalkenes having 3 to 6 carbon atoms, and more preferred are cyclopentene or cyclohexene.

[0082] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by bonding with each other may be a condensed ring. Specific examples of the condensed ring include indan.

[0083] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by bonding with each other may have a substituent. Examples of the substituent include the above-mentioned Ra x5 etc.

[0084] Ra' 11a Or Ra' 11b And, Ra' 12 and may be bonded to each other to form a ring, and the ring may include Ra' 10 and Ra' 11a Or Ra' 11b and the like are similar to the ring formed by bonding with each other.

[0085] Specific examples of the group represented by formula (a1-r-4) are shown below.

[0086] [ka]

[0087] Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, a structural unit derived from an acrylamide, a structural unit derived from hydroxystyrene or a hydroxystyrene derivative in which at least a portion of the hydrogen atoms in the hydroxyl groups are protected with a substituent containing the above-mentioned acid-decomposable group, and a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative in which at least a portion of the hydrogen atoms in -C(═O)-OH are protected with a substituent containing the above-mentioned acid-decomposable group.

[0088] Of the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. Preferred specific examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1), (a1-2) and (a1-3).

[0089] [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. 1 is a divalent hydrocarbon group which may have an ether bond. a1 is an integer from 0 to 2. 1 is an acid-dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4). 1 is a2 +1 valent hydrocarbon group. n a2 is an integer from 1 to 3. 2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3). 001 is a single bond or a divalent linking group. 01 is a single bond or a divalent linking group. 01 is an acid dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4). q is an integer of 0 to 3. n is an integer of 1 or more, provided that n≦q×2+4.]

[0090] In the formulas (a1-1) to (a1-3), the alkyl group of R having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The 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. As the halogen atom, a fluorine atom is particularly preferable. 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 from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

[0091] In the formula (a1-1), Va 1 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0092] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in the formula (I) may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0093] 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 the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0094] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group. 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. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, specifically cycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0095] Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. Such an 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 the substituents. Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0096] In the formula (a1-1), Ra 1 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4), and among these, a group represented by general formula (a1-r2-1) or an acid dissociable group represented by general formula (a1-r-4) is more preferable.

[0097] In the 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, and is usually preferably saturated. The aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group that combines a straight-chain or branched-chain aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in its structure. The above n a2 The +1 valency is preferably 2 to 4, more preferably 2 or 3. In the formula (a1-2), Ra 2 is preferably an acid dissociable group represented by the above general formula (a1-r-1).

[0098] In the formula (a1-3), Ya 001 The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 001 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, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Among these, Ya 001is preferably a combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group, or a single bond, and more preferably a single bond.

[0099] In the formula (a1-3), Ya 01 The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 01 Among the above, Ya 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. 01 is preferably a combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group, or a single bond, and more preferably a single bond.

[0100] In the formula (a1-3), Rax 01 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4), and among these, an acid dissociable group represented by general formula (a1-r-2) is more preferable, and a group represented by general formula (a1-r2-1) is even more preferable.

[0101] In the formula (a1-3), q is an integer of 0 to 3. When q is 0, the structure is a benzene structure, when q is 1, the structure is a naphthalene structure, when q is 2, the structure is an anthracene structure, and when q is 3, the structure 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 formula (a1-3), n≦q×2+4. For example, when q is 1 and the naphthalene structure is a naphthalene structure, all six hydrogen atoms of the naphthalene may be substituted with hydroxy groups. 001 , -Ya 01 -C(=O)-O-Ra01 The substitution positions of the group and the hydroxy group are not particularly limited.

[0102] Specific examples of the structural unit (a1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[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 structural unit (a1) contained in the component (A1) may be of one type, or two or more types. As the structural unit (a1), a structural unit represented by the above formula (a1-1) or a structural unit represented by the above formula (a1-3) is more preferable, since these structural units are capable of more easily improving the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography. Among these, the acid dissociable group (Ra 1 , Rax 01 ) are preferably acid-dissociable groups represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), respectively, and among these, it is particularly preferable to select those which are cyclic groups.

[0117] When the component (A1) contains the structural unit (a1), the proportion of the structural unit (a1) in the component (A1) is preferably 20 to 80 mol %, more preferably 25 to 75 mol %, even more preferably 30 to 70 mol %, and particularly preferably 40 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a1) is at least the lower limit of the preferred range described above, lithography properties such as sensitivity, rectangularity of the pattern shape, reduced roughness, etc. can be improved. On the other hand, by ensuring that the proportion is at most the upper limit of the preferred range described above, a balance with other structural units can be achieved, resulting in various good lithography properties.

[0118] Regarding the structural unit (a10): The structural unit (a10) is a structural unit represented by general formula (a10-1) below (however, this does not include those that correspond to the structural unit (a1)).

[0119] [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. x1 is a single bond or a divalent linking group. x1 is an aromatic hydrocarbon group which may have a substituent. ax1 is an integer greater than or equal to 1.

[0120] In the above formula (a10-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon 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, and from the viewpoint of industrial availability, more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0121] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0122] Ya x1is preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, and more preferably a single bond or an ester bond [-C(=O)-O-, -OC(=O)-].

[0123] In the formula (a10-1), Wa x1 is an aromatic hydrocarbon group which may have a substituent. Wa x1 The aromatic hydrocarbon group in the formula (n) is an aromatic ring which may have a substituent. ax1 4n+1) hydrogen atoms are removed. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Also, Wa x1 The aromatic hydrocarbon group in the formula (n) may be an aromatic compound having an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.). ax1 +1) hydrogen atoms may also be removed. Among the above, Wa x1 As the aryl group, benzene, naphthalene, anthracene, or biphenyl (n ax1 A group in which (n +1) hydrogen atoms have been removed is preferred, and a group in which (n ax1 A group in which (n +1) hydrogen atoms have been removed from benzene is more preferable. ax1 A group in which +1) hydrogen atoms have been removed is more preferred.

[0124] Wa x1The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent include Ya x1 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, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. x1 The aromatic hydrocarbon group in the formula (I) preferably does not have a substituent.

[0125] In the formula (a10-1), n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0126] Specific examples of the structural unit (a10) represented by the aforementioned formula (a10-1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] The structural unit (a10) contained in the component (A1) may be of one type, or two or more types. When the component (A1) contains the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol %, more preferably 25 to 75 mol %, even more preferably 30 to 70 mol %, and particularly preferably 40 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a10) is at least as large as the lower limit of the above range, it is possible to further increase the sensitivity, whereas by ensuring that the proportion is at most the upper limit of the above range, it is easier to achieve a balance with other structural units.

[0131] Regarding the structural unit (a2): The component (A1) may further include a structural unit (a2) that includes a lactone-containing cyclic group (provided that this does not fall under the category of the structural unit (a1)). The lactone-containing cyclic group of the structural unit (a2) is effective in increasing the adhesion of the resist film to the substrate when the (A1) component is used to form a resist film. In addition, the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, increasing the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, thereby improving the lithography properties, etc.

[0132] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- in its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is further a ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. The lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any suitable group can be used. Specific examples include the groups represented by the following general formulae (a2-r-1) to (a2-r-7).

[0133] [ka] [In the formula, Ra' 21are each 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, n' is an integer of 0 to 2, and m' is 0 or 1. * represents a bond (the same applies hereinafter).]

[0134] In the general formulas (a2-r-1) to (a2-r-7), 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. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Among these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred. Ra' 21 The alkoxy group in the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. 21 Examples of the alkyl group include those groups in which the alkyl groups mentioned above are linked to an oxygen atom (-O-). Ra' 21 As the halogen atom in, a fluorine atom is preferable. Ra' 21 As the halogenated alkyl group in the above, Ra' 21 and groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the above halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0135] Ra' 21 In -COOR" and -OC(=O)R", R" is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group. When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Examples of the lactone-containing cyclic group in R″ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7) above. Ra' 21 The hydroxyalkyl group in Ra' is preferably one having 1 to 6 carbon atoms. 21 In the above formula, at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0136] Ra' 21 Among the above, it is preferable that each of them independently is a hydrogen atom or a cyano group.

[0137] In the general formulae (a2-r-2), (a2-r-3) and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A" is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between the carbon atoms of the alkylene group, and examples thereof include -O-CH2-, -CH2-O-CH2-, -S-CH2- and -CH2-S-CH2-. A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

[0138] Specific examples of the groups represented by general formulas (a2-r-1) to (a2-r-7) are listed below.

[0139] [ka]

[0140] [ka]

[0141] Of the various possibilities, the structural unit (a2) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

[0142] [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. 21 is a single bond or a divalent linking group. 21is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. 21 If -O-, Ya 21 does not become -CO-. Ra 21 is a lactone-containing cyclic group.

[0143] In the formula (a2-1), R is the same as defined 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 from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferable.

[0144] In the formula (a2-1), Ya 21 The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 21 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0145] In the formula (a2-1), Ya 21 is a single bond, La 21 is preferably -COO- or -OCO-.

[0146] In the above formula (a2-1), Ra 21 is a lactone-containing cyclic group. Ra 21 Suitable examples of the lactone-containing cyclic group in include the groups represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7), respectively.

[0147] The structural unit (a2) contained in the component (A1) may be of one type, or two or more types. When the component (A1) contains the structural unit (a2), the proportion of the structural unit (a2) relative to the total (100 mol%) of all structural units constituting the component (A1) is preferably 20 mol% or less, more preferably from 1 to 20 mol%, even more preferably from 1 to 15 mol%, and particularly preferably from 1 to 10 mol%. When the proportion of the structural unit (a2) is at least as large as the preferred lower limit, the effects achieved by including the structural unit (a2) as described above can be fully obtained. When the proportion of the structural unit (a2) is at most the upper limit, a balance with other structural units can be achieved, and various lithography properties become favorable.

[0148] Regarding the structural unit (a8): The structural unit (a8) is a structural unit derived from a compound represented by general formula (a8-1) shown below.

[0149] [ka] [In the formula, W 2 is a polymerizable group-containing group. x2 is a single bond or (n ax2 +1)valent linking group. x2 and W 2 R may form a condensed ring. 1 R is a fluorinated alkyl group having 1 to 12 carbon atoms. 2 R is a hydrogen atom or an organic group having 1 to 12 carbon atoms which may have a fluorine atom. 2 and Ya x2 may be bonded to each other to form a ring structure. ax2 is an integer from 1 to 3.

[0150] W 2 The "polymerizable group" in the polymerizable group-containing group is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.

[0151] The polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group. Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Examples of the polymerizable group-containing group include those represented by the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 A preferred example is a group represented by the formula: In this chemical formula, R X11 , R X12 and R X13 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; x0 is a single bond or a divalent linking group.

[0152] Ya x2 and W 2 The condensed ring formed by the above is W 2 Polymerizable group of the site and Ya x2 and W 2 Other groups than the polymerizable group at the Ya site x2 and Ya x2 and W 2 The condensed ring formed by these may have a substituent.

