Resist composition, resist pattern formation method, compound, and acid diffusion control agent

Abstract

To provide a resist composition that enhances temporal stability during storage and prevents reduction in fine resolution after storage, a resist pattern forming method using the resist composition, and a compound suitable as an acid diffusion controller for use in the resist composition.SOLUTION: A resist composition is adopted that comprises a base component (A) with a varying solubility to developers due to the action of an acid, and a compound (D0) represented by the general formula (d0). In the formula (d0), R1 is a saturated hydrocarbon group, and I is an iodine atom. R2 is a substituent. Yd0 is a divalent linking group or a single bond. j is an integer of 0-3. k is an integer of 1-4. At least one of Rb11, Rb12, Rb13 and Rb14 is a fluorine atom or fluorinated alkyl group. Rb2 and Rb3 are hydrocarbon groups, or mutually bind to form a ring with a sulfur atom.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

[0004] In the formation of resist patterns, the behavior of acids generated from acid-generating agent components upon exposure is considered a significant factor influencing lithography characteristics. In response to this, a chemically amplified resist composition has been proposed that includes both an acid generating agent component and an acid diffusion control agent that controls the diffusion of the acid generated from the acid generating agent component upon exposure.

[0005] For example, Patent Document 1 discloses a resist composition containing a resin component whose solubility in a developer changes due to the action of an acid, an acid generator component, and a photoreactive quencher having a specific structured cationic portion as an acid diffusion control agent. This photoreactive quencher is a component that exhibits a quenching effect by undergoing an ion exchange reaction with the acid generated from the acid generator component. By incorporating such a photoreactive quencher, the diffusion of the acid generated from the acid generator component from the exposed area to the unexposed area of ​​the resist film is controlled, thereby improving the lithography characteristics. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2021-103232 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, conventional resist compositions, such as those described in Patent Document 1 above, have the drawback that their fine resolution deteriorates during storage. Therefore, the present invention aims to provide a resist composition in which the stability over time during storage is enhanced and the decrease in fine resolution after storage is suppressed, a method for forming a resist pattern using the resist composition, and a compound useful as an acid diffusion control agent for use in the resist composition. [Means for solving the problem]

[0008] To solve the above problems, the present invention employs the following configuration. In other words, a first aspect of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid, comprising a base component (A) whose solubility in a developer solution changes due to the action of the acid, and a compound (D0) represented by the following general formula (d0).

[0009] [ka] [In the formula, R 1 is a saturated hydrocarbon group. I is an iodine atom. R 2 Yd is a substituent. 0 is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb 11 , Rb 12 , Rb 13 and Rb 14is, independently of each other, a fluorine atom, a fluorinated alkyl group or a hydrogen atom. Rb 11 Rb 12 Rb 13 and Rb 14 At least one of is a fluorine atom or a fluorinated alkyl group. Rb 2 and Rb 3 are, independently of each other, a hydrocarbon group which may have a substituent, or Rb[[ID={13}]] 2 and Rb 3 are bonded to each other to form a ring together with the sulfur atom in the formula.]

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

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

[0012]

Chemical formula

[0013] A fourth aspect of the present invention is an acid diffusion control agent containing the compound according to the third aspect. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a resist composition in which the stability over time during storage is enhanced and the decrease in fine resolution after storage is suppressed, a method for forming a resist pattern using the resist composition, and a compound useful as an acid diffusion control agent used in the resist composition. [Modes for carrying out the invention]

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

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

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

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

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

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

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

[0022] (Resist composition) The resist composition of this embodiment generates acid upon exposure, and its solubility in the developer changes due to the action of the acid. Such a resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in the developer solution changes due to the action of an acid, and a compound (D0) (hereinafter also referred to as "component (D0)") represented by the general formula (d0) described later.

[0023] In the resist composition of this embodiment, component (A) may generate acid upon exposure, or an additive component formulated separately from component (A) may generate acid upon exposure. The resist composition of this embodiment may specifically (1) further contain an acid generating agent component (B) (hereinafter referred to as "component (B)") that generates acid upon exposure; (2) component (A) may be a component that generates acid upon exposure; or (3) component (A) may be a component that generates acid upon exposure and also contains component (B). In other words, in the cases of (2) and (3) above, component (A) is a "base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid." When component (A) is a base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1), described later, is a resin that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid. As such a resin, a polymer compound having a constituent unit that generates acid upon exposure can be used. Known constituent units that generate acid upon exposure can be used.

[0024] In this embodiment, the resist composition is preferably the one described in (1) above. That is, the resist composition of this embodiment preferably contains component (A) and component (B).

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

[0026] The resist composition of this embodiment may be a positive-type resist composition or a negative-type resist composition. Furthermore, the resist composition of this embodiment may be for an alkaline development process that uses an alkaline developer for the development process during resist pattern formation, or for a solvent development process that uses a developer containing an organic solvent (organic developer) for the development process.

[0027] <(A) component> In the resist composition of this embodiment, component (A) preferably includes a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in the developer solution changes due to the action of an acid. By using component (A1), the polarity of the substrate component changes before and after exposure, so good development contrast can be obtained not only in the alkaline development process but also in the solvent development process. (A) Component (A1) may be used in combination with other high-molecular-weight compounds and / or low-molecular-weight compounds.

[0028] In the resist composition of this embodiment, component (A) may be used alone or in combination of two or more types.

[0029] (A1) About the ingredients Component (A1) is a resin component whose solubility in the developer changes due to the action of acid. (A1) Component is preferably one that has a constituent unit (a1) containing an acid-degradable group whose polarity increases due to the action of an acid. Component (A1) may have other constituent units in addition to the constituent unit (a1) as needed.

[0030] ≪Component Unit (a1)≫ The constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid.

[0031] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Specifically, proposed acid-dissociable groups for base resins used in chemically amplified resist compositions include the following: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "tertiary alkyloxycarbonyl acid-dissociable groups."

[0032] Acetal type acid dissociable group: Examples of acid-dissociable groups that protect a carboxyl group or a hydroxyl group among the aforementioned polar groups include the acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0033] [ka] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. 3 Ra' is a hydrocarbon group. 3 Ra' 1 , Ra' 2 It may combine with any of the following to form a ring.

[0034] In formula (a1-r-1), Ra' 1 and Ra' 2 Preferably, at least one of them is a hydrogen atom, and more preferably, both are hydrogen atoms. Ra' 1 Or Ra' 2 If the alkyl group is an alkyl group, the alkyl group can be the same as those listed in the description of the α-substituted acrylic acid ester above as substituents that may be bonded to the carbon atom at the α position, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc., with methyl group or ethyl group being more preferred, and methyl group being particularly preferred.

[0035] In formula (a1-r-1), Ra' 3 Examples of hydrocarbon groups include linear or branched alkyl groups, or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0036] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0037] Ra' 3 When the hydrocarbon group 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. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic group, a alicyclic hydrocarbon group is preferred, which is a group obtained by removing one hydrogen atom from a polycycloalkane, and as a polycycloalkane, those having 7 to 12 carbon atoms are preferred, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0038] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Ra' 3Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); groups obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups 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, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0039] Ra' 3 The cyclic hydrocarbon group in may have substituents. Examples of substituents include -R P1 ,-R P2 -OR P1 ,-R P2 -CO-R P1 ,-R P2 -CO-OR P1 ,-R P2 -O-CO-R P1 ,-R P2 -OH, -R P2 -CN or -R P2 -COOH (These substituents are collectively referred to as "Ra" below) x5 It is also called "[...]." Examples include [...]. Here, R P1 This is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 R is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, R P1 and R P2Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the substituents individually, or it may have one or more of each of the substituents. Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

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

[0041] Tertiary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-2). Furthermore, among the acid-dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may, for convenience, be referred to below as "tertiary alkyl ester type acid-dissociable groups."

[0042] [ka] [In the formula, Ra' 4 ~Ra' 6 Each of these is a hydrocarbon group, Ra' 5 , Ra' 6 They may be joined to each other to form a ring.

[0043] Ra' 4 Examples of hydrocarbon groups include linear or branched alkyl groups, linear or cyclic alkenyl groups, linear alkynyl groups, or cyclic hydrocarbon groups. Ra' 4 In the above, linear or branched alkyl groups, cyclic hydrocarbon groups (monocyclic alicyclic hydrocarbon groups, polycyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups) are defined as the Ra' 3 Similar examples include the above. Ra' 4 The linear or cyclic alkenyl group in this is preferably an alkenyl group having 2 to 10 carbon atoms. Ra' 5 , Ra' 6 The hydrocarbon group is the aforementioned Ra' 3 Similar examples include the above.

[0044] Ra' 5 and Ra' 6 When these groups bond to each other to form a ring, the following groups are preferred: the group represented by the general formula (a1-r2-1), the group represented by the general formula (a1-r2-2), and the group represented by the general formula (a1-r2-3). Meanwhile, Ra' 4 ~Ra' 6 When these are independent hydrocarbon groups that are not bonded to each other, the groups represented by the following general formula (a1-r2-4) are preferred.

[0045] [Chemical formula] In 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. Ra’ 11 is a group that forms an aliphatic cyclic group together with the carbon atom to which Ra’ 10 is bonded. 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 of this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 each independently represents a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Ra 101 ~Ra 103 two or more of them may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra 104 is an aromatic hydrocarbon group that may have a substituent. In formula (a1-r2-4), Ra’ 12 and Ra’ 13 each independently represents a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra’ 14 is a hydrocarbon group that may have a substituent. * represents a bond (the same applies hereinafter).

[0046] In the above formula (a1-r2-1), Ra’ 10 is 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’ 10In this context, 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 In this, the branched alkyl group is the Ra' 3 Similar examples include the above.

[0048] Ra' 10 In this case, the alkyl group 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. Also, some of the carbon atoms constituting the alkyl group (such as a methylene group) may be substituted with a heteroatom-containing group. Examples of heteroatoms used here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

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

[0050] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in formula (a1-r-1). 3 Examples include groups obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (alicyclic hydrocarbon group). The cyclic hydrocarbon group formed by Xa and Ya may have substituents. Examples of such substituents include the above-mentioned Ra' 3Examples of the substituents that the cyclic hydrocarbon group in [compound name] may have are the same as those described above. In formula (a1-r2-2), Ra 101 ~Ra 103 Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in [compound name] 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, a decyl group, and the like. Ra 101 ~Ra 103 Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in [compound name] 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, a cyclododecyl group; 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, an adamantyl group, and the like. Ra 101 ~Ra 103 Among them, from the viewpoint of ease of synthesis, a hydrogen atom and a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms are preferable, and among them, a hydrogen atom, a methyl group, and an ethyl group are more preferable, and a hydrogen atom is particularly preferable.

[0051] The above Ra 101 ~Ra 103 Examples of the substituents that the linear saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by [compound name] has include, for example, the same groups as those of Ra described above. x5 and the like.

[0052] Ra 101 ~Ra 103Examples of the group containing a carbon-carbon double bond formed by bonding two or more of them to each other to form a cyclic structure include, for example, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, and the like. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferred.

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

[0054] Examples of the substituent that Ra in formula (a1-r2-3) 104 may have include, for example, 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, a butoxy group, etc.), an alkyloxycarbonyl group, and the like.

[0055] In formula (a1-r2-4), Ra’ 12 and Ra’ 13 are each independently a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Ra’ 12 and Ra’ 13In this context, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above-mentioned Ra 101 ~Ra 103 Examples include monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 Among these, alkyl groups having 1 to 5 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. The above Ra' 12 and Ra' 13 When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Ra x5 Similar bases can be cited.

[0056] In formula (a1-r2-4), Ra' 14 Ra' is a hydrocarbon group that may have substituents. 14 Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0057] Ra' 14 The linear alkyl group in this compound preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0058] Ra' 14 The branched alkyl group in this compound preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0059] Ra'14 When the hydrocarbon group 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. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic group, a alicyclic hydrocarbon group is preferred, which is a group obtained by removing one hydrogen atom from a polycycloalkane, and as a polycycloalkane, those having 7 to 12 carbon atoms are preferred, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0060] Ra' 14 As for aromatic hydrocarbon groups in this context, Ra 104 Examples include those similar to aromatic hydrocarbon groups in [the text]. Among them, Ra' 14 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from naphthalene or anthracene with one or more hydrogen atoms removed; and most preferably a group from naphthalene with one or more hydrogen atoms removed. Ra' 14 A substituent that may be present is Ra 104 Examples of substituents that may be present include those similar to those that the molecule may have.

[0061] Ra' in equation (a1-r2-4) 14 If is a naphthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in equation (a1-r2-4) 14When it is an antryl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be any of the 1-position, 2-position or 9-position of the antryl group.

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

[0063]

Chemical formula

[0064]

Chemical formula

[0065]

Chemical formula

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

[0067]

Chemical formula

[0068]

Chemical formula

[0069]

Chemical formula

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

[0071]

Chemical formula

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

[0073] [ka]

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

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

[0076] In formula (a1-r-3), Ra' 7 ~Ra' 9 Each of these is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Furthermore, 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-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-4).

[0078] [ka] [In the formula, Ra' 10 Ra' is a hydrocarbon group. 11a and Ra' 11b Each of these is independently 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 These elements may be joined together to form a ring. 11a Or Ra' 11b And, Ra' 12 These elements may be joined together to form a ring.

[0079] In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in this is the Ra' 3 Similar examples include the above. In the formula, Ra' 11a and Ra' 11b The alkyl group in is the aforementioned Ra' 1 Examples include alkyl groups similar to those in the above. In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in, and Ra' 11a and Ra' 11b The alkyl group in may have substituents. For example, the above-mentioned Ra is an example of such substituent. x5 These are some examples.

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

[0081] Ra' 10 and Ra' 11a Or Ra' 11b The rings formed by the bonding of these elements are preferably monocycloalkenes, rings in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), monocycloalkadienes, cycloalkenes having 3 to 6 carbon atoms, and cyclopentene or cyclohexene.

[0082] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may be a fused ring. Specific examples of such fused rings include indane.

[0083] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may have substituents. For example, the above-mentioned Ra x5 These are some examples.

[0084] Ra' 11a Or Ra' 11b And, Ra' 12 These elements may be bonded together to form a ring, and the ring may be Ra' 10 and Ra' 11a Or Ra' 11b Examples include rings formed by the bonding of these elements together.

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

[0086] [ka]

[0087] Examples of constituent units (a1) include constituent units derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent, constituent units derived from acrylamide, constituent units derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group of a constituent unit are protected by a substituent containing the acid-degradable group, and constituent units derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group are protected by a substituent containing the acid-degradable group.

[0088] As for the constituent unit (a1), among the above, a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent is preferred. A preferred specific example of such a constituent unit (a1) is a constituent unit represented by the following general formula (a1-1) or (a1-2).

[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. Va 1 n is a divalent hydrocarbon group which may have an ether bond. a1 is an integer between 0 and 2. 1 This is an acid-dissociable group represented by the general formula (a1-r-1), (a1-r-2), or (a1-r-4) above. 1 is n a2 It is a +1 valent hydrocarbon group, n a2 is an integer between 1 and 3, and Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above.

[0090] In formula (a1-1), the C1-C5 alkyl group of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The C1-C5 halogenated alkyl group is a group in which some or all of the hydrogen atoms of the C1-C5 alkyl group are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

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

[0092] Va 1 The aliphatic hydrocarbon group as a divalent hydrocarbon group in this compound may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

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

[0094] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear or branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a monocycloalkane with two hydrogen atoms removed. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a polycycloalkane with two hydrogen atoms removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0095] Va 1 In this context, an aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings in aromatic hydrocarbon groups include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0096] In the above formula (a1-1), Ra 1 This is an acid-dissociable group represented by the above formula (a1-r-1), (a1-r-2), or (a1-r-4).

[0097] In the above formula (a1-2), Wa 1 n in a2The +1 valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group that is a combination of a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure. The aforementioned n a2 The +1 valent is preferably 2 to 4 valent, and more preferably 2 or 3 valent.

[0098] In the above formula (a1-2), Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above.

[0099] The following are specific examples of constituent units (a1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] The constituent units (a1) of component (A1) may be one type or two or more types. As for the constituent unit (a1), the constituent unit represented by formula (a1-1) is more preferable because it is easier to improve the characteristics (LWR, etc.) in lithography using electron beams or EUV. Among these, the constituent unit (a1) is particularly preferred if it includes a constituent unit represented by the following general formula (a1-1-1).

[0109] [ka] [In the formula, Ra 1 " is an acid-dissociable group represented by the general formula (a1-r2-1) or (a1-r2-2). * indicates a bond.

[0110] In the above formula (a1-1-1), R, Va 1 and n a1 R, Va in the above formula (a1-1) 1 and n a1 It is similar to that. The explanation of the acid-dissociable group represented by the general formula (a1-r2-1) or (a1-r2-2) is as described above. In particular, it is preferable to select an acid-dissociable group that is a cyclic group, as it is suitable for EB or EUV applications because it enhances reactivity, and the acid-dissociable group represented by the general formula (a1-r2-1) is more preferable.

[0111] The proportion of constituent units (a1) in component (A1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of the constituent unit (a1) to be above the lower limit of the preferred range described above, lithography characteristics such as sensitivity, CDU, resolution, and roughness improvement are enhanced. On the other hand, if it is below the upper limit of the preferred range described above, a balance can be achieved with other constituent units, resulting in good lithography characteristics across various fields.

[0112] <<Other constituent units>> Component (A1) may have other constituent units in addition to the constituent unit (a1) described above, as needed. Other constituent units include, for example, the constituent unit (a10) represented by the general formula (a10-1) described below; the constituent unit (a2) containing a lactone-containing cyclic group; and the constituent unit (a8) derived from the compound represented by the general formula (a8-1) described below.

[0113] Regarding the constituent unit (a10): A constituent unit (a10) is a constituent unit represented by the following general formula (a10-1) (excluding those corresponding to constituent unit (a1)).