[0153] Specific examples of the structural unit (a8) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0154] [ka]

[0155] The structural unit (a8) contained in the component (A1) may be of one type, or two or more types. When the component (A1) contains the structural unit (a8), the proportion of the structural unit (a8) is preferably no greater than 20 mol %, and more preferably from 0 to 10 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).

[0156] The component (A1) contained in the resist composition may use either a single type of compound, or a combination of two or more types of compounds. In the resist composition of this embodiment, a preferred example of the component (A1) is a polymeric compound having a repeating structure of the structural unit (a1). Of the above, particularly preferred examples of the component (A1) include polymeric compounds having a repeating structure of the structural unit (a1) and the structural unit (a10). More specifically, preferred examples of the (A1) component include polymeric compounds having a repeating structure of the structural unit represented by the formula (a1-1) and the structural unit (a10), and polymeric compounds having a repeating structure of the structural unit represented by the formula (a1-3) and the structural unit (a10).Of these, from the viewpoint of increasing sensitivity, polymeric compounds having a repeating structure of the structural unit represented by the formula (a1-3) and the structural unit (a10) are more preferred.

[0157] In a polymeric compound having a repeating structure of the structural unit (a1) and the structural unit (a10), the proportion of the structural unit (a1) relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%. Furthermore, the proportion of the structural unit (a10) in the polymer compound is preferably from 20 to 80 mol %, more preferably from 25 to 75 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, based on the total (100 mol %) of all structural units constituting the polymer compound.

[0158] The (A1) component can be produced by dissolving monomers that derive each structural 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 solution and polymerizing the resulting mixture. Alternatively, the component (A1) can be produced by dissolving a monomer that derives the structural unit (a1) and, if necessary, a monomer that derives a structural unit other than the structural unit (a1) (for example, the structural unit (a10)) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the resulting solution to polymerize, and then carrying out a deprotection reaction. In addition, 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 to the end. In this way, a copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms is introduced, which is effective in reducing development defects and LER (line edge roughness: unevenness of the line sidewall).

[0159] The weight average molecular weight (Mw) of the component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 40,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 10,000. When the Mw of the component (A1) is no more than the preferred upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is no less than the preferred lower limit of this range, the dry etching resistance and cross-sectional shape of the resist pattern are excellent. The dispersity (Mw / Mn) of the component (A1) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.

[0160] Regarding component (A2) The resist composition of this embodiment may use, in combination with the component (A), a base component (hereafter referred to as “component (A2)”) that does not fall under the category of the component (A1) above and whose solubility in a developer changes under the action of an acid. There are no particular restrictions on the component (A2), and it may be selected from the many conventional base components for chemically amplified resist compositions. The component (A2) may be a polymeric compound or a low molecular weight compound, and may be used either alone or in combination of two or more.

[0161] The proportion of the (A1) component in the (A) component is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of the (A) component. When this proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, resolution, and reduced roughness is easily formed.

[0162] The amount of the component (A) in the resist composition of this embodiment may be adjusted depending on factors such as the thickness of the resist film to be formed.

[0163] <Component (D): Base Component> In the present embodiment, the component (D) includes a compound (D0) (hereinafter also referred to as "component (D0)") represented by the following general formula (d0): The component (D0) is capable of functioning as a quencher (acid diffusion controller) in the resist composition, trapping acid generated upon exposure.

[0164] Regarding the (D0) component The component (D0) is a compound represented by the following general formula (d0).

[0165] [ka] [In the formula, Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 1 and L3 are each independently a divalent linking group. x is an integer of 1 to 4. When x is an integer of 2 or more, a plurality of -L 1 -L 2 -L 3 -Rf may be the same or different. d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. z is an integer of 0 to 3, provided that 2≦x+y+z≦5. (M m+ ) 1 / m is a counter cation. m is an integer of 1 or more.

[0166] {Anion part of component (D0)} In the above formula (d0), Rf is a hydrocarbon group which may have a fluorine atom. The hydrocarbon group in Rf may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0167] Aliphatic hydrocarbon group in Rf The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. Examples of the aliphatic hydrocarbon group include a chain aliphatic hydrocarbon group (a linear or branched aliphatic hydrocarbon group) and an aliphatic hydrocarbon group containing a ring in the structure.

[0168] Linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkyl group is preferable. The branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6. As the branched aliphatic hydrocarbon group, a branched alkyl group is preferable.

[0169] The linear or branched aliphatic hydrocarbon group may have a fluorine atom as a substituent, and from the viewpoint of the pattern shape (rectangularity), it is preferable that the linear or branched aliphatic hydrocarbon group has fluorinated hydrogen atoms of 25% or more, more preferably 50% or more, and even more preferably 60% or more. The linear or branched aliphatic hydrocarbon group may contain a substituent other than a fluorine atom. Examples of the substituent other than a fluorine atom include a halogen atom other than a fluorine atom.

[0170] Aliphatic hydrocarbon groups containing rings in the structure Examples of the aliphatic hydrocarbon group containing a ring in its structure include a cyclic aliphatic hydrocarbon group (a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom (excluding fluorine atoms) in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group 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 include the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0171] The cyclic aliphatic hydrocarbon group may have a fluorine atom or a fluorinated hydrocarbon group as a substituent, and from the viewpoint of the pattern shape (rectangularity), it is preferable that the cyclic aliphatic hydrocarbon group has a fluorine atom or a fluorinated hydrocarbon group as a substituent. The fluorinated hydrocarbon group as the substituent here is preferably a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorinated alkyl group having 1 to 3 carbon atoms. In the cyclic aliphatic hydrocarbon group, preferably 25% or more of the hydrogen atoms in the cyclic aliphatic hydrocarbon group are fluorinated, more preferably 50% or more, and even more preferably 60% or more. The cyclic aliphatic hydrocarbon group may contain a substituent other than a fluorine atom or a fluorinated hydrocarbon group. Examples of the substituent other than a fluorine atom or a fluorinated hydrocarbon group include a halogen atom other than a fluorine atom and an alkyl group having 1 to 5 carbon atoms.

[0172] Aromatic hydrocarbon group in Rf 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 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom (excluding fluorine atom). Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom is removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom 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, and 2-naphthylethyl group). The number of carbon atoms of 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.

[0173] The aromatic hydrocarbon group may have a fluorine atom or a fluorinated hydrocarbon group as a substituent, and from the viewpoint of the pattern shape (rectangularity), it is preferable that the aromatic hydrocarbon group has a fluorine atom or a fluorinated hydrocarbon group as a substituent. The fluorinated hydrocarbon group as the substituent here is preferably a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorinated alkyl group having 1 to 3 carbon atoms. The aromatic hydrocarbon group has preferably 25% or more of the hydrogen atoms fluorinated, more preferably 50% or more, and even more preferably 60% or more of the hydrogen atoms fluorinated. The aromatic hydrocarbon group may contain a substituent other than a fluorine atom or a fluorinated hydrocarbon group. Examples of the substituent other than a fluorine atom or a fluorinated hydrocarbon group include a halogen atom other than a fluorine atom and an alkyl group having 1 to 5 carbon atoms.

[0174] From the viewpoint of easily controlling the distribution of the component (D0) in the resist film (uneven distribution on the resist film surface), Rf is preferably a fluorinated hydrocarbon group, more preferably a chain-like aliphatic hydrocarbon group having a fluorine atom as a substituent, or an aromatic hydrocarbon group having a fluorine atom or a fluorinated hydrocarbon group as a substituent, even more preferably a straight-chain aliphatic hydrocarbon group having a fluorine atom as a substituent, or an aromatic hydrocarbon group having a fluorine atom or a fluorinated alkyl group as a substituent, and particularly preferably a straight-chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom as a substituent, or an aromatic hydrocarbon group having a fluorine atom or a fluorinated alkyl group having 1 to 3 carbon atoms as a substituent.

[0175] In the formula (d0), x is an integer of 1 to 4, and is preferably 1 or 2, and more preferably 1, from the viewpoint of synthesis. In the formula (d0), the total number of fluorine atoms contained in x Rfs is preferably 5 or more, more preferably 5 to 11, even more preferably 5 to 10, and particularly preferably 5 to 9. When the total number of fluorine atoms is within the above preferred range, lithography properties such as rectangularity of the pattern shape and reduced roughness can be improved in the formation of a resist pattern. When x is 2 or more, the total number of fluorine atoms contained in Rf means the total number of all fluorine atoms contained in two or more Rfs.

[0176] In the above formula (d0), L 2 is a divalent cyclic group which may have a substituent. L 2 The divalent cyclic group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0177] L 2In the above, the aliphatic hydrocarbon group of the monocyclic group is preferably a group in which two or more hydrogen atoms have been removed 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. L 2 In the above, the aliphatic hydrocarbon group of the polycyclic group is preferably a group in which two or more hydrogen atoms have been removed from a polycycloalkane or polycycloalkene, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. Furthermore, the polycycloalkene is preferably one having 7 to 12 carbon atoms, specifically, adamantene, norbornane, isobornene, tricyclodecene, tetracyclododecene, etc.

[0178] L 2 In the above formula, the aromatic hydrocarbon group is preferably a group in which two or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, more preferably a group in which two or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, and even more preferably a group in which two or more hydrogen atoms have been removed from benzene.

[0179] L 2 In the above, examples of the substituent that the divalent cyclic group may have include the above-mentioned Ra x5 The same groups as those shown below can be mentioned. In addition, in the cyclic group, a part of the carbon atoms (such as a methylene group) constituting the cyclic group may be substituted with a heteroatom-containing group. The heteroatom includes an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, and -S(=O)2-O-. That is, L2 The optionally substituted divalent cyclic group in the formula (I) may be a group in which two or more hydrogen atoms have been removed from an aromatic heterocycle such as a pyridine ring or a thiophene ring; or a group in which two or more hydrogen atoms have been removed from an aliphatic heterocycle such as a tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, or lactone ring.

[0180] L 2 The divalent cyclic group in may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system, to which one or more aromatic rings are fused. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring system is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane.

[0181] In the above general formula (d0), L 2 Of the above, from the viewpoint of improving the dispersion uniformity of the component (D0) in the resist film, is preferably an aromatic hydrocarbon group which may have a substituent, or a polycyclic alicyclic hydrocarbon group which may have a substituent, and more preferably a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon group, a polycycloalkane, or a polycycloalkene, or a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused.

[0182] L 2 Specifically, the compound represented by the following chemical formula (L 2 -1)~(L 2 -8), which is preferably a group represented by the following chemical formula (L 2 -1)~(L 2 It is more preferable that the group is a group represented by any one of the following chemical formulas (L 2 -2), (L 2 -3) or (L 2 It is more preferable that the group is represented by the formula (4). In addition, the following chemical formula (L 2 -1)~(L2 The hydrogen atoms of the groups represented by the formulas (R-8) may each be independently substituted with a substituent. x5 The same can be mentioned.

[0183] [ka]

[0184] In the above formula (d0), L 1 and L 3 are each independently a divalent linking group. L 1 and L 3 The divalent linking group in is preferably a divalent linking group containing an oxygen atom. L 1 and L 3 is a divalent linking group containing an oxygen atom, L 1 and L 3 may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of divalent linking groups containing an oxygen atom include non-hydrocarbon oxygen-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-OC(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-OC(=O)-O-); and combinations of the non-hydrocarbon oxygen-containing linking groups with alkylene groups. A sulfonyl group (-SO2-) may be further linked to this combination.

[0185] L 1 and L 3 More specifically, the divalent linking group in 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 non-hydrocarbon oxygen atom-containing linking group and an alkylene group. a are each independently a hydrogen atom or an alkyl group.

[0186] In the above formula (d0), L 1 Among the above, is preferably a divalent linking group containing an oxygen atom, and is preferably -OCO-, -COO-, or -C(=O)-N(R a )-, and particularly preferably -OCO-, -COO-, -NH-C(=O)- or -C(=O)-NH-.

[0187] In the above formula (d0), L 3 Among the above, is preferably a divalent linking group containing an oxygen atom, and more preferably -OCO-, -COO-, -NH-C(=O)-, -C(=O)-NH- or -OC(=O)-alkylene group -O-.

[0188] In the formula (d0), R d0 is an iodine atom or a bromine atom, and is preferably an iodine atom since it is easier to increase the sensitivity. y is an integer of 1 to 4, and is preferably 1, 2 or 3 from the viewpoint of synthesis, and more preferably 2 or 3 from the viewpoint of achieving high sensitivity. z is an integer of 0 to 3, and may be 0, 1 or 2, or may be 0 or 1. From the viewpoint of solubility in the developer and effect of reducing roughness, z is preferably 1 or 2, and more preferably 1.

[0189] Preferred specific examples of the anion moiety of the component (D0) are shown below. The anions represented by the following chemical formulas (d0-an-101) to (d0-an-113) are examples of the anion moiety when y in the above formula (d0) is 1. The anions represented by the following chemical formulas (d0-an-201) to (d0-an-242) are examples of the anion moiety when y in the above formula (d0) is 2. The anions represented by the following chemical formulas (d0-an-301) to (d0-an-310) are examples of the anion moiety when y in the above formula (d0) is 3.

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] The anion portion of the (D0) component is preferably at least one selected from the group consisting of the anions represented by the above chemical formulas (d0-an-101) to (d0-an-113), (d0-an-201) to (d0-an-242), and (d0-an-301) to (d0-an-310). Among these, the anion portion of the (D0) component is preferably one corresponding to an anion in which the total number of fluorine atoms contained in Rf in general formula (d0) is 5 or more and 9 or less, from the viewpoints of reducing roughness and pattern shape (rectangularity). Alternatively, from the viewpoint of increasing sensitivity, the anion portion of the component (D0) may be, among the above, R d0 is an iodine atom and y is 2 or 3, and the anions represented by the above chemical formulas (d0-an-201) to (d0-an-240), and the anions represented by the above chemical formulas (d0-an-301) to (d0-an-310), are more preferred. Alternatively, as the anion portion of the component (D0), from the viewpoints of increasing sensitivity, reducing roughness, and pattern shape (rectangularity), among the above, R d0 is an iodine atom, y is 2 or 3, and the total number of fluorine atoms contained in Rf is 5 or more and 9 or less.

[0200] {Cation part of component (D0)} In the above formula (d0), (M m+ ) 1 / m is the counter cation, and M m+ is a cation with a valence of m, where m is an integer of 1 or greater. Preferred cationic moieties ((M m+ ) 1 / m) includes onium cations, preferably sulfonium cations and iodonium cations, and more preferably onium cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0201] [ka] [In the formula, R 201 ~R 207 R each independently represents an aryl group, an alkyl group, or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 L 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 represents -C(=O)- or -C(=O)-O-.

[0202] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7), respectively.

[0203] [ka] [In the formula, R' 201 are each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0204] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0205] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring of the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0206] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in 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 straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. 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 a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

[0207] Among them, R' 201The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0208] 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, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0209] Also, R' 201 The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle, etc. Examples include lactone-containing cyclic groups, -SO2--containing cyclic groups, and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16), respectively.

[0210] [ka]

[0211] R' 201 Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a fluorine atom is preferred. Examples of halogenated alkyl groups 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 have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0212] A chain alkyl group which may have a substituent: R' 201 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0213] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0214] R' 201 Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above R' 201 and the like.

[0215] R' 201 In addition to those mentioned above, the optionally substituted cyclic group, the optionally substituted chain alkyl group, or the optionally substituted chain alkenyl group also includes the same as the acid-dissociable group represented by formula (a1-r-2) above as the optionally substituted cyclic group or the optionally substituted chain alkyl group.

[0216] Among them, R' 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group, an -SO2- containing cyclic group, etc. are preferred.

[0217] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they do not include a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R N is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, in which a ring containing a sulfur atom in the ring skeleton in the formula is a 3- to 10-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0218] R 208 ~R 209 each 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, and when they are alkyl groups they may be bonded to each other to form a ring.

[0219] R 210 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 210The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 210 In the above, the -SO2- containing cyclic group is not particularly limited and any group can be used. Specifically, the groups represented by the following general formulae (b5-r-1) to (b5-r-4) can be mentioned, with the "-SO2- containing polycyclic group" being preferred, and the group represented by the general formula (b5-r-1) being more preferred.

[0220] [ka] [In the formula, Rb' 51 are each 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 of 0 to 2. * represents a bond.]

[0221] In the general formulae (b5-r-1) and (b5-r-2) above, 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. B" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0222] In the general formulae (b5-r-1) to (b5-r-4), Rb' 51are each 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, they are preferably each independently a hydrogen atom or a cyano group.

[0223] Specific examples of the groups represented by general formulas (b5-r-1) to (b5-r-4) are shown below, in which "Ac" represents an acetyl group.

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas.

[0228] [ka]

[0229] [ka]

[0230] [ka] [In the formula, g1, g2, and g3 each represent a repeating number, where g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20.]

[0231] [ka]

[0232] [ka]

[0233] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the above-mentioned R 201 ~R 207 , and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the

[0234] [ka]

[0235] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0236] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0237] [ka]

[0238] Cationic part ((M m+ ) 1 / m) is preferably at least one selected from the group consisting of cations represented by the general formulas (ca-1) to (ca-3), more preferably at least one selected from the group consisting of cations represented by the general formulas (ca-1) to (ca-2), and among these, the cation represented by the general formula (ca-1) is even more preferable. Particularly from the viewpoint of achieving high sensitivity, the preferred cations represented by the formula (ca-1) are those having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent, and for example, cations selected from the group consisting of the cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferred.

[0239] Alternatively, the cationic moiety ((M m+ ) 1 / m From the viewpoint of increasing sensitivity, the cationic portion ((M m+ ) 1 / m ) is preferably a cation represented by the following formula (ca-1-1).

[0240] [ka] [In the formula, Rf 201 ~Rf 203 Rf each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 201 ~Rf 203 may be bonded to each other to form a ring together with the sulfur atom in the formula. 201 ~Rf 203 At least one of contains at least one fluorine atom.

[0241] Rf in the above formula (ca-1-1) 201 ~Rf 203 is R in the formula (ca-1). 201 ~R 203 However, Rf 201 ~Rf203 At least one of Rf contains at least one fluorine atom. The cation represented by formula (ca-1-1) preferably contains three or more fluorine atoms. 201 ~Rf 203 may have three or more fluorine atoms, 201 ~Rf 203 may contain three or more fluorine atoms in total.

[0242] Specific examples of the component (D0) are listed below, but are not limited to these.

[0243] [ka]

[0244] [ka]

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] Of the above, the component (D0) is preferably one selected from the group consisting of the compounds represented by the above chemical formulas (D0-1) to (D0-24). Alternatively, from the viewpoints of reducing roughness and pattern shape (rectangularity), the component (D0) is preferably a compound having an anion in which the total number of fluorine atoms contained in Rf in general formula (d0) is 5 to 9, and more preferably a compound selected from the group consisting of the compounds represented by the above chemical formulas (D0-3), (D0-7), (D0-9), (D0-10), (D0-13), (D0-14), (D0-17), (D0-18), and (D0-20) to (D0-24). Alternatively, from the viewpoint of increasing sensitivity, the component (D0) may be, among the above, R d0 is an iodine atom and y is 2 or 3, and more preferably is a compound selected from the group consisting of the compounds represented by the above chemical formulas (D0-4) to (D0-20) and (D0-22) to (D0-24). Alternatively, from the viewpoints of increasing sensitivity, reducing roughness, and pattern shape (rectangularity), it is particularly preferable that the (D0) component is selected from the group consisting of the compounds represented by the above chemical formulas (D0-7), (D0-9), (D0-10), (D0-13), (D0-14), (D0-17), (D0-18), (D0-20), and (D0-22) to (D0-24).

[0251] In the resist composition of this embodiment, the component (D0) may be used either as a single type, or in a combination of two or more types. In the resist composition of this embodiment, the content of the component (D0) relative to 100 parts by mass of the component (A) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, even more preferably 2 to 15 parts by mass, and particularly preferably 3 to 12.5 parts by mass. When the content of the component (D0) is at least the lower limit of the preferred range, high sensitivity can be achieved in resist pattern formation, and lithography properties such as rectangularity of the pattern shape and reduced roughness can be improved. On the other hand, when the content is at most the upper limit of the preferred range, sensitivity can be maintained at a better level. In addition, when each component of the resist composition is dissolved in an organic solvent, a homogeneous solution is easily obtained, and the storage stability of the resist composition is improved, which is preferable.

[0252] The proportion of the (D0) component in the entire (D) component is, for example, 50 mass% or more, preferably 70 mass% or more, and more preferably 95 mass% or more. The proportion of the (D0) component in the entire (D) component may be 100 mass%.

[0253] The component (D) in the resist composition of this embodiment may contain a base component other than the above-mentioned component (D0). Examples of base components other than component (D0) include photodegradable bases (D1) (hereinafter referred to as "component (D1)") that decompose upon exposure and lose their ability to control acid diffusion, and nitrogen-containing organic compounds (D2) (hereinafter referred to as "component (D2)") that do not fall under component (D1). Among these, photodegradable bases (component (D1)) are preferred because they are likely to enhance all of the following characteristics: high sensitivity, in-plane uniformity of pattern dimensions (CDU), fine resolution, and suppression of the occurrence of coating defects.

[0254] Regarding component (D1) The component (D1) is not particularly limited as long as it decomposes upon exposure to light and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"): The components (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion control ability (basicity), but they act as quenchers in the unexposed areas of the resist film.

[0255] [ka] [In the formula, Rd 1 ~Rd 4 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. 2 In the formula, no fluorine atom is bonded to the carbon atom adjacent to the S atom. 1 is a single bond or a divalent linking group; m is an integer of 1 or more; M m+ are each independently a cation having a valence of m.