[0114] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. x1 Wa is a single bond or a divalent linking group. x1 n is an aromatic hydrocarbon group which may have substituents. ax1 [ is an integer greater than or equal to 1.]

[0115] In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. For R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and due to their industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is particularly preferred.

[0116] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0117] Ya x1 Preferably, the group is 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, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0118] In the above formula (a10-1), Wa x1 This is an aromatic hydrocarbon group which may have substituents. Wa x1 The aromatic hydrocarbon group in this context may be an aromatic ring that may have substituents (n ax1 A group with 1+1 hydrogen atoms removed is an example. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Also, Wax1 The aromatic hydrocarbon group in this context is an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.) (n ax1 Another example is a group with (+1) hydrogen atoms removed. Among the above, Wa x1 Examples include benzene, naphthalene, anthracene, or biphenyl (n ax1 A group with (+1) hydrogen atoms removed is preferred, and (n ax1 A group with (+1) hydrogen atoms removed is more preferable, and from benzene (n ax1 A group with (+1) hydrogen atoms removed is even more preferable.

[0119] Wa x1 The aromatic hydrocarbon group in may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents include Ya x1 Examples of substituents include those similar to those listed for the cyclic alicyclic hydrocarbon group in [the relevant section]. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, even more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. x1 In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0120] In the above formula (a10-1), n ax1 is an integer greater than or equal to 1, preferably an integer between 1 and 10, more preferably an integer between 1 and 5, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0121] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] (A1) The constituent units (a10) that component (A1) may have may be one type or two or more types. If component (A1) has constituent units (a10), the proportion of constituent units (a10) in component (A1) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 35 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of constituent unit (a10) above the lower limit, sensitivity can be more easily increased. On the other hand, by setting it below the upper limit, it becomes easier to balance it with other constituent units.

[0126] Regarding the constituent unit (a2): Component (A1) may further have a constituent unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to constituent unit (a1)). The lactone-containing cyclic group of component (a2) is effective in improving the adhesion of the resist film to the substrate when component (A1) is used to form a resist film. Furthermore, the presence of component (a2) improves lithography characteristics, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0127] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Any lactone-containing cyclic group can be used in the constituent unit (a2) without any particular limitations. Specifically, examples include the groups represented by the following general formulas (a2-r-1) to (a2-r-7).

[0128] [ka] [In the formula, Ra' 21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom, where n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond (the same applies below).

[0129] 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. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. Among these, the methyl group or ethyl group is preferred, and the methyl group is particularly preferred. Ra' 21 The alkoxy group in is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' 21Examples of alkyl groups in this context include groups formed by linking an alkyl group with an oxygen atom (-O-). Ra' 21 In this mixture, a fluorine atom is preferred as the halogen atom. Ra' 21 The halogenated alkyl group in is the Ra' 21 Examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. Fluorinated alkyl groups are preferred as the halogenated alkyl group, and perfluoroalkyl groups are particularly preferred.

[0130] Ra' 21 In -COOR'' and -OC(=O)R'', R'' is either a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' can be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R'' is a linear or branched alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When R'' is a cyclic alkyl group, it is preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of lactone-containing cyclic groups in R'' include those similar to those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above. Ra'21 The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, specifically the Ra' 21 Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0131] Ra' 21 Among the above, it is preferable that each is independently a hydrogen atom or a cyano group.

[0132] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5) above, the alkylene group having 1 to 5 carbon atoms in A'' is preferably a linear or branched alkylene group, such as a methylene group, ethylene group, n-propylene group, isopropylene group, etc. If the alkylene group contains an oxygen atom or a sulfur atom, specific examples include a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A'', an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0133] The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-7).

[0134] [ka]

[0135] [ka]

[0136] Among the constituent units (a2), those derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent are preferred. The constituent unit (a2) is preferably a constituent unit represented by the following general formula (a2-1).

[0137] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. 21 It is a single bond or a divalent linking group. 21 The R' is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La 21 If -O-, Ya 21 It does not become -CO-. 21 It is a lactone-containing cyclic group.

[0138] In formula (a2-1) above, R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0139] In the above formula (a2-1), Ya 21 The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0140] Ya 21 Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0141] In the above formula (a2-1), Ya 21 It is a single bond, La 21 It is preferable that it be -COO- or -OCO-.

[0142] In the above formula (a2-1), Ra 21 It is a lactone-containing cyclic group. Ra 21 Suitable lactone-containing cyclic groups in this compound include those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above.

[0143] (A1) The constituent units (a2) that the component may have may be one type or two or more types. If component (A1) has constituent units (a2), the proportion of constituent units (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 1 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is set above a preferred lower limit, the effects of including constituent unit (a2) are fully obtained due to the effects described above, and if it is below the upper limit, a balance can be achieved with other constituent units, resulting in good lithography characteristics.

[0144] Regarding the constituent unit (a8): The constituent unit (a8) is a constituent unit derived from the compound represented by the following general formula (a8-1). However, those corresponding to constituent unit (a0) are excluded.

[0145] [ka] [In the formula, W 2 This is a polymerizable group-containing group. x2 is a single bond or (n ax2 It is a linking group with a +1 valence. x2 and W 2 It may form a fused ring with R. 1 R is a fluorinated alkyl group having 1 to 12 carbon atoms. 2 R is an organic group having 1 to 12 carbon atoms, which may contain a fluorine atom, or a hydrogen atom. 2 and Ya x2 These may be bonded to each other to form a ring structure. ax2 [This is an integer between 1 and 3.]

[0146] W 2 In the context of polymerizable group-containing groups, "polymerizable group" refers to a group that enables a compound containing a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond.

[0147] The polymerizable group-containing group may be a group composed solely of a polymerizable group, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of other groups other than the polymerizable group include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Examples of polymerizable groups include those with the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 The group represented by - is preferably mentioned. In this chemical formula, R X11 , R X12 and R X13 These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 It is a single bond or a divalent linking group.

[0148] Ya x2 and W 2 The condensed ring formed by these is W 2 Polymerizable groups of the site and Ya x2 The condensed ring formed by and W 2 Other groups besides the polymerizable group of the site and Ya x2 A condensed ring formed by these is one example. Ya x2 and W 2 The fused ring formed by these two components may have substituents.

[0149] The following are specific examples of constituent units (a8). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0150] [ka]

[0151] Among the examples above, the constituent unit (a8) is preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0152] (A1) The constituent units (a8) that the component may have may be one type or two or more types. If component (A1) has constituent units (a8), the proportion of constituent units (a8) in component (A1) is preferably 30 mol% or less, more preferably 0 to 20 mol%, and even more preferably 0 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0153] The (A1) component contained in the resist composition may be used alone or in combination of two or more types. In the resist composition of this embodiment, component (A1) is a polymer compound having a repeating structure of the constituent unit (a1). (A1) Among the above, polymer compounds containing a repeating structure of constituent unit (a1) and constituent unit (a10) are preferred as component (A1), and polymer compounds consisting only of a repeating structure of constituent unit (a1) and constituent unit (a10) are more preferred.

[0154] In a polymer compound having a repeating structure of constituent units (a1) and constituent units (a10), the proportion of constituent units (a1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. Furthermore, the proportion of constituent units (a10) in the polymer compound is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0155] Such component (A1) can be produced by dissolving monomers that induce each constituent unit in a polymerization solvent and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the mixture and polymerizing it. Alternatively, such component (A1) can be produced by dissolving a monomer that induces constituent unit (a1) and, if necessary, a monomer that induces a constituent unit other than constituent unit (a1) (for example, constituent unit (a10)) in a polymerization solvent, adding a radical polymerization initiator as described above to this solution, polymerizing it, and then carrying out a deprotection reaction. Furthermore, during polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group at the terminal. Copolymers in which a hydroxyalkyl group, in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, are introduced are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0156] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance and a good cross-sectional shape of the resist pattern. (A1) The degree of dispersion of component (Mw / Mn) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0157] (A2) About the ingredients The resist composition of this embodiment may also include, as component (A), a base component (hereinafter referred to as "component (A2)") that does not correspond to component (A1) and whose solubility in the developer changes due to the action of an acid. (A2) The component is not particularly limited and can be arbitrarily selected from a large number of components that have been conventionally known as base components for chemically amplified resist compositions. (A2) Component may be a single high-molecular-weight compound or a low-molecular-weight compound, or two or more may be used in combination.

[0158] The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, it becomes easier to form a resist pattern that is excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement.

[0159] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0160] <Compound (D0)> Compound (D0) (hereinafter also referred to as "component (D0)") is a compound represented by the following general formula (d0). The resist composition of this embodiment, by containing component (D0), can improve the stability of the resist composition over time during storage and suppress the decrease in the fine resolution of the resist composition after storage.

[0161] [ka] [In the formula, R 1is a saturated hydrocarbon group. I is an iodine atom. R 2 Yd is a substituent. 0 is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb 11 , Rb 12 , Rb 13 and Rb 14 Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb 11 , Rb 12 , Rb 13 and Rb 14 At least one of them is a fluorine atom or a fluorinated alkyl group. Rb 2 and Rb 3 Each of these is independently a hydrocarbon group which may have substituents, or Rb 2 and Rb 3 These atoms are bonded to each other, forming a ring with the sulfur atom in the formula.