[0256] {(d1-1) component} Anion part In formula (d1-1), Rd 1 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, each of which is represented by the R' 201 The same can be mentioned. Among these, Rd 1 is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-8), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5). Note that Rd 1In the case where the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in the formula (d3-1) has a linking group represented by the above general formulas (y-al-1) to (y-al-7) as a substituent, in the above general formulas (y-al-1) to (y-al-7), Rd 1 The carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in the above formula (y-al-1) to (y-al-7) is bonded to V' 101 It is. 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 another ring structure). The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0257] When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or 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 further preferably 1 to 4. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0258] Preferred specific examples of the anion moiety of the component (d1-1) are shown below.

[0259] [ka]

[0260] ··Cation part In formula (d1-1), M m+ is an m-valent cation. M m+ Suitable examples of the cation include the same cations represented by the general formulas (ca-1) to (ca-3) above, more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the general formulas (ca-1-1) to (ca-1-84). The component (d1-1) may be used alone or in combination of two or more.

[0261] {Component (d1-2)} Anion part In formula (d1-2), Rd 2 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and the R' 201 The same can be mentioned. However, Rd 2 In the above, the carbon atom adjacent to the S atom does not have a fluorine atom bonded thereto (is not substituted with fluorine), and this makes the anion of the (d1-2) component an appropriate weak acid anion, thereby improving the quenching ability of the (D) component. Rd 2 As the alkyl group, a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent is preferable, and an aliphatic cyclic group which may have a substituent is more preferable.

[0262] The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms. The aliphatic cyclic group is preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor.

[0263] Rd 2 The hydrocarbon group may have a substituent, and examples of the substituent include Rd 1 Examples of the substituent include the same as the substituents that may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above.

[0264] Preferred specific examples of the anion moiety of the component (d1-2) are shown below.

[0265] [ka]

[0266] ··Cation part In formula (d1-2), M m+ is an m-valent cation, and M in the formula (d1-1) m+ is the same as: The component (d1-2) may be used alone or in combination of two or more.

[0267] {Component (d1-3)} Anion part In formula (d1-3), Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and R' 201 The Rd is preferably a fluorine atom-containing cyclic group, a chain alkyl group, or a chain alkenyl group. Among these, a fluorinated alkyl group is preferred, and the Rd 1 More preferred are the same fluorinated alkyl groups as those mentioned above.

[0268] In formula (d1-3), Rd 4is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and the R' 201 The same can be mentioned. Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent, is preferable. Rd 4 The alkyl group in Rd is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. 4 A part of the hydrogen atoms of the alkyl group may be substituted with a hydroxyl group, a cyano group, or the like. Rd 4 The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.

[0269] Rd 4 The alkenyl group in R' 201 Examples of the alkenyl group include the same as the alkenyl group in the above, and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferred. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

[0270] Rd 4 The cyclic group in R' 201 Examples of the cyclic groups include those similar to those in the above formula, and preferred are alicyclic groups obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane, or aromatic groups such as a phenyl group or a naphthyl group. 4When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, and the lithography properties become good. 4 When is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition exhibits excellent light absorption efficiency and exhibits favorable sensitivity and lithography properties.

[0271] In formula (d1-3), Yd 1 is a single bond or a divalent linking group. Yd 1 The divalent linking group in is not particularly limited, but examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. 21 Examples of the divalent linking group include the same divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom as mentioned in the description of the divalent linking group in the above. Yd 1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.

[0272] Preferred specific examples of the anion moiety of the component (d1-3) are shown below.

[0273] [ka]

[0274] [ka]

[0275] ··Cation part In formula (d1-3), M m+ is an m-valent cation, and M in the formula (d1-1) m+ is the same as: The component (d1-3) may be used alone or in combination of two or more.

[0276] The component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them. When the resist composition contains the component (D1), the amount of the 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, relative to 100 parts by mass of the component (A).

[0277] The component (D1) preferably contains the above-mentioned component (d1-1). Of the entire (D1) component, the content of the (d1-1) component is preferably 50 mass% or more, preferably 70 mass% or more, and more preferably 90 mass% or more. The (D1) component may consist solely of the compound (d1-1) component.

[0278] Manufacturing method of component (D1): The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods. The method for producing the component (d1-3) is not particularly limited, and it can be produced, for example, in a manner similar to that described in US2012-0149916.

[0279] Regarding component (D2) The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not fall under the category of the above component (D1). The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under the category of 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 the aliphatic group preferably has 1 to 12 carbon atoms. Examples of aliphatic amines include amines in which at least one hydrogen atom of ammonia NH3 has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), or cyclic amines. Specific examples of alkylamines and alkyl alcohol amines 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 alcohol amines 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 is particularly preferred.

[0280] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specific examples thereof 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.

[0281] 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, and the like, with triethanolamine triacetate being preferred.

[0282] Furthermore, an aromatic amine may be used as the component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, and 2,6-di-tert-butylpyridine.

[0283] The component (D2) may be used alone or in combination of two or more types. When the resist composition contains the component (D2), the amount of the component (D2) in the resist composition is usually within the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the component (A). By ensuring that the amount is within this range, the resist pattern shape, the storage stability over time, and the like are improved.

[0284] <Other ingredients> The resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A) and (D). Examples of other components include the following components (B), (E), (F), and (S).

[0285] <Component (B): Acid generator component> The resist composition of this embodiment preferably further contains an acid generator component (B) (excluding the compound (D0)) that generates an acid upon exposure. There are no particular limitations on the component (B), and any of the compounds that have been proposed as acid generators 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, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

[0286] Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), a compound represented by general formula (b-2) (hereinafter also referred to as "component (b-2)"), or a compound represented by general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0287] [ka] [In the formula, R 101 and R 104 ~R 108 R each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. 104 and R 105 R may be bonded to each other to form a ring structure. 102 Y is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 101 is a divalent linking group containing an oxygen atom or a single bond. 101 ~V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group. 101 and V 101 Both of L cannot be single bonds. 101 ~L 102 Each of L is independently a single bond or an oxygen atom. 103 ~L 105are each independently a single bond, -CO- or -SO2-. m is an integer of 1 or more, and M' m+ is an onium cation with a valence of m.

[0288] {anion part} Anion in component (b-1) In formula (b-1), R 101 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0289] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group is preferably saturated.

[0290] R 101 The aromatic hydrocarbon group in the formula (I) 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, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R 101 Specific examples of the aromatic ring of the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R 101Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, etc.), etc. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0291] R 101 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in 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 straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. 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 a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

[0292] Among them, R 101The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0293] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0294] Also, R 101The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specific examples include lactone-containing cyclic groups represented by the above general formulae (a2-r-1) to (a2-r-7), -SO2--containing cyclic groups represented by the above general formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the above chemical formulae (r-hr-1) to (r-hr-16). * in the formula represents Y in formula (b-1). 101 Represents a bond that bonds to .

[0295] R 101 Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms. As the halogen atom as a substituent, a fluorine atom, a bromine atom or an iodine atom is preferred. Examples of the halogenated alkyl group as a substituent 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 have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0296] R 101The cyclic hydrocarbon group in may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system to which one or more aromatic rings are fused. Specific examples of the bridged 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 in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. 101 Specific examples of the fused cyclic group in the formula (b-1) include those represented by the following formulas (r-br-1) to (r-br-2). 101 Represents a bond that bonds to .

[0297] [ka]

[0298] R 101 Examples of the substituent that the fused cyclic group in the formula (I) may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the fused cyclic group are defined as R 101 Examples of the substituents of the cyclic group in the above formula (I) include the same as those exemplified as the substituents of the cyclic group in the above formula (I). Examples of the aromatic hydrocarbon group as the substituent of the fused ring group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), and the heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; groups obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane; lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above; -SO2- containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above; and heterocyclic groups represented by the formulae (r-hr-7) to (r-hr-16) above.

[0299] A chain alkyl group which may have a substituent: R 101 The chain 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. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0300] An optionally substituted chain alkenyl group: R 101 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0301] R 101 Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above-mentioned R 101 and the like.

[0302] In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 When Y is a divalent linking group containing an oxygen atom, 101 may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of the divalent linking group containing an oxygen atom include the linking groups represented by the above-mentioned general formulae (y-al-1) to (y-al-8).

[0303] In formula (b-1), V 101 is a single bond, an alkylene group or a fluorinated alkylene group. 101 The alkylene group and fluorinated alkylene group in the formula (I) preferably have 1 to 4 carbon atoms. 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0304] In formula (b-1), R 102 R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0305] Specific examples of the anion moiety represented by the formula (b-1) include, for example, Y 101When Y is a single bond, examples of the anion include a fluorinated alkylsulfonate anion such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion; 101 When is a divalent linking group containing an oxygen atom, examples of the anions include those represented by any of the following formulas (an-1) to (an-3).

[0306] [ka] [In the formula, R” 101 R" is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a chain alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent. 102 R" is an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or an -SO2- containing cyclic group represented by each of the above general formulas (b5-r-1) to (b5-r-4). 103 V" is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. 101 R is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Each v" is independently an integer of 0 to 3, each q" is independently an integer of 0 to 20, and n" is 0 or 1.

[0307] R” 101 , R.” 102 and R.” 103 The aliphatic cyclic group which may have a substituent is represented by R 101 As the substituent, R in the formula (b-1) is preferably a group exemplified as the cyclic aliphatic hydrocarbon group. 101Examples of the substituents which may substitute the cyclic aliphatic hydrocarbon group in the above formula (1) include the same as those in the above formula (1).

[0308] R” 101 and R.” 103 The aromatic cyclic group which may have a substituent in the formula (b-1) is 101 The substituent is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in the formula (b-1). 101 The substituents which may substitute the aromatic hydrocarbon group in the above formula (I) are the same as those in the above formula (I).

[0309] R” 101 The chain alkyl group which may have a substituent in the formula (b-1) is R 101 The alkyl group is preferably one of the groups exemplified as the chain alkyl group in the above formula (I). R” 103 The chain alkenyl group which may have a substituent is R 101 Preferably, it is a group exemplified as the chain alkenyl group in the above formula.

[0310] Anion in component (b-2) In formula (b-2), R 104 , R 105 each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each represents R 101 However, R 104 , R 105 may be bonded to each other to form a ring. R 104 , R 105 is preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. 104 , R105 The number of carbon atoms in the chain-like alkyl group of R is preferably as small as possible within the above range of carbon atoms, for reasons such as good solubility in a resist solvent. 104 , R 105 In the chain alkyl group, the more hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes, and the more the transparency to high-energy light of 250 nm or less and electron beams improves, which is preferable. The ratio of fluorine atoms in the chain alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 each independently represents a single bond, an alkylene group, or a fluorinated alkylene group, and each represents V in formula (b-1). 101 The same can be mentioned. In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0311] Anion in component (b-3) In formula (b-3), R 106 ~R 108 each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each represents R 101 The same can be mentioned. In formula (b-3), L 103 ~L 105 are each independently a single bond, -CO- or -SO2-.

[0312] Among the above, the anion moiety of the component (B) is preferably the anion in the component (b-1).

[0313] {cationic part} In the above formula (b-1), formula (b-2), and formula (b-3), M' m+represents an onium cation having a valence of m. Among these, a sulfonium cation and an iodonium cation are preferred. m is an integer of 1 or greater.

[0314] Preferred cationic moieties ((M' m+ ) 1 / m ) are preferably the same as the cations represented by the above general formulas (ca-1) to (ca-3), more preferably the cations represented by the above general formula (ca-1), and even more preferably the cations represented by the above formulas (ca-1-1) to (ca-1-84).

[0315] In the resist composition of this embodiment, the component (B) may use either a single type, or a combination of two or more types. When the resist composition contains the component (B), the amount of the component (B) in the resist composition is preferably less than 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the component (A). By setting the content of the component (B) within the above-mentioned preferred range, sufficient pattern formation can be achieved. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a homogeneous solution is easily obtained, and the storage stability of the resist composition is also favorable.

[0316] <At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof> 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 derivatives thereof (hereafter referred to as "component (E)") for the purposes of preventing deterioration of sensitivity and improving the resist pattern shape and stability over time after exposure. Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among these, salicylic acid is preferred. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.

[0317] In the resist composition of this embodiment, the component (E) may use either a single type, or a combination of two or more types. When the resist composition contains the component (E), the amount of the 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 the component (A). By setting the amount in this range, the lithography properties are further improved.

[0318] <Fluorine additive component (F)> The resist composition of this embodiment may contain a fluorine additive component (hereafter referred to as "component (F)") as a hydrophobic resin. The component (F) is used to impart water repellency to the resist film, and when used as a resin separate from the component (A), it can improve lithography properties. As the component (F), for example, fluorine-containing polymeric compounds described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226 can be used. More specifically, the component (F) may be a polymer having a structural unit (f1) represented by the following general formula (f1-1). The polymer may be a polymer (homopolymer) consisting of only the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1); a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1), and more preferably a copolymer of the structural unit (f1) and the structural unit (a1). Here, the structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, or a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate, and more preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate.

[0319] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103 each 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; Rf 102 and Rf 103 may be the same or different. 1 is an integer from 0 to 5, and Rf 101 is an organic group containing a fluorine atom.

[0320] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as defined above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf 102 and Rf 103 The halogen atom in Rf is preferably a fluorine atom. 102 and Rf 103 Examples of the alkyl group having 1 to 5 carbon atoms in R include the same alkyl groups having 1 to 5 carbon atoms as those in R, and a methyl group or an ethyl group is preferred. 102 and Rf 103 Specific examples of the halogenated alkyl group 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 have been substituted with halogen atoms. As the halogen atom, a fluorine atom is preferred. Among these, Rf 102 and Rf 103 is preferably 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 further preferably a hydrogen atom. In formula (f1-1), nf 1 represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

[0321] In formula (f1-1), Rf 101is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom. The fluorine atom-containing hydrocarbon group may be linear, branched or cyclic and preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and particularly preferably has 1 to 10 carbon atoms. Furthermore, in the hydrocarbon group containing fluorine atoms, preferably 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more, and particularly preferably 60% or more are fluorinated, as this enhances the hydrophobicity of the resist film during immersion exposure. Among them, Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, or -CH2-CH2-CF2-CF2-CF2-CF3.

[0322] The weight average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1000 to 50000, more preferably 5000 to 40000, and most preferably 10000 to 30000. When it is below the upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is above the lower limit of this range, the resist film has good water repellency. The dispersity (Mw / Mn) of the component (F) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.

[0323] In the resist composition of this embodiment, the component (F) may use either a single type, or a combination of two or more types. When the resist composition contains the component (F), the amount of the 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 the component (A).

[0324] <Organic solvent component (S)> The resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as “component (S)”). In the resist composition of this embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0325] As the component (S), a mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, etc. As the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, the mixing ratio of the former to the latter is preferably 70:30 to 95:5 by mass. The amount of the component (S) used is not particularly limited, and is set appropriately depending on the coating film thickness at a concentration that allows application to a substrate, etc. In general, the component (S) is used so that the solids concentration of the resist composition falls within the range of 0.1 to 20 mass %, and preferably 0.2 to 15 mass %.

[0326] In the resist composition of this embodiment, after dissolving the resist material in the component (S), impurities and the like may be removed using a polyimide porous film, a polyamideimide porous film, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film. Examples of the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.

[0327] The resist composition of this embodiment described above contains a base component (A) and a compound (D0) represented by general formula (d0) (component (D0)). The component (D0) generates a carboxylic acid upon exposure, and can act as a quencher (acid diffusion controller) in the unexposed areas of the resist film. In the component (D0), an iodine atom or a bromine atom (R d0 ) and a linking group (-L 1 -L 2 -L 3 It is bonded to a hydrocarbon group (Rf) which may have a fluorine atom via an intermediate (-). Iodine or bromine atom (R d0 ) is highly hydrophobic and has a high absorption of EUV light with a wavelength of 13.5 nm. In this embodiment, the anion portion of the (D0) component is an iodine atom or a bromine atom (R d0 ), the hydrophobicity of the unexposed areas of the resist film is increased, making it easier to obtain dissolution contrast. In addition, the anion portion of the component (D0) contains an iodine atom or a bromine atom (R d0 ) and therefore exhibits high absorption upon exposure to light. However, on the other hand, the amount of light that reaches the bottom of the resist film (the interface with the substrate) is likely to decrease. In other words, the amount of acid generated in the resist film is relatively small at the bottom of the resist film and large at the top of the resist film. In contrast, in this embodiment, the anion portion of the component (D0) is a divalent cyclic group (L 2 ) containing a linking group (-L 1 -L 2 -L 3 The component (D0) has a hydrocarbon group (Rf) which may have a fluorine atom connected via a divalent cyclic group (L -) which may have a substituent. Therefore, the component (D0) tends to be unevenly distributed in the upper part of the resist film. This reduces the difference in the amount of acid generated by exposure at the bottom and top of the resist film. In addition, the component (D0) has a divalent cyclic group (L 2 ), it has a relatively bulky structure, which appropriately suppresses the diffusion length of the acid. Furthermore, it has a high affinity with the base material components, which makes it easy to distribute uniformly within the resist film. Furthermore, the component (D0) is designed so that a hydroxy group can be bonded to the benzene ring of the anion moiety at will, which makes it possible to control the solubility in the developer. It is presumed that with the resist composition of this embodiment, the above-mentioned actions occur synergistically, thereby achieving both high sensitivity and reduced roughness, and enabling the formation of a pattern with a good shape with high rectangularity.

[0328] (Method of forming resist pattern) A method for forming a resist pattern 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, exposing the resist film to light, and developing the exposed resist film to form a resist pattern. One embodiment of the resist pattern forming method is, for example, a resist pattern forming method carried out as follows.

[0329] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and then baked (post-applied bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film. Next, the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF exposure device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by lithography using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C. Next, the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.

[0330] After the development process, a rinse process is preferably carried out. In the case of an alkaline development process, the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse liquid containing an organic solvent is preferably used. In the case of a solvent development process, after the development treatment or rinsing treatment, a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed by using a supercritical fluid. After the development treatment or rinsing treatment, drying is performed. In some cases, a baking treatment (post-baking) may be performed after the development treatment.

[0331] The support is not particularly limited, and may be a conventionally known support, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, it may be a silicon wafer, a substrate made of metal such as copper, chromium, iron, or aluminum, or a glass substrate. As the material for the wiring pattern, for example, copper, aluminum, nickel, or gold may be used.

[0332] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used. The method of forming a resist pattern of the present embodiment is particularly useful when the step of exposing the resist film includes exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam).

[0333] The exposure method for the resist film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography. Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure tool is 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. The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of such a solvent include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent. As the liquid immersion medium, water is preferably used.

[0334] An example of an alkaline developer used in the development treatment in the alkaline development process is a 0.1 to 10 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0335] Examples of ester-based 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.

[0336] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0337] The organic developer may contain known additives as necessary. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants.

[0338] The development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it there for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), and a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0339] The organic solvent contained in the rinse solution used in the rinsing treatment after the development treatment in the solvent development process can be appropriately selected from the organic solvents listed above as the organic solvents used in the organic developer, which do not easily dissolve the resist pattern. Usually, at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more thereof, and may be used in combination with other organic solvents or water.

[0340] The rinse treatment (cleaning treatment) using a rinse liquid can be carried out by a known rinse method, such as a method of continuously applying the rinse liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), or a method of spraying the rinse liquid onto the surface of the support (spray method).

[0341] According to the method of forming a resist pattern of the present embodiment as described above, the resist composition described above is used, so when forming a resist pattern, it is possible to achieve both high sensitivity and reduced roughness, and to form a resist pattern with a good shape that has high rectangularity.

[0342] The resist composition of the above-mentioned embodiment and various materials used in the resist pattern forming method of the above-mentioned embodiment (for example, resist solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) preferably do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur atoms or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. The content of impurities contained 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).

[0343] (Compound represented by general formula (d0)) The compound according to the third aspect of the present invention is a compound represented by the following general formula (d0) (compound (D0)).

[0344] [ka] [In the formula, Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 1 and L 3 are each independently a divalent linking group. x is an integer of 1 to 4. When x is an integer of 2 or more, a plurality of -L 1 -L 2 -L 3 -Rf may be the same or different. d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. z is an integer of 0 to 3, provided that 2≦x+y+z≦5. (M m+ ) 1 / m is a counter cation. m is an integer of 1 or more.

[0345] The compound represented by general formula (d0) above (compound (D0)) is the same as the component (D0) in the resist composition related to the first aspect of the present invention. The compound of this embodiment is preferably a compound represented by formula (d0) in which Rf is a fluorinated hydrocarbon group. Alternatively, the compound of this embodiment is preferably a compound in which the total number of fluorine atoms contained in x Rfs in formula (d0) is 5 or more and 9 or less. Alternatively, the compound of this embodiment is preferably a compound in which y is 2 or 3 in the formula (d0). Specific examples of the compound of this embodiment include a compound in which the anion portion is an anion represented by each of the above chemical formulas (d0-an-101) to (d0-an-113) (when y in the above formula (d0) is 1), a compound in which the anion portion is an anion represented by each of the above chemical formulas (d0-an-201) to (d0-an-242) (when y in the above formula (d0) is 2), and a compound in which the anion portion is an anion represented by each of the above chemical formulas (d0-an-301) to (d0-an-310) (when y in the above formula (d0) is 3). The counter cation (M m+ ) 1 / m Examples of the cation include onium cations and metal cations. Examples of the onium cation include sulfonium cation, iodonium cation, ammonium cation, etc. Examples of the metal cation include alkali metal ions such as sodium ion and lithium ion; alkaline earth metal ions; rubidium ion, strontium ion, yttrium ion, etc. Further, specific examples of the compound of this embodiment preferably include the compounds represented by the above-mentioned chemical formulas (D0-1) to (D0-24).