[0162] ((D0) component anion part) In the above equation (d0), R 1 This is a saturated hydrocarbon group. Examples of the saturated hydrocarbon group include a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms and a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups.

[0163] R 1 The saturated hydrocarbon group in is preferably a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent chain saturated hydrocarbon group having 1 to 6 carbon atoms, even more preferably a monovalent chain saturated hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0164] In the above equation (d0), R 2 R is a substituent. 2 Substituents in this compound include alkyl groups, nitro groups, chlorine atoms, and -C(=O)-O-Rd 01 -OC(=O)-Rd 02 , amino group, -NH-C(=O)-Rd 02 These are some examples. R 2 The alkyl group used as a substituent may be an alkyl group having 1 to 5 carbon atoms. Rd 01 This is an alkyl group, and may be a linear or branched alkyl group having 1 to 5 carbon atoms. Rd 02 This is a hydrocarbon group that may have substituents.

[0165] In the above formula (d0), j is an integer between 0 and 3. From the viewpoint of the solubility of the resist composition in the resist solvent, j is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. If j is an integer greater than or equal to 2, multiple R 2 These can be the same or different.

[0166] In the above formula (d0), k is an integer from 1 to 4. From the viewpoint of achieving both high sensitivity and solubility of the resist composition in the resist solvent, k is preferably an integer from 2 to 4, more preferably 2 or 3, and even more preferably 3.

[0167] In the above equation (d0), Yd 0 It is a single bond or a divalent linking group. Yd 0 The divalent linking group in the above general formula (a10-1) is Ya x1Examples include divalent linking groups similar to those in [the relevant context].

[0168] Yd 0 The divalent linking groups in are preferably -C(=O)-O-, -OC(=O)-, -O-, -C(=O)-, -NH-, -S-, linear or branched aliphatic hydrocarbon groups, or combinations thereof. The linear or branched aliphatic hydrocarbon groups are preferably linear or branched alkylene groups having 1 to 6 carbon atoms, or linear or branched alkenylene groups having 2 to 6 carbon atoms. The divalent linking groups in Ld are more preferably -C(=O)-O-, -OC(=O)-, -O-, or -C(=O)-.

[0169] From the viewpoint of improving solubility in the developer, Yd 0 A single bond is preferred.

[0170] The following shows a specific example of the anion portion of component (D0).

[0171] [ka]

[0172] ((D0) component cation) In the above equation (d0), Rb 11 , Rb 12 , Rb 13 and Rb 14 Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb 11 , Rb 12 , Rb 13 and Rb 14 At least one of them is a fluorine atom or a fluorinated alkyl group. Examples of fluorinated alkyl groups include fluorinated alkyl groups having 1 to 5 carbon atoms, with a trifluoromethyl group being preferred.

[0173] Rb 2 and Rb 3 Each of these is independently a hydrocarbon group which may have substituents, or Rb2 and Rb 3 These atoms are bonded to each other, forming a ring with the sulfur atom in the formula.

[0174] Rb 2 or Rb 3 If Rb is a hydrocarbon group which may have substituents, 2 and Rb 3 Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0175] Rb 2 and Rb 3 The linear alkyl group in this may have, for example, 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc.

[0176] Rb 2 and Rb 3 The branched alkyl group in the compound may have, for example, 3 to 10 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, and 2,2-dimethylbutyl group.

[0177] Rb 2 or Rb 3 If the hydrocarbon group 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 may be, for example, a monocycloalkane from which one hydrogen atom has been removed. The monocycloalkane may have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group may be, for example, a polycycloalkane from which one hydrogen atom has been removed. The polycycloalkane may have 7 to 12 carbon atoms, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0178] Rb 2 or Rb 3 Examples of aromatic hydrocarbon groups in this context include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Rb 2 or Rb 3 Preferably, the group is an aromatic hydrocarbon ring having 6 to 15 carbon atoms from which one or more hydrogen atoms have been removed; more preferably, a group is obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene; even more preferably, a group is obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene; particularly preferably, a group is obtained by removing one or more hydrogen atoms from benzene or naphthalene; and most preferably, a group is obtained by removing one or more hydrogen atoms from benzene.

[0179] Rb 2 or Rb 3 Examples of substituents that the hydrocarbon group in the compound may have include methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atoms, alkoxy groups (such as methoxy, ethoxy, propoxy, and butoxy groups), and alkyloxycarbonyl groups.

[0180] Rb 2 and Rb 3 These can be the same or different. Rb 2 and Rb 3 As such, aromatic hydrocarbon groups are preferred, phenyl groups which may have substituents are more preferred, and groups represented by the following formula (D0-ca-s1) are even more preferred. Rb 2 and Rb 3 Preferably, these atoms are bonded to each other, forming a ring together with the sulfur atom in the formula.

[0181] [ka] [In the formula, Rb 11 , Rb 12 , Rb 13and Rb 14 Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb 11 , Rb 12 , Rb 13 and Rb 14 At least one of these atoms is a fluorine atom or a fluorinated alkyl group. * represents a bond with a sulfur atom.

[0182] Rb in the above general formula (d0) 11 , Rb 12 , Rb 13 and Rb 14 The total number of fluorine atoms contained is preferably two or more, and more preferably three or more. The cation portion of the general formula (d0) preferably has at least one phenyl group with two or more fluorine atoms.

[0183] The following shows a specific example of the cation moiety of component (D0).

[0184] [ka]

[0185] The following are specific examples of the (D0) component.

[0186] [ka]

[0187] [ka]

[0188] In the resist composition of this embodiment, component (D0) may be used alone or in combination of two or more types. In the resist composition of this embodiment, the content of component (D0) is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). If the content of component (D0) is above the lower limit of the preferred range described above, the stability of the resist composition over time during storage can be improved, and the decrease in the fine resolution of the resist composition after storage can be suppressed. On the other hand, if the content of component (D0) is below the upper limit of the preferred range described above, it is easier to maintain good sensitivity and the solubility in the developer can also be improved.

[0189] <Other ingredients> The resist composition of this embodiment may further contain other components in addition to the above-described components (A) and (D0). Examples of other components include components (B), (D) (excluding component (D0)), (E), (F), and (S), as shown below.

[0190] ≪Acid Generating Agent Component (B)≫ The resist composition of this embodiment preferably further contains an acid-generating component (B) that generates acid upon exposure. (B) The component is not particularly limited, and any acid generators previously proposed for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts; oximesulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators, among many others.

[0191] Examples of onium salt-based acid generators include the compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), the compound represented by the general formula (b-2) (hereinafter also referred to as "component (b-2)"), or the compound represented by the general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0192] Examples of onium salt-based acid generators include the compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), the compound represented by the general formula (b-2) (hereinafter also referred to as "component (b-2)"), or the compound represented by the general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0193] [ka] [In the formula, R 101 and R 104 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 104 and R 105 These may be bonded to each other to form a ring structure. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 This is a divalent linking group or single bond containing an oxygen atom. 101 ~V 103 Each of these is independently a single bond, an alkylene group, or a fluorinated alkylene group. However, Y 101 and V 101 L cannot be a single bond at the same time. 101 ~L 102 Each of these is independently either a single bond or an oxygen atom. 103 ~L 105 These are, independently, single bonds, -CO-, or -SO2-. m is an integer greater than or equal to 1, and M' m+ This is an onium cation with a valence of m.

[0194] {Anion Division} • Anion in component (b-1) In formula (b-1), R 101 This is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents.

[0195] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated.

[0196] R 101 The aromatic hydrocarbon group in this formula is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R 101 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R 101 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, benzyl groups, phenethyl groups, 1-naphthylmethyl groups, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0197] R 101 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0198] Among them, R 101 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0199] 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, even more preferably 1 to 4, and most preferably 1 to 3. Examples of linear aliphatic hydrocarbon groups include linear alkylene groups, specifically methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(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, even more preferably 3 or 4, and most preferably 3. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0200] Also, R 101 The cyclic hydrocarbon group in the formula may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), the -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * represents Y in formula (b-1). 101 This represents a coupling that connects to something.

[0201] [ka] [In the formula, Rb' 51 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or a -SO2--containing cyclic group; B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n' is an integer from 0 to 2. * indicates a bond.

[0202] In the above general formulas (b5-r-1) to (b5-r-2), B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, or an oxygen atom or a sulfur atom. For B'', an alkylene group or -O- having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.

[0203] In the above general formulas (b5-r-1) to (b5-r-4), Rb' 51 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group, and among these, each is preferably independently a hydrogen atom or a cyano group.

[0204] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group.

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] [ka]

[0209] R 101 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As the alkyl group used as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. Preferred halogen atoms as substituents are fluorine, bromine, and iodine atoms. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0210] R 101The cyclic hydrocarbon group in may be a fused ring group containing a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridging ring system with one or more aromatic rings fused to it. Specific examples of the bridging ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to a bicycloalkane, and more preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to bicyclo[2.2.2]octane. 101 Specific examples of fused ring groups in this context include those represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in formula (b-1). 101 This represents a coupling that connects to something.