[0346] [Method for producing the compound represented by formula (d0)] The component (D0) can be produced by a known production method. As an embodiment of the method for producing the component (D0), L in the general formula (d0) 1The production method for the compound in which is -OC(=O)- (ester bond) is shown below.

[0347] 1st step: First, a compound (CA0) represented by the following general formula (CA0) is used as a starting material, and this compound (CA0) is reacted with a tertiary alcohol to obtain a first intermediate (H01) represented by the following general formula (H01).

[0348] [ka] [In the formula, R d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. x is an integer from 1 to 4. z is an integer from 0 to 3, provided that 2≦x+y+z≦5. R S represents a tertiary alkyl group.

[0349] In the first step, the starting compound (CA0) is subjected to a reaction with the number and position of hydroxyl groups, as well as the amount of iodine or bromine atoms (R d0 The number and positions of bonds of ) are appropriately selected. In the above formula, R d0 , x, y, and z are R in the above general formula (d0). d0 , x, y, z.

[0350] Tertiary alcohol (R S As the alkyl group (—OH), tert-butyl alcohol, 1-methylcyclopentanol, etc. can be used. In the reaction of the compound (CA0) with a tertiary alcohol, a condensation agent is appropriately selected and used. Examples of the condensation agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyldiimidazole (CDI). The organic solvent used when reacting compound (CA0) with a tertiary alcohol is one in which compound (CA0) can be dissolved but does not react with it; any organic solvent that has good compatibility with the tertiary alcohol may be used, and examples of such organic solvents include dichloromethane, dichloroethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethylsulfoxide. In the first step, the reaction temperature is, for example, 40 to 80° C., and the reaction time is, for example, from 1 hour to 10 hours.

[0351] Second step: A second intermediate (H02) represented by the following general formula (H02) is prepared. In the following formula (H02), Rf and L 2 , L 3 Rf, L in the above general formula (d0) 2 , L 3 is the same as: The second intermediate (H02) may be a commercially available product if available, or may be a synthesized product. When the synthesized intermediate is used, the second intermediate (H02) is a divalent cyclic group (L 2 The compound can be obtained by alkylating or fluoroalkylating acetic anhydride having the same structure as that of the compound (e1). Examples of the reagent for alkylating or fluoroalkylating include the compounds represented by the chemical formulas (e1) to (e10) described below.

[0352] [ka] [In the formula, Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 3 is a divalent linking group.

[0353] Third step: Next, the first intermediate (H01) is reacted with the second intermediate (H02) in the presence of a base to obtain a third intermediate (H03) represented by the following general formula (H03).

[0354] [ka] [In the formula, R d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. x is an integer from 1 to 4. z is an integer from 0 to 3, provided that 2≦x+y+z≦5. R S represents a tertiary alkyl group. Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 3 is a divalent linking group.

[0355] In the third step, the structure and other properties of the second intermediate (H02) are appropriately selected depending on the target compound (component (D0)). In the above formula, R d0 , x, y, z, Rf, L 2 , L 3 is R in the above general formula (d0). d0 , x, y, z, Rf, L 2 , L 3 is the same as:

[0356] Examples of the base include sodium hydride, K2CO3, Cs2CO3, lithium diisopropylamide (LDA), triethylamine, 4-dimethylaminopyridine, and the like. In the reaction between the first intermediate (H01) and the second intermediate (H02), a condensation agent is appropriately selected and used. Examples of the condensation agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyldiimidazole (CDI). The organic solvent used when reacting the first intermediate (H01) with the second intermediate (H02) may be any solvent that dissolves the first intermediate (H01) and the second intermediate (H02) and does not react with them, and examples of the organic solvent include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethylsulfoxide. In the third step, the reaction temperature is, for example, 0 to 50° C., and the reaction time is, for example, from 1 hour to 24 hours.

[0357] 4th step: The third intermediate (H03) is then hydrolyzed to give the precursor (D'0).

[0358] [ka] [In the formula, R d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. x is an integer from 1 to 4. z is an integer from 0 to 3, provided that 2≦x+y+z≦5. R S represents a tertiary alkyl group. Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 3 is a divalent linking group.

[0359] In the hydrolysis of the third intermediate (H03), an acid can be used as a catalyst, such as trifluoroacetic acid (TFA) or methanesulfonic acid. The organic solvent used in hydrolysis of the third intermediate (H03) may be any solvent that can dissolve the third intermediate and the acid catalyst and does not react with them, and examples of the solvent include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethylsulfoxide. In the fourth step, the reaction temperature is, for example, 10 to 60° C., and the reaction time is, for example, from 1 hour to 24 hours.

[0360] Fifth step: Next, the precursor (D'0) and a compound (S0) represented by the following general formula (S0) are subjected to a salt exchange reaction to obtain a target compound represented by general formula (d0').

[0361] [ka] [In the formula, R d0 is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R d0 may be the same or different. x is an integer from 1 to 4. z is an integer from 0 to 3, provided that 2≦x+y+z≦5. R S represents a tertiary alkyl group. Rf is a hydrocarbon group which may have a fluorine atom. 2 L is a divalent cyclic group which may have a substituent. 3 is a divalent linking group. M m+ represents a cation having a valence of m, where m is an integer of 1 or more. Z - is the counter anion.

[0362] In the above formula, Z - In the formula (D'), the counter anion may be an ion that can become an acid having a lower acidity than the precursor represented by the formula (D'0). Specifically, examples of the counter anion include halogen ions such as bromide ion and chloride ion; BF4 - , AsF6 - , SbF6- , PF6 - , ClO4 - Among these, Z - is preferably a halogen ion, more preferably a bromide ion. In the above formula, M m+ , m is M in the above general formula (d0). m+ , m.

[0363] In the fifth step, a base may be used in the salt exchange reaction between the precursor (D'0) and the compound (S0), such as tetramethylammonium hydroxide (TMAH), sodium hydride, K2CO3, Cs2CO3, lithium diisopropylamide (LDA), triethylamine, 4-dimethylaminopyridine, etc.

[0364] The solvent used in the salt exchange reaction between the precursor (D'0) and the compound (S0) may be an organic solvent or a mixed solvent of an organic solvent and water. Examples of the organic solvent include ketone-based solvents such as cyclohexanone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; ether-based solvents such as diethyl ether, t-butyl methyl ether, and diisopropyl ether; halogen-based solvents such as tetrahydrofuran, 1,3-dioxolane, dichloromethane, and 1,2-dichloroethane; ester-based solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, propionitrile, and mixed solvents thereof. In the fifth step, the reaction temperature is, for example, 0 to 50° C., and the reaction time is, for example, 10 minutes or more and 5 hours or less.

[0365] After the salt exchange reaction is completed, the compound in the reaction solution may be isolated and purified. For the isolation and purification, a conventionally known method can be used, and for example, a suitable combination of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used. The structure of the compound obtained as above is 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19Identification can be achieved by common organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.

[0366] The raw materials, reagents, etc. used in each step may be commercially available or may be synthesized. In the above-mentioned method for producing the component (D0), L in the general formula (d0) 1 The production method for the compound in which L in the general formula (d0) is -OC(=O)- (ester bond) has been described above. 1 In the method for producing a compound in which is -C(=O)-NH- (amide bond), a compound in which the x hydroxy groups (-OH) in the compound (CA0) are replaced with amino groups (-NH2) may be used as a starting material.

[0367] The compound of this embodiment described above is a suitable compound as a base component for the resist composition according to the first aspect of the present invention. The compound of this embodiment can also be used as an acid diffusion controller according to the fourth aspect described below.

[0368] (Acid diffusion control agent) The acid diffusion controller according to the fourth aspect of the present invention contains the compound according to the third aspect (compound (D0)) described above. The acid diffusion controller of this embodiment is particularly suitable as the base component for the resist composition according to the first aspect described above. Such an acid diffusion controller is useful as an acid diffusion controller for a chemically amplified resist composition. The compound related to the third aspect described above has a carboxylate anion in the anion moiety, and therefore generates, upon exposure, an acid whose acid strength is weaker than that of, for example, a fluorinated alkylsulfonate anion in the anion moiety of an acid generator that is generally used in a chemically amplified resist composition. By using such an acid diffusion controller in a chemically amplified resist composition, lithography properties such as pattern shape (rectangularity) and reduced roughness are further improved in resist pattern formation. By using such an acid diffusion controller, lithography properties such as sensitivity, pattern shape (rectangularity) and reduced roughness are further improved in resist pattern formation, particularly when an EB or EUV light source is used. EXAMPLES

[0369] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In this example, the compound represented by the chemical formula (X-1-1) is referred to as "compound (X-1-1)", and compounds represented by other chemical formulas are similarly referred to.

[0370] <Production of the first intermediate> (Production Example 1-1) In a 300mL three-neck flask, 1,1'-carbonyldiimidazole (CDI) (8.60g, 41.7mmol) and tetrahydrofuran (THF) (20g) were added, and then 4-iodosalicylic acid (ca1) (10.0g, 37.9mmol) dissolved in THF (20g) was added dropwise over 30 minutes and stirred for 1 hour. Then, tert-butyl alcohol (3.37g, 45.5mmol) was added and reacted at 65°C for 3 hours. After cooling, ultrapure water (250g) and methyl tert-butyl ether (MTBE) (150g) were added, stirred for 30 minutes, and the aqueous layer was removed. The organic layer was then washed three times with ultrapure water (100 g), the solvent was distilled off from the organic layer, and the resulting crude material was dissolved again in THF (20 g), and methanol (80 g) was added dropwise to precipitate a solid, which was filtered and dried under reduced pressure to obtain 9.46 g of the first intermediate (pre-a01).

[0371] [ka]

[0372] (Production Examples 1-2 to 1-7) The starting material, 4-iodosalicylic acid (ca1) (10.0 g, 37.9 mmol), was changed to the following starting materials (ca2) to (ca7) in equimolar amounts, and the first intermediates (pre-a02) to (pre-a07) were obtained in the same manner as above (Manufacturing Example 1-1).

[0373] [ka]

[0374] The obtained first intermediates (pre-a01) to (pre-a07) are shown below.

[0375] [ka]

[0376] <Production of the second intermediate> (Production Example 2-1) In a 300 mL three-neck flask, 60% sodium hydride (NaH) (2.92 g, 73.1 mmol) and THF (30 g) were added, and then 1-butanol (E1) (4.51 g, 60.9 mmol) was added dropwise over 30 minutes under ice cooling, and the mixture was allowed to react for 30 minutes. Then, 5-norbornene-2,3-dicarboxylic anhydride (DA1) (10.0 g, 60.9 mmol) dissolved in THF (20 g) was added dropwise over 20 minutes, and the mixture was stirred at room temperature for 7 hours. The reaction solution was added dropwise to a 5 wt% aqueous hydrochloric acid solution (64.33 g) under ice cooling, and after stirring for 1 hour, the aqueous layer was removed. Then, the solvent was distilled off from the organic layer, and the obtained crude product was recrystallized with methanol, and the precipitated solid was filtered and dried under reduced pressure to obtain 8.7 g of the second intermediate (pre-B01).