[0211] [ka]

[0212] R 101 Examples of substituents that the fused ring group in the compound may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as substituents of the fused cyclic group are as described above in R 101 Examples of substituents on cyclic groups include those similar to those listed in [reference]. Examples of aromatic hydrocarbon groups as substituents on the fused ring group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups as substituents on the fused cyclic group include: groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7); -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4); and heterocyclic groups represented by the formulas (r-hr-7) to (r-hr-16).

[0213] Chain-like alkyl groups that may have substituents: R 101 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0214] A chain-like alkenyl group which may have substituents: R 101 The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0215] R 101 Examples of substituents in the chain-like alkyl or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R 101 Examples include cyclic groups in this context.

[0216] In formula (b-1), Y 101 It is a single bond or a divalent linking group containing an oxygen atom. Y 101 If Y is a divalent linking group containing an oxygen atom, 101 It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of divalent linking groups containing an oxygen atom include the linking groups represented by the following general formulas (y-al-1) to (y-al-7). Note that in the following general formulas (y-al-1) to (y-al-7), R in formula (b-1) above 101 The V' in the following general formulas (y-al-1)~(y-al-7) is what combines with it. 101 That is the case.

[0217] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group with 1 to 5 carbon atoms. 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0218] V' 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0219] V'101 and V' 102 The alkylene group in this product may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. V' 101 and V' 102 Specifically, the alkylene groups in these include: methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2 Examples include alkylethylene groups such as -CH2CH2CH2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-]. Also, oshiV' 101 or V' 102 Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is Ra' in formula (a1-r-1). 3 A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred.

[0220] In formula (b-1), V 101 These are single bonds, alkylene groups, or fluorinated alkylene groups. Among them, V 101 It is preferable that the fluorinated alkylene group is a single bond or a linear chain having 1 to 4 carbon atoms.

[0221] In formula (b-1), R 102R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 It is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0222] A specific example of the anion part represented by the above formula (b-1) is, for example, Y 101 When it is a single bond, examples include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions; Y 101 When is a divalent linking group containing an oxygen atom, the anions can be represented by any of the following formulas (an-1) to (an-3).

[0223] [ka] [In the formula, R” 101 R” is an optionally substituted aliphatic cyclic group, 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), an optionally substituted linear alkyl group, or an optionally substituted aromatic cyclic group. 102 R” is an aliphatic cyclic group which may have substituents, a fused cyclic group represented by formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively, or a -SO2-containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4), respectively. 103 V” is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted linear alkenyl group. 101 This 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 [wherein 'v' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; where 'v' is an independent integer from 0 to 3, where 'q' is an independent integer from 0 to 20, and where 'n' is 0 or 1.]

[0224] R" 101 , R” 102 and R” 103 The aliphatic cyclic group which may have substituents is R in formula (b-1) above. 101 It is preferable that the substituent is the group exemplified as a cyclic aliphatic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the cyclic aliphatic hydrocarbon group in the above.

[0225] R" 101 and R” 103 The aromatic cyclic group which may have substituents in formula (b-1) is R 101 It is preferable that the substituent is the aromatic hydrocarbon group exemplified in the cyclic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the aromatic hydrocarbon group in the above.

[0226] R" 101 The chain-like alkyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkyl group in the compound. R" 103 The chain-like alkenyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkenyl group in the formula.

[0227] • Anion in component (b-2) In formula (b-2), R 104 , R 105 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples can be given. However, R 104 , R 105 These may be bonded to each other to form a ring. R 104 , R 105The alkyl group is preferably a linear alkyl group which may have substituents, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 104 , R 105 The number of carbon atoms in the chain-like alkyl group is preferably small within the above range of carbon atoms, for reasons such as good solubility in the resist solvent. 104 , R 105 In the chain-like alkyl group, a larger number of hydrogen atoms substituted with fluorine atoms is preferable because it increases the acid strength and improves transparency to high-energy light and electron beams below 250 nm. The proportion of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 These are, independently, a single bond, an alkylene group, or a fluorinated alkylene group, and each is V in formula (b-1). 101 Similar examples include the above. In formula (b-2), L 101 , L 102 Each of these is either a single bond or an oxygen atom, independently of the others.

[0228] • Anion in component (b-3) In formula (b-3), R 106 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples include the above. In formula (b-3), L 103 ~L 105 These are, independently, single bonds, -CO-, or -SO2-.

[0229] Among the above, the anion portion of component (B) is preferably the anion in component (b-1), and more preferably the anion represented by the formula (an-1).

[0230] {cation part} In the above equations (b-1), (b-2), and (b-3), M' m+ This represents an onium cation with an m-valence. Among these, sulfonium cations and iodonium cations are preferred. m is an integer greater than or equal to 1.

[0231] Preferred cation portion ((M' m+ ) 1 / m Examples of these include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0232] [ka] [In the formula, R 201 ~R 207 Each of these independently represents an aryl group, alkyl group, or alkenyl group, which may have substituents. 201 ~R 203 , R 206 ~R 207 These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-.

[0233] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0234] [ka] [In the formula, R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0235] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not possess aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0236] R' 201 The aromatic hydrocarbon group in this context is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: e.g., phenyl group, naphthyl group, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0237] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0238] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0239] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0240] Also, R' 201 The cyclic hydrocarbon group in the above formula may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16).

[0241] R' 201 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As alkyl groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. As the halogen atom used as a substituent, a fluorine atom is preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0242] Chain-like alkyl groups that may have substituents: R' 201 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0243] A chain-like alkenyl group which may have substituents: R' 201 The linear alkenyl group may be linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0244] R' 201 Substituents in the chain-like alkyl or alkenyl group include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R' 201 Examples include cyclic groups in this context.

[0245] R' 201 In addition to those mentioned above, the optionally substituted cyclic groups, optionally substituted linear alkyl groups, or optionally substituted linear alkenyl groups may also include those similar to the acid-dissociable group represented by formula (a1-r-2) above, as optionally substituted cyclic groups or optionally substituted linear alkyl groups.

[0246] Among them, R' 201 The cyclic group is preferably a cyclic group which may have substituents, and more preferably a cyclic hydrocarbon group which may have substituents. More specifically, preferred groups include, for example, a phenyl group, a naphthyl group, a polycycloalkane from which one or more hydrogen atoms have been removed; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7); and -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4).

[0247] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R Nis an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring preferably has 3 to 10 members, and particularly preferably 5 to 7 members, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0248] R 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond with other elements to form a ring.

[0249] R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 210 In this context, the -SO2-containing cyclic group which may have substituents is preferably a "-SO2-containing polycyclic group," and more preferably a group represented by the general formula (b5-r-1) described above.

[0250] Specific examples of the cation represented by the above formula (ca-1) are shown below.

[0251] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas.

[0252] [ka]

[0253] [ka]

[0254] [ka] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0255] [ka]

[0256] [ka]

[0257] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the aforementioned R 201 ~R 207 , and R 210 ~R 212 These are the same as those listed as substituents that may be present.

[0258] [ka]

[0259] Suitable cations represented by the formula (ca-2) include, specifically, diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0260] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0261] [ka]

[0262] Among the above, a sulfonium cation is preferred as the cation portion of component (B), and a cation represented by the formula (ca-1) is more preferred.

[0263] In the resist composition of this embodiment, component (B) may be used alone or in combination of two or more types. If the resist composition contains component (B), the content of component (B) in the resist composition is preferably less than 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of component (A). (B) By setting the content of component (B) within the above-mentioned preferred range, pattern formation is sufficiently achieved. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability of the resist composition is good, which is preferable.

[0264] ≪Basic component (D) (excluding component (D0))≫ The resist composition of this embodiment may contain, in addition to component (D0), a basic component (hereinafter also referred to as "component (D) (excluding component (D0))") that traps the acid generated by exposure (i.e., controls the diffusion of the acid). Component (D) (excluding component (D0)) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition.

[0265] Examples of components (D) other than component (D0) include photodegradable bases (D1) that decompose upon exposure and lose their acid diffusion control properties (hereinafter referred to as "component (D1)"), and nitrogen-containing organic compounds (D2) that do not fall under component (D1) (hereinafter referred to as "component (D2)"). Among these, a photodegradable base (component (D1)) is preferred because it is easier to improve roughness reduction. Furthermore, including component (D1) makes it easier to improve both sensitivity and the suppression of coating defects.

[0266] • About the (D1) component Component (D) may include a photodegradable base (D1) (hereinafter referred to as "component (D1)") that does not fall under component (D0) above. By using a resist composition containing component (D1), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern. The (D1) component is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), the compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Components (d1-1) to (d1-3) decompose in the exposed areas of the resist film and lose their acid diffusion control properties (basicity), so they do not act as quenchers, but they act as quenchers in the unexposed areas of the resist film.