[0377] [ka]

[0378] (Production Examples 2-2 to 2-11) In the same manner as in the above (Example 2-1), the following dicarboxylic anhydride (DA1) and dicarboxylic anhydride (DA2) were reacted with the following reagents (E2) to (E10) in the combinations shown below to obtain the second intermediates (PRE-B02) to (PRE-B11).

[0379] [ka]

[0380] Second intermediate (Pre-B02): Combination of dicarboxylic anhydride (DA1) and reagent (E2) Second intermediate (Pre-B03): Combination of dicarboxylic anhydride (DA1) and reagent (E3) Second intermediate (Pre-B04): Combination of dicarboxylic anhydride (DA1) and reagent (E4) Second intermediate (Pre-B05): Combination of dicarboxylic anhydride (DA1) and reagent (E5) Second intermediate (Pre-B06): Combination of dicarboxylic anhydride (DA1) and reagent (E6) Second intermediate (Pre-B07): Combination of dicarboxylic anhydride (DA1) and reagent (E7) Second intermediate (Pre-B08): Combination of dicarboxylic anhydride (DA1) and reagent (E8) Second intermediate (Pre-B09): Combination of dicarboxylic anhydride (DA1) and reagent (E9) Second intermediate (Pre-B10): Combination of dicarboxylic anhydride (DA1) and reagent (E10) Second intermediate (Pre-B11): Combination of dicarboxylic anhydride (DA2) and reagent (E4)

[0381] The obtained second intermediates (pre-b01) to (pre-b11) are shown below.

[0382] [ka]

[0383] (Production Example 2-12) 2-((2,2,3,3,4,4,4-heptafluorobutyl)oxy)acetic acid (20.0 g, 77.5 mmol), thionyl chloride (18.4 g, 155 mmol), and N,N-dimethylformamide (DMF) (40 g) were added to a 200 mL three-neck flask, and the mixture was stirred at 70° C. for 4 hours. The solvent was then distilled off to obtain 15.4 g of compound (cac1).

[0384] [ka]

[0385] In a 500mL three-neck flask, 3-hydroxy-1-adamantane carboxylic acid (7.8g, 40.0mmol), THF (54.6g), and triethylamine (6.1g) were added, and the compound (cac1) (12.1g, 44.1mmol) dissolved in THF (15.6g) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 3 hours. The solvent of the reaction solution was distilled off, and the concentrate was dissolved in dichloromethane (80g), washed twice with 5wt% aqueous hydrochloric acid solution (80g) and three times with ultrapure water (80g), and the solvent was distilled off from the organic layer. The obtained crude product was recrystallized with methanol, and the precipitated solid was filtered and dried under reduced pressure to obtain 14.1g of the second intermediate (pre-b12).

[0386] [ka]

[0387] <Production of the third intermediate> (Production Example 3-1) The second intermediate (pre-b01) (7.1 g, 30.0 mmol), dichloromethane (71 g), diisopropylcarbodiimide (4.5 g, 36.0 mmol), and dimethylaminopyridine (0.37 g, 3.0 mmol) were added to a 300 mL three-neck flask and stirred at room temperature for 30 minutes. Then, the first intermediate (pre-a01) (9.12 g, 28.5 mmol) was added and stirred at room temperature for 5 hours. The reaction solution was filtered, the solvent was distilled off from the filtrate, and the concentrate was dissolved in acetonitrile (16 g) and methanol (32 g), after which MTBE (160 g) was dropped and the precipitated solid was filtered. This operation was repeated three times, and the residue was dried under reduced pressure to obtain 12.0 g of the third intermediate (pre-c01).

[0388] [ka]

[0389] (Production Example 3-2 to Production Example 3-21) In the same manner as described above (Production Example 3-1), the first intermediates (pre-a01) to (pre-a07) were reacted with the second intermediates (pre-b01) to (pre-b12) in the combinations shown below to obtain the third intermediates (pre-c02) to (pre-c21).

[0390] The third intermediate (pre-c02): a combination of the first intermediate (pre-a01) and the second intermediate (pre-b02) The third intermediate (pre-c03): a combination of the first intermediate (pre-a01) and the second intermediate (pre-b04) The third intermediate (pre-c04): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b01) The third intermediate (pre-c05): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b05) The third intermediate (pre-c06): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b02) The third intermediate (pre-c07): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b03) The third intermediate (pre-c08): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b06) The third intermediate (pre-c09): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b04) The third intermediate (pre-c10): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b07) The third intermediate (pre-c11): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b08) The third intermediate (pre-c12): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b09)

[0391] The third intermediate (pre-c13): a combination of the first intermediate (pre-a03) and the second intermediate (pre-b04) The third intermediate (pre-c14): a combination of the first intermediate (pre-a04) and the second intermediate (pre-b04) The third intermediate (pre-c15): a combination of the first intermediate (pre-a05) and the second intermediate (pre-b04) The third intermediate (pre-c16): a combination of the first intermediate (pre-a05) and the second intermediate (pre-b10) The third intermediate (pre-c17): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b11) The third intermediate (pre-c18): a combination of the first intermediate (pre-a02) and the second intermediate (pre-b12) The third intermediate (pre-c19): a combination of the first intermediate (pre-a06) and the second intermediate (pre-b02) The third intermediate (pre-c20): a combination of the first intermediate (pre-a06) and the second intermediate (pre-b04) The third intermediate (pre-c21): a combination of the first intermediate (pre-a07) and the second intermediate (pre-b07)

[0392] The obtained third intermediates (pre-c01) to (pre-c21) are shown below.

[0393] [ka]

[0394] [ka]

[0395] <Production of Precursor (D')> (Production Example 4-1) The third intermediate (pre-c01) (10.8 g, 20.0 mmol), dichloromethane (100 g), and trifluoroacetic acid (TFA) (22.8 g, 200 mmol) were added to a 200 mL three-neck flask and stirred at 30°C for 8 hours. After the reaction, ultrapure water (100 g) was added and stirred for 30 minutes, after which the aqueous layer was removed. The organic layer was then washed three times with ultrapure water (100 g), and the solvent was distilled off from the organic layer to obtain 8.8 g of precursor (D'-01).

[0396] [ka]

[0397] (Production Example 4-2 to Production Example 4-21) In the same manner as in the above (Production Example 4-1), the third intermediates (pre-c02) to (pre-c21) were reacted with trifluoroacetic acid (TFA), respectively, to obtain precursors (D'-02) to (D'-21).

[0398] The obtained precursors (D'-01) to (D'-21) are shown below.

[0399] [ka]

[0400] [ka]

[0401] <Production of compound (D0)> (Production Example 5-1) Precursor (D'-01) (6.0 g, 12.4 mmol) and compound A (4.7 g, 13.6 mmol) were dissolved in dichloromethane (50 g), and 5% tetramethylammonium hydroxide (TMAH) aqueous solution (25 g) was added and reacted at room temperature for 30 minutes. After the reaction was completed, the aqueous phase was removed and the organic phase was washed five times with ultrapure water (50 g). The solvent was distilled off from the organic phase to obtain 8.4 g of compound (D0-1).

[0402] [ka]

[0403] (Production Example 5-2 to Production Example 5-24) In the same manner as in the above (Production Example 5-1), the precursors (D'-02) to (D'-21) were reacted with the following salt-exchange compounds A to D in the following combinations to obtain the target compounds (D0-2) to (D0-24).

[0404] [ka]

[0405] NMR measurements were carried out on each of the obtained compounds, and their structures were identified from the following analytical results.

[0406] Compound (D0-1): combination of precursor (D'-01) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=7.91 (1H, dd), 7.72 (1H, d), 7.62 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4.06 (2H, t), 3.75-3.63 (2H, m), 3.04-2.96 (2H, m), 1.79-1.71 (1H, m), 1.58-1.30 (5H, m), 0.90 (3H, t).

[0407] Compound (D0-2): combination of precursor (D'-02) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=7.91 (1H, dd), 7.72 (1H, d), 7.62 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4.60 (2H, dd), 3.75-3.63 (2H, m), 3.03-2.97 (2H. m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0408] Compound (D0-3): combination of precursor (D'-03) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=7.91 (1H, dd), 7.72 (1H, d), 7.62 (1H, d), 7.42-7.28 (15H, m), 6.09-6.02 (2H, m), 4.39 (2H, t), 3.76-3.64 (2H, m), 3.03-2.97 (2H, m), 1.80-1.72 (1H, m), 1.55-1.47 (1H, m).

[0409] Compound (D0-4): combination of precursor (D'-04) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4.06 (2H, t), 3.75-3.63 (2H, m), 3.04-2.96 (2H, m), 1.79-1.71 (1H, m), 1.58-1.30 (5H, m), 0.90 (3H, t).

[0410] [ka]

[0411] Compound (D0-5): combination of precursor (D'-05) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.43-7.29 (15H, m), 7.26-7.19 (4H, m), 6.09-6.01 (2H, m), 5.34 (2H, s), 3.75-3.62 (2H, m), 3.04-2.98 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0412] Compound (D0-6): combination of precursor (D'-06) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4,38 (2H, t), 3.75-3.63 (2H, m), 3.03-2.97 (2H, m), 1.80-1.72(1H, m), 1.55-1.47 (1H, m).

[0413] Compound (D0-7): combination of precursor (D'-07) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.09-6.01 (2H, m), 4,42 (2H, t), 3.75-3.63 (2H, m), 3.03-2.97 (2H, m), 1.80-1.72 (1H, m), 1.55-1.47 (1H, m).

[0414] Compound (D0-8): combination of precursor (D'-08) and salt-exchanging compound A 1H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.09-6.01 (2H, m), 5.64 (2H, s), 3.75-3.63 (2H, m), 3.03-2.97 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0415] [ka]

[0416] Compound (D0-9): combination of precursor (D'-09) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.09-6.02 (2H, m), 4,43 (2H, t), 3.75-3.63 (2H, m), 3.03-2.97 (2H, m), 1.80-1.71 (1H, m), 1.55-1.47 (1H, m).

[0417] Compound (D0-10): combination of precursor (D'-10) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.10-6.01 (2H, m), 4,42 (2H, t), 3.75-3.63 (2H, m), 3.03-2.97 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0418] Compound (D0-11): combination of precursor (D'-11) and salt-exchanging compound A 1H-NMR(DMSO,400MHz):δ(ppm)=8.31 ​​(1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4.38 (2H, t), 3.75-6.63 (2H, m), 3.03-2.97 (2H. m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0419] Compound (D0-12): Combination of precursor (D'-12) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.19 (1H, d), 7.42-7.28 (15H, m), 6.08-6.02 (2H, m), 4.38 (2H, t), 3.75-3.63 (2H, m), 3.03-2.97 (2H. m), 1.80-1.71 (1H, m), 1.54-1.46 (1H, m).