[0267] [ka] [In the formula, Rd 1 ~Rd 4 Rd in formula (d1-2) is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 2 In this example, assume that no fluorine atoms are bonded to the carbon atoms adjacent to the sulfur atoms.1 is a single bond or a divalent linking group. m is an integer greater than or equal to M m+ These are each independently m-valent organic cations.

[0268] {(d1-1) component} ··Anion Club In formula (d1-1), Rd 1 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of the above R' is... 201 Similar examples include the above. Among these, Rd 1 Preferred substituents are optionally substituted aromatic hydrocarbon groups, optionally substituted aliphatic cyclic groups, or optionally substituted linear alkyl groups. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and in this case, preferred substituents are the linking groups represented by the general formulas (y-al-1) to (y-al-5). Note that Rd 1 If the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in has a linking group represented by the general formulas (y-al-1) to (y-al-7) as a substituent, then in the general formulas (y-al-1) to (y-al-7), Rd in formula (d3-1) 1 The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in the above general formula (y-al-1) to (y-al-7) is V'. 101 That is the case. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably one with 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0269] When the chain-like alkyl group is a fluorinated alkyl group having a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.

[0270] The following are preferred specific examples of the anionic portion of component (d1-1).

[0271] [ka]

[0272] ··Cation section In formula (d1-1), M m+ This is an m-valent organic cation. M m+ Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-3), respectively, with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the formulas (ca-1-1) to (ca-1-83) being even more preferred. (d1-1) Component may be used alone or in combination of two or more types.

[0273] (d1-1) Component may be used alone or in combination of two or more types.

[0274] {(d1-2) component} ··Anion Club In formula (d1-2), Rd 2 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. However, Rd 2 In this mixture, we assume that the carbon atom adjacent to the S atom is not bonded to a fluorine atom (i.e., not fluorine-substituted). This results in the anions of components (d1-2) becoming appropriately weak acid anions, improving the quenching ability of component (D). Rd 2 The alkyl group is preferably a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents, and more preferably an aliphatic cyclic group which may have substituents.

[0275] The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (it may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0276] Rd 2 The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). 1 Examples include substituents similar to those that may be present on hydrocarbon groups (aromatic hydrocarbon groups, aliphatic cyclic groups, and linear alkyl groups) in the above.

[0277] The following are preferred specific examples of the anionic portion of component (d1-2).

[0278] [ka]

[0279] ··Cation section In formula (d1-2), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-2) Components may be used individually or in combination of two or more.

[0280] {(d1-3) components} ··Anion Club In formula (d1-3), Rd 3 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and the R' 201 Similar to the above, it is preferable that the group is a cyclic group containing a fluorine atom, a linear alkyl group, or a linear alkenyl group. Among these, a fluorinated alkyl group is preferred, and the above Rd 1 A fluorinated alkyl group similar to the one shown is more preferable.

[0281] In formula (d1-3), Rd 4 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. In particular, alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups, which may have substituents, are preferred. Rd 4 The alkyl group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. 4Some of the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups, cyano groups, etc. Rd 4 The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specifically, examples of alkoxy groups having 1 to 5 carbon atoms include the methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group. Among these, the methoxy group and ethoxy group are preferred.

[0282] Rd 4 The alkenyl group in R' 201 Examples of alkenyl groups similar to those in the above include vinyl groups, propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups, which are preferred. These groups may further have substituents of an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0283] Rd 4 The cyclic group in is the R' 201 Examples of cyclic groups similar to those in the above include alicyclic groups obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, or aromatic groups such as phenyl groups and naphthyl groups. 4 When Rd is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in good lithography properties. 4 When the group is an aromatic group, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithographic characteristics in lithography using EUV or the like as the exposure light source.

[0284] In formula (d1-3), Yd 1 It is a single bond or a divalent linking group. Yd 1 The divalent linking group in formula (a2-1) is not particularly limited, but may include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) which may have substituents, and divalent linking groups containing heteroatoms.21 Examples include divalent hydrocarbon groups that may have substituents, and divalent linking groups containing heteroatoms, as mentioned in the explanation of divalent linking groups in [reference]. Yd 1 The preferred members are carbonyl groups, ester bonds, amide bonds, alkylene groups, or combinations thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0285] The following are preferred specific examples of the anionic parts of components (d1-3).

[0286] [ka]

[0287] [ka]

[0288] ··Cation section In formula (d1-3), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-3) Components may be used individually or in combination of two or more.

[0289] Component (D1) may consist of only one of the above components (d1-1) to (d1-3), or it may consist of a combination of two or more components. If the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of component (A). When the content of component (D1) is above the preferred lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, when it is below the upper limit, good sensitivity can be maintained and throughput is also excellent.

[0290] (D1) Method for producing component: The methods for producing the aforementioned components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Furthermore, the method for producing components (d1-3) is not particularly limited and may be, for example, similar to the method described in US2012-0149916.

[0291] • About the (D2) component Component (D) may include nitrogen-containing organic compounds that do not fall under component (D1) above (hereinafter referred to as "component (D2)"). Component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and it is preferable that the aliphatic group has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0292] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0293] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0294] Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, trimenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.

[0295] Among the above, component (D2) is preferably an alkylamine, and more preferably a trialkylamine having 5 to 10 carbon atoms.

[0296] (D2) Component may be used alone or in combination of two or more types. If the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). When the content of component (D2) is above the preferred lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, when it is below the upper limit, good sensitivity can be maintained and throughput is also excellent.

[0297] <<At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and their derivatives>> The resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and their derivatives (hereinafter referred to as "component (E)"). Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, among which salicylic acid is preferred. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred among these.

[0298] In the resist composition of this embodiment, component (E) may be used alone or in combination of two or more types. If the resist composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A). By setting the content within the above range, the lithography characteristics are further improved.

[0299] ≪Fluorine additive component (F)≫ The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water repellency to the resist film and, by being used as a separate resin from component (A), improves lithography properties. As component (F), for example, fluorine-containing polymer compounds described in Japanese Patent Publication No. 2010-002870, Japanese Patent Publication No. 2010-032994, Japanese Patent Publication No. 2010-277043, Japanese Patent Publication No. 2011-13569, and Japanese Patent Publication No. 2011-128226 can be used. More specifically, component (F) includes polymers having a constituent unit (f1) represented by the following general formula (f1-1). This polymer is preferably a polymer (homopolymer) consisting only of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the constituent unit (a1); and more preferably a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid and the constituent unit (a1). Here, the constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, and more preferably a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0300] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 They may be the same or different. 1 Rf is an integer between 0 and 5. 101 It is an organic group containing a fluorine atom.

[0301] In formula (f1-1), R bonded to the α-carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf 102 and Rf 103 A fluorine atom is preferred as the halogen atom. Rf 102 and Rf 103 Examples of alkyl groups having 1 to 5 carbon atoms in R include those similar to the alkyl groups having 1 to 5 carbon atoms in R above, with methyl or ethyl groups being preferred. 102 and Rf103 Specifically, examples of halogenated alkyl groups having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are preferred as the halogen atoms, particularly Rf. 102 and Rf 103 Preferably, the element is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; more preferably, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group; and even more preferably, a hydrogen atom. In formula (f1-1), nf 1 is an integer between 0 and 5, preferably between 0 and 3, and more preferably 1 or 2.

[0302] In formula (f1-1), Rf 101 This is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing fluorine atoms may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Furthermore, in hydrocarbon groups containing fluorine atoms, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and particularly preferable that 60% or more are fluorinated, as this increases the hydrophobicity of the resist film during immersion exposure. Among them, Rf 101 More preferably, fluorinated hydrocarbon groups having 1 to 6 carbon atoms are used, with trifluoromethyl groups, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3 being particularly preferred.

[0303] Furthermore, component (F) may also include a polymer having the aforementioned structural unit (a8). A copolymer of structural unit (a8) and structural unit (a2) is preferred for this polymer.

[0304] The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in resist solvents for use as a resist, and if it is above the lower limit of this range, the water repellency of the resist film is good. The degree of dispersion of component (F) (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0305] In the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. If the resist composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A).

[0306] ≪Organic solvent component (S)≫ The resist composition of this embodiment can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "component (S)"). The (S) component can be any solvent that can dissolve each component used to form a homogeneous solution, and any solvent that is conventionally known as a solvent for chemically amplified resist compositions can be appropriately selected and used. In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, PGMEA, PGME, γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0307] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred as component (S). The mixing ratio (mass ratio) can be appropriately determined considering the compatibility between PGMEA and the polar solvent. Furthermore, as the (S) component, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited and is set appropriately according to the coating thickness, at a concentration that can be applied to a substrate or the like. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0308] The resist composition of this embodiment may be subjected to removal of impurities after dissolving the resist material in component (S), using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include those described in Japanese Patent Application Publication No. 2016-155121.

[0309] The resist composition of this embodiment described above contains a compound (D0) (component (D0)) represented by the general formula (d0). Conventional resist compositions had a drawback: their fine resolution deteriorated during storage. Component (D0) has an alkoxy group R attached to the benzene ring of the anionic part. 1 O and iodine atoms are bonded to it. Furthermore, the substituent bonded to the benzene ring in the cation part contains a fluorine atom. (D0) component R of the anion part 1 Due to the presence of oxygen (O) and fluorine atoms in the cation portion, the resist composition of this embodiment exhibits enhanced stability over time during storage and suppresses a decrease in fine resolution after storage. The reason for these effects is not entirely clear, but it is presumed to be as follows. In conventional resist compositions, the cations of the acid generator decompose during storage due to the anions of the acid diffusion control agent, resulting in a decrease in fine resolution. In the resist composition of this embodiment, the decomposition of the acid generator cation by the anion of component (D0) is suppressed during storage. As a result, it is presumed that the acid generator is stably preserved during storage, and the decrease in fine resolution after storage is suppressed.

[0310] Iodine atoms have high absorption of EUV light at a wavelength of 13.5 nm. Therefore, the (D0) component readily generates secondary electrons during exposure. The secondary electrons generated from the (D0) component upon exposure transfer their energy to the acid-generating component (substrate component (A) or acid-generating agent component (B)), thereby promoting the decomposition of the acid-generating component. As a result, sensitivity is increased when forming a resist pattern using the resist composition of this embodiment.

[0311] (Method for forming resist patterns) A resist pattern formation method according to a second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of such a resist pattern formation method is, for example, a resist pattern formation method carried out as follows.

[0312] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-application bake (PAB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus, either through exposure via a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without going through a mask pattern. After this, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C. Next, the resist film is subjected to a developing process. In the case of an alkaline developing process, an alkaline developer is used, and in the case of a solvent developing process, a developer containing an organic solvent (organic developer) is used.

[0313] After the developing process, a rinsing process is preferably performed. In the case of an alkaline developing process, a water rinse using pure water is preferred, and in the case of a solvent developing process, a rinsing solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing process, a process may be performed to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After development or rinsing, the film is dried. In some cases, a bake (post-bake) process may be performed after the development process.

[0314] The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. As for the wiring pattern material, for example, copper, aluminum, nickel, and gold can be used.

[0315] The wavelength used for exposure is not particularly limited, and exposure can be performed using radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays, with EUV or EB being preferred.

[0316] The method for exposing the resist film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography. Immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is first filled with a solvent (immersion medium) that has a refractive index greater than that of air, and then exposure (immersion exposure) is performed in that state. The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film being exposed. Examples include water, fluorinated inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is preferably used as the immersion medium.

[0317] Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. The organic solvent contained in the organic developer solution used in the solvent development process can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0318] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0319] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0320] Organic developers may contain known additives as needed. Examples of such additives include surfactants.

[0321] The development process can be carried out by known development methods, such as immersing the support in a developer solution for a certain period of time (dip method), piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time (paddle method), spraying the developer solution onto the surface of the support (spray method), or continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method).

[0322] In the solvent-based development process, the rinsing solution used for rinsing after development can contain an organic solvent that is less likely to dissolve the resist pattern, selected from among the organic solvents listed above for use in the organic developer. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used individually or in combination of two or more. They may also be used in mixtures with other organic solvents or water.

[0323] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method).

[0324] It is preferable that the resist composition of the above-described embodiment and the various materials used in the resist pattern formation method of the above-described embodiment (for example, resist solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The amount 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 absent (below the detection limit of the measuring device).

[0325] (compound) The compound of this embodiment is represented by the following general formula (d0).

[0326] [ka] [In the formula, R 1 is a saturated hydrocarbon group. I is an iodine atom. R 2 Yd is a substituent. 0 is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb 11 , Rb 12 , Rb 13 and Rb 14 Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb 11 , Rb 12 , Rb 13 and Rb 14 At least one of them is a fluorine atom or a fluorinated alkyl group. Rb 2 and Rb 3 Each of these is independently a hydrocarbon group which may have substituents, or Rb 2 and Rb 3 These atoms are bonded to each other, forming a ring with the sulfur atom in the formula.

[0327] The compound of this embodiment is the same as component (D0) of the resist composition according to the first embodiment. The compounds of this embodiment are useful as acid diffusion control agents used in resist compositions.

[0328] (Acid diffusion control agent) The acid diffusion control agent of this embodiment contains compound (d0) represented by formula (d0) in the above embodiment.

[0329] (Method of producing compounds) The method for producing the compound of this embodiment is not particularly limited, but may include, for example, the following reactions 1 and 2. In reaction 1, for example, a compound represented by the following general formula (d0-preA0) is reacted with a reaction solvent containing a base compound represented by the following general formula (bs0) to obtain a compound represented by the following general formula (d0-preB0).

[0330] [ka] [In the formula, R 1 is a saturated hydrocarbon group. I is an iodine atom. R 2 Yd is a substituent. 0 is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. R b+ These are either organic or inorganic cations.

[0331] In the above equations (d0-preA0) and (d0-preB0), R 1 , R 2 , Yd 0 ,j and k are R in the above formula (d0). 1 , R 2 , Yd 0 , the same applies to j and k.

[0332] Examples of base compounds represented by the general formula (bs0) include tetramethylammonium hydroxide (TMAH). R b+ Examples include ammonium cations such as tetramethylammonium cation, tetrabutylammonium cation, and triethylammonium cation, as well as pyridinium cations. Examples of reaction solvents include water, dichloromethane, acetonitrile, and chloroform.

[0333] In reaction 1, the reaction temperature is, for example, 0 to 100°C, and the reaction time is, for example, 10 minutes to 24 hours.

[0334] Next, in reaction 2, for example, the compound represented by formula (d0-preB0) is reacted with the compound represented by the following general formula (d0-s0) to obtain the compound represented by general formula (d0).

[0335] [ka] [In the formula, R 1 is a saturated hydrocarbon group. I is an iodine atom. R 2 Yd is a substituent. 0 is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb 11 , Rb 12 , Rb 13 and Rb 14 Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb 11 , Rb 12 , Rb 13 and Rb 14 At least one of them is a fluorine atom or a fluorinated alkyl group. Rb 2 and Rb 3 Each of these is independently a hydrocarbon group which may have substituents, or Rb 2 and Rb 3 These atoms are bonded to each other, forming a ring with the sulfur atom in the formula. b+ X is an organic cation or an inorganic cation. d- It is a halogen anion.

[0336] In the above equation (d0-s0), Rb 2 , Rb 3 , Rb 11 , Rb 12 , Rb13 and Rb 14 Rb in the above formula (d0) 2 , Rb 3 , Rb 11 , Rb 12 , Rb 13 and Rb 14 It is similar to that. In the above equation (d0-s0), X d- Chloride ions and bromide ions are preferred, with chloride ions being more preferred.

[0337] The reaction solvent in reaction 2 is the same as the reaction solvent that can be used in reaction 1. In reaction 2, the reaction temperature is, for example, 0 to 100°C, and the reaction time is, for example, 10 minutes to 24 hours.

[0338] After the salt exchange reaction is complete, the compound (d0) in the reaction solution may be isolated and purified. Conventional methods can be used for isolation and purification, and for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc., can be used in appropriate combinations. The structure of compound (d0) obtained in the manner described above is: 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19 It can be identified by common organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction. [Examples]

[0339] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0340] <Examples of compound manufacturing> [Manufacturing Example 1: Manufacturing of Compound (D0-1)] 20.0 g of compound (D0-preA1) and 90.3 g of an aqueous solution of 5% tetramethylammonium hydroxide (BS1) were placed in a three-necked flask and stirred at room temperature for 3 hours to obtain an aqueous solution of compound (D0-preB1).

[0341] [ka]

[0342] Next, 18.2 g of (D0-S1) and 200 g of dichloromethane were placed in an aqueous solution of compound (D0-preB1) in a three-necked flask and stirred for 3 hours. The organic layer was washed with deionized water and recovered. The organic layer was concentrated using a rotary evaporator to obtain 26.9 g of compound (D0-1).

[0343] [ka]

[0344] Compound (D0-1) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),7.43(14H,m),8.18(1H,d),8.30(1H,d)

[0345] [Manufacturing Examples 2-10: Manufacturing of Compounds (D0-2)-(D0-10)] Compounds (D0-2) to (D0-10) were obtained in the same manner as in "Production Example 1: Production of Compound (D0-1)" above, except that the combinations of the following compounds (D0-preA2) to (D0-preA4) and the following compounds (D0-s2) to (D0-s7) were changed.