[0420] [ka]

[0421] Compound (D0-13): combination of precursor (D'-13) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.18 (2H, s), 7.42-7.28 (15H, m), 6.27-6.19 (2H, m), 4.38 (2H, t), 3.76-3.64(2H, m), 3.04-2.98 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0422] Compound (D0-14): combination of precursor (D'-14) and salt-exchanging compound A 1H-NMR(DMSO,400MHz):δ(ppm)=21.38 (1H, brs), 8.01 (1H, s), 7.42-7.28 (15H, m), 6.26-6.20 (2H, m), 4.39 (2H, t), 3.76-3.64(2H, m), 3.03-2.97 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0423] Compound (D0-15): combination of precursor (D'-15) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=10.02 (1H, brs), 8.40 (1H, d), 8.28 (1H, d), 7.42-7.28 (15H, m), 6.26-6.20 (2H, m), 4.38 (2H, t), 3.74-3.61(2H, m), 3.41-3.31 (1H, m), 2.67 (1H, t), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0424] Compound (D0-16): combination of precursor (D'-16) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=10.02 (1H, brs), 8.40 (1H, d), 8.28 (1H, d), 8.01 (1H, brs), 7.42-7.28 (15H, m), 6.25-6.21 (2H, m), 3.50 (2H, t), 3.43-3.29 (2H, m), 2.94 (1H, t), 2.78 (1H, t), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0425] [ka]

[0426] Compound (D0-17): combination of precursor (D'-17) and salt-exchanging compound A 1 H-NMR (DMSO, 400MHz): δ(ppm)=8.31 ​​(1H, d), 8.20 (1H, d), 7.42-7.14 (23H, m), 4.48-3.34 (4H, m), 3.48-3.40 (2H, m).

[0427] Compound (D0-18): combination of precursor (D'-18) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.29 (1H, d), 8.18 (1H, d), 7.42-7.28 (15H, m), 4.33 (2H, s), 3.67 (2H, t), 2,05 (1H, s), 1.83-1.69 (4H, m), 1.58-1.25 (6H, m), 1.19-1.04 (3H, m).

[0428] [ka]

[0429] Compound (D0-19): combination of precursor (D'-19) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.20 (1H, s), 7.42-7.28 (15H, m), 6.26-6.20 (2H, m), 4.60 (2H, dd), 3.76-3.62 (2H, m), 3.03-2.97 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0430] Compound (D0-20): combination of precursor (D'-20) and salt-exchanging compound A 1H-NMR(DMSO,400MHz):δ(ppm)=8.20 (1H, s), 7.42-7.28 (15H, m), 6.27-6.20 (2H, m), 4.38 (2H, t), 3.76-3.62 (2H, m), 3.03-2.97 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0431] Compound (D0-21): Combination of precursor (D'-21) and salt-exchanging compound A 1 H-NMR(DMSO,400MHz):δ(ppm)=8.23 (1H, d), 7.97 (1H, d), 7.42-7.28 (15H, m), 6.26-6.20 (2H, m), 4.38 (2H, t), 3.74-3.60 (2H, m), 3.05-2.98 (2H, m), 1.79-1.71 (1H, m), 1.54-1.46 (1H, m).

[0432] [ka]

[0433] Compound (D0-22): Combination of precursor (D'-09) and salt-exchanging compound B 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.20 (1H, d), 7.80 (2H d), 7.68 (2H, d), 7.41-7.30 (10H, m), 6.09-6.02 (2H, m), 4,43 (2H, t), 3.75-3.63 (2H, m), 3.03-2.92 (3H, m), 2.15-2.03 (2H, m), 1.91-1.71 (3H, m), 1.60-1.36 (7H, m).

[0434] Compound (D0-23): combination of precursor (D'-09) and salt-exchanging compound C 1H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.18 (1H, d), 7.80-7.74 (2H, m), 7.56-7.44 (6H, m), 7.40-7.30 (5H, m), 6.10-6.02 (2H, m), 4,44 (2H, t), 3.75-3.62 (2H, m), 3.03-2.97 (2H, m), 1.80-1.71 (1H, m), 1.55-1.47 (1H, m).

[0435] Compound (D0-24): Combination of precursor (D'-09) and salt-exchanging compound D 1 H-NMR(DMSO,400MHz):δ(ppm)=8.30 (1H, d), 8.19 (1H, d), 7.41-7.30 (5H, m), 6.71-6.83 (6H, m), 6.09-6.02 (2H, m), 4,43 (2H, t), 3.74-3.63 (2H, m), 3.03-2.96 (2H, m), 1.80-1.71 (1H, m), 1.55-1.48 (1H, m).

[0436] [ka]

[0437] <Preparation of Resist Composition> (Examples 1 to 30, Comparative Examples 1 to 4) The components shown in Tables 1 to 4 were mixed and dissolved to prepare resist compositions of each example. However, Examples 1 and 4 are reference examples.

[0438] [Table 1]

[0439] [Table 2]

[0440] [Table 3]

[0441] [Table 4]

[0442] In Tables 1 to 4, the abbreviations have the following meanings: The numbers in brackets [ ] are the blend amounts (parts by mass). (A)-1: A polymer compound represented by the following chemical formula (A1-1): The weight average molecular weight (Mw) of this polymer compound (A1-1) calculated using standard polystyrene standards by GPC measurement is 5,800, and the molecular weight dispersity (Mw / Mn) is 1.54. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 50 / 50. (A)-2: A polymer compound represented by the following chemical formula (A1-2): This polymer compound (A1-2) has a weight average molecular weight (Mw) of 6000 and a molecular weight dispersity (Mw / Mn) of 1.55, calculated based on standard polystyrene, as determined by GPC measurement. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 50 / 50. (A)-3: A polymer compound represented by the following chemical formula (A1-3): The weight average molecular weight (Mw) of this polymer compound (A1-3) calculated using standard polystyrene standards by GPC measurement is 5900, and the molecular weight dispersity (Mw / Mn) is 1.54. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 50 / 50.

[0443] [ka]

[0444] (B)-1: An acid generator comprising the following compound (B1-1): (B)-2: An acid generator comprising the following compound (B1-2):

[0445] [ka]

[0446] (D)-1 to (D)-24: Compounds (D0-1) to (D0-24) above. (D)-31: An acid diffusion controller comprising the following compound (D1-1): (D)-32: An acid diffusion controller consisting of the following compound (D1-2). (D)-33: An acid diffusion controller consisting of the following compound (D1-3). (D)-34: An acid diffusion controller consisting of the following compound (D1-4).

[0447] [ka]

[0448] (S)-1: a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0449] <Formation of Resist Pattern> Each resist composition of the example was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then pre-baked (PAB) on a hot plate at 110°C for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm. Next, the resist film was subjected to drawing (exposure) using an electron beam drawing apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV to form a 1:1 line and space pattern (hereinafter referred to as "LS pattern") with a target size of a line width of 50 nm. This was followed by a post-exposure bake (PEB) treatment at 100° C. for 60 seconds. Thereafter, alkaline development was carried out for 60 seconds using a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C. Then, water rinsing was carried out for 15 seconds using pure water. As a result, a 1:1 LS pattern with a line width of 50 nm was formed.

[0450] [Sensitivity evaluation] The optimum exposure dose Eop (μC / cm) at which the LS pattern of the target size is formed by the above <Formation of resist pattern> 2 The result was called Eop (μC / cm 2 ) are shown in Tables 5 and 6.

[0451] [Evaluation of LWR (Line Width Roughness)] For the LS pattern formed by the above <Formation of Resist Pattern>, 3σ, which is a scale indicating LWR, was obtained. "3σ" indicates three times the standard deviation (σ) (unit: nm) obtained from the measurement results of 400 line positions measured in the longitudinal direction of the line using a scanning electron microscope (accelerating voltage 800V, product name S-9380, manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 5 to 6 as "LWR (nm)". The smaller the 3σ value, the less rough the line sidewall is, meaning that a LS pattern with a more uniform width is obtained.

[0452] [Evaluation of pattern shape] In the above <Formation of Resist Pattern>, the cross-sectional shape of the lines in each obtained LS pattern was observed with a scanning electron microscope (accelerating voltage 300V, product name SU8000, manufactured by Hitachi High-Technologies Corporation). The cross-sectional shape of the lines was observed at any 20 points of the line pattern. The line width (Lt) at the top of the line and the line width (Lm) at the middle of the line in the height direction of the LS pattern were measured, and the ratio (Lt / Lm) between them was calculated from the average of 20 measured values ​​of Lt and Lm. The closer the Lt / Lm value is to 1, the better the rectangularity of the cross-sectional shape of the line is (i.e., the higher the rectangularity is). Regarding the pattern shape, the ratio (Lt / Lm) was used as an index, and the rectangularity of the cross-sectional shape of the line was evaluated according to the following evaluation criteria. 0.95≦(Lt / Lm)≦1.05 is "◎: particularly good"; 0.90≦(Lt / Lm)<0.95 or 1.05<(Lt / Lm)≦1.10: "Good" The cases where (Lt / Lm) was < 0.90 or 1.10 < (Lt / Lm) were evaluated as "x: poor". As evaluations of the pattern shape, the Lt / Lm value and the evaluation results of rectangularity are shown in Tables 5 and 6.

[0453] [Table 5]

[0454] [Table 6]

[0455] From the results shown in Tables 5 to 6, by comparing Examples 1 to 30 with Comparative Examples 1 to 4, it can be seen that the resist compositions of Examples 1 to 30 to which the present invention is applied achieve both high sensitivity and reduced roughness, and in addition, are capable of forming patterns with a good shape and high rectangularity. Furthermore, it can also be confirmed that, compared to the resist compositions of Comparative Examples 1-4, the resist compositions of Examples 1-30 have an even greater effect of reducing roughness.

Claims

1. A resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid, a base component (A) whose solubility in a developer changes under the action of an acid; A compound (D0) represented by the following general formula (d0), A resist composition comprising: 【Chemistry 1】 [In the formula, Rf is a fluorinated hydrocarbon group. ２ is a divalent cyclic group which may have a substituent, and the divalent cyclic group in L 2 is an aromatic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane or polycycloalkene, or a fused cyclic group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. L 1 is -OCO-, -COO-, -NH-C(=O)-, or -C(=O)-NH-. L 3 is -OCO-, -COO-, -NH-C(=O)-, -C(=O)-NH-, or -O-C(=O)-alkylene group -O-. x is an integer from 1 to 4. When x is an integer of 2 or more, multiple -L １ -L ２ -L ３ Rf may be the same or different. ｄ０ is an iodine atom or a bromine atom. y is an integer of 1 to 4. When y is an integer of 2 or more, a plurality of R ｄ０ may be the same or different. z is 0 or 1, provided that 2≦x+y+z≦5. (M ｍ＋ ) １／ｍ is a counter cation; and m is an integer of 1 or more.

2. 2. The resist composition according to claim 1, wherein in said formula (d0), a total number of fluorine atoms contained in x Rf's is 5 or more and 9 or less.

3. The resist composition according to claim 1, wherein in formula (d0), y is 2 or 3.

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

5. 5. The method for forming a resist pattern according to claim 4, wherein in the step of exposing the resist film, the resist film is exposed to EUV (extreme ultraviolet) or EB (electron beam).

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