[0346] [ka]

[0347] [ka]

[0348] [ka]

[0349] Compound (D0-2) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),7.43(14H,m),8.18(2H,s)

[0350] [ka]

[0351] Compound (D0-3) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.34(3H,t),4.07(q.2H),7.43(14H,m),8.18(1H,d),8.30(1H,d)

[0352] [ka]

[0353] Compound (D0-4) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.93(3H,s),7.16(2H,s),7.43(14H,m)

[0354] [ka]

[0355] Compound (D0-5) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),6.77(9H,m),8.18(1H,d),8.30(1H,d)

[0356]

change

[0357] Compound (D0-6) 1 The H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),6.77(6H,m),7.34(5H,m),8.18(1H,d),8.30(1H,d)

[0358]

change

[0359] Compound (D0-7) 1 The H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),7.30(2H,m),7.48(8H,m),7.77(2H,m),8.18(1H,d),8.30(1H,d)

[0360]

change

[0361] Compound (D0-8) 1 The H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),7.24(6H,m),7.35(3H,m),7.47(3H,m),8.18(1H,d),8.30(1H,d)

[0362] [ka]

[0363] Compound (D0-9) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),7.09(3H,m),7.35(11H,m),8.18(1H,d),8.30(1H,d)

[0364] [ka]

[0365] Compound (D0-10) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=3.83(3H,s),6.78(3H,m),7.35(10H,m),8.18(1H,d),8.30(1H,d)

[0366] <Preparation of the resist composition> (Examples 1-13, Comparative Examples 1-5) Each of the components shown in Table 1 was mixed and dissolved to prepare the resist compositions for each example.

[0367] [Table 1]

[0368] In Table 1, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients.

[0369] (A)-1: A polymer compound represented by the following chemical formula (A1)-1. For polymer compound (A1)-1, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, was 6900, and the molecular weight dispersion (Mw / Mn) was 1.74.13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0370] (A)-2: A polymer compound represented by the following chemical formula (A1)-2. For polymer compound (A1)-2, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, was 7200, and the molecular weight dispersion (Mw / Mn) was 1.72. 13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0371] (A)-3: A polymer compound represented by the following chemical formula (A1)-3. For polymer compound (A1)-3, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, was 7100, and the molecular weight dispersion (Mw / Mn) was 1.72. 13 The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0372] [ka]

[0373] (B)-1: An acid generator consisting of the following compound (B1-1). (B)-2: An acid generator consisting of the following compounds (B1-2).

[0374] [ka]

[0375] (D0)-1: An acid diffusion control agent comprising the compound (D0-1) mentioned above. (D0)-2: An acid diffusion control agent comprising the compound (D0-2) mentioned above. (D0)-3: An acid diffusion control agent comprising the compound (D0-3) mentioned above. (D0)-4: An acid diffusion control agent comprising the compound (D0-4) mentioned above. (D0)-5: An acid diffusion control agent comprising the compound (D0-5) mentioned above. (D0)-6: An acid diffusion control agent comprising the compound (D0-6) mentioned above. (D0)-7: An acid diffusion control agent comprising the compound (D0-7) mentioned above. (D0)-8: An acid diffusion control agent comprising the compound (D0-8) mentioned above. (D0)-9: An acid diffusion control agent comprising the compound (D0-9) mentioned above. (D0)-10: An acid diffusion control agent comprising the compound (D0-10) mentioned above. (D1)-1: An acid diffusion control agent consisting of the following compound (D1-1). (D1)-2: An acid diffusion control agent consisting of the following compounds (D1-2). (D1)-3: Acid diffusion control agent consisting of the following compounds (D1-3). (D1)-4: An acid diffusion control agent consisting of the following compounds (D1-4). (D1)-5: Acid diffusion control agent consisting of the following compounds (D1-5).

[0376] [ka]

[0377] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0378] <Resist pattern formation> Each example of the resist composition was stored at -20°C for 3 weeks. Each of the resist compositions, stored at -20°C, was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner. A 50 nm thick resist film was then formed by pre-baking (PAB) on a hot plate at 110°C for 60 seconds and drying. Next, the resist film was subjected to lithography (exposure) using an electron beam lithography system JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100kV, with a target size of a 1:1 line-and-space pattern (hereinafter referred to as "LS pattern") with a line width of 50nm. Subsequently, a post-exposure heating (PEB) treatment was performed at 100°C for 60 seconds. Next, alkaline development was performed at 23°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). After that, a water rinse was performed with pure water for 15 seconds. As a result, a 1:1 LS pattern with a line width of 50 nm was formed. In the above resist pattern formation method, the exposure amount at which the target-sized LS pattern is formed is the optimal exposure amount Eop(μC / cm²). 2 ) was calculated as follows.

[0379] Furthermore, each of the resist compositions was stored at 40°C for three weeks. Using the resist compositions stored at 40°C for each example, resist patterns were formed in the same manner as when using the resist compositions stored at -20°C. The exposure amount was set to the optimal exposure amount Eop determined above.

[0380] [Evaluation of changes in line pattern dimensions over time] CD1 was defined as the line pattern dimension of the obtained LS pattern when using a resist composition stored at -20°C. When a resist composition stored at 40°C was used, the line pattern dimension of the obtained LS pattern was defined as CD2. The change in line pattern dimensions over time (ΔCD) was calculated as the difference between CD1 and CD2. The results are shown in Table 2 as "ΔCD(nm)". A smaller ΔCD value indicates better long-term stability of the resist composition.

[0381] [Evaluation of changes in LWR (Linewise Roughness) over time] When a resist composition stored at -20°C was used, the 3σ of the obtained LS pattern was defined as LWR1. When using a resist composition stored at 40°C, the 3σ of the obtained LS pattern was defined as LWR2. "3σ" refers to three times the standard deviation (σ) (unit: nm) obtained by measuring the line position at 400 points along the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). The change in LWR over time (ΔLWR) was defined as LWR1 - LWR2, i.e., the difference between LWR1 and LWR2. The results are shown in Table 2 as "ΔLWR(nm)". A smaller ΔLWR value indicates better long-term stability of the resist composition.

[0382] [Table 2]

[0383] As shown in Table 2, in the resist compositions of Examples 1 to 13 to which the present invention was applied, the anionic portion of compound (D0) had an alkoxy group, and in the benzene ring of the cation portion of compound (D0), a fluorine atom or a trifluoromethyl group was bonded to the sulfur atom at the ortho or meta position. The resist compositions of Examples 1 to 13 had a ΔCD of 1.5 nm or less and a ΔLWR of 2 nm or less. On the other hand, the resist compositions of Comparative Examples 1 to 5, which are outside the scope of the present invention, all had a ΔCD of more than 1.5 nm and a ΔLWR of more than 2 nm.

[0384] In Example 10, where the cation of compound (D0) has two fluorine atoms, both ΔCD and ΔLWR were lower than in Example 9, where the cation of compound (D0) has one fluorine atom. In Example 6, where the compound (D0) cation has four fluorine atoms, both ΔCD and ΔLWR were lower than in Example 10, where the compound (D0) cation has two fluorine atoms. In Example 5, where the compound (D0) cation had six fluorine atoms, both ΔCD and ΔLWR were lower than in Example 6, where the compound (D0) cation had four fluorine atoms.

[0385] In the cation of compound (D0), Rb 2 and Rb 3 In Example 7, the cation of compound (D0) contains Rb, which is bonded to each other and forms a ring with the sulfur atom. 2 and Rb 3 Compared to Example 1, in which the atoms were not bonded to each other and did not form a ring with the sulfur atoms, both ΔCD and ΔLWR were reduced.

Claims

1. A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, A base component (A) whose solubility in the developer changes due to the action of acid, Compound (D0) represented by the following general formula (d0), It contains, The resist composition further contains an acid generating agent component (B) that generates acid upon exposure, or the substrate component (A) is a substrate component that generates acid upon exposure. 【Chemistry 1】 [In the formula, R １ is a saturated hydrocarbon group. I is an iodine atom. R ２ is a substituent. Yd ０ is a divalent linking group or a single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb １１ , Rb １２ , Rb １３ and Rb １４ are each independently a fluorine atom, a fluorinated alkyl group or a hydrogen atom. At least one of Rb １１ , Rb １２ , Rb １３ and Rb １４ is a fluorine atom or a fluorinated alkyl group. Rb ２ and Rb ３ are each independently a hydrocarbon group which may have a substituent, or Rb ２ and Rb ３ are bonded to each other to form a ring together with the sulfur atom in the formula.]

2. Rb in the above general formula (d0) １１ , Rb １２ , Rb １３ and Rb １４ The resist composition according to claim 1, wherein the total number of fluorine atoms contained is two or more.

3. Rb in the above general formula (d0) ２ and Rb ３ The resist composition according to claim 1, wherein each of them is independently a phenyl group which may have substituents.

4. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using a resist composition according to any one of claims 1 to 3; exposing the resist film; and developing the exposed resist film to form a resist pattern.

5. The resist pattern formation method 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).

6. A compound represented by the following general formula (d0). 【Chemistry 2】 [In the formula, R １ is a saturated hydrocarbon group. I is an iodine atom. R ２ Yd is a substituent. ０ is a divalent linking group or single bond. j is an integer from 0 to 3. k is an integer from 1 to 4. 1 ≤ j + k ≤ 4. Rb １１ , Rb １２ , Rb １３ and Rb １４ Each of these is independently a fluorine atom, a fluorinated alkyl group, or a hydrogen atom. Rb １１ , Rb １２ , Rb １３ and Rb １４ At least one of them is a fluorine atom or a fluorinated alkyl group. Rb ２ and Rb ３ Each of these is independently a hydrocarbon group which may have substituents, or Rb ２ and Rb ３ These atoms are bonded to each other, forming a ring with the sulfur atom in the formula.

7. An acid diffusion control agent containing the compound described in claim 6.

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