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

Abstract

To provide a resist composition which has high sensitivity and good lithographic characteristics such as uniformity of pattern dimensions, a resist pattern forming method, and a compound useful as an acid diffusion control agent component.SOLUTION: A resist composition generates an acid upon exposure, changes its solubility in a developer by the action of an acid, and contains a compound (D0) represented by a general formula (d0). (In the formula, Rar represents an optionally substituted aromatic ring; R01 represents a C1-10 chain saturated hydrocarbon group; R02 represents an optionally substituted C1-10 chain saturated hydrocarbon group or a hydrogen atom; R03 represents a halogen atom; j represents an integer of 1 or more, valence permitting; k represents an integer of 1 or more, valence permitting; and Yd0 represents a divalent linking group or a single bond.)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, in the production of semiconductor devices and liquid crystal display devices, pattern miniaturization has been rapidly progressing due to the advancement of lithography technology. As a miniaturization technique, generally, the wavelength of the exposure light source is shortened (energy is increased).

[0003] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition containing a base material component whose solubility in a developer changes by the action of an acid and an acid generator component that generates an acid upon exposure has been conventionally used.

[0004] In the formation of a resist pattern, the behavior of the acid generated from the acid generator component upon exposure is regarded as one factor that greatly affects the lithography characteristics. On the other hand, a chemically amplified resist composition having an acid diffusion control agent that controls the diffusion of the acid generated from the acid generator component upon exposure together with the acid generator component has been proposed.

[0005] For example, Patent Document 1 discloses a resist composition containing a resin component whose solubility in a developer changes by the action of an acid, an acid generator component, and a photoreactive quencher having an anion part with a specific structure as an acid diffusion control agent. This photoreactive quencher is a component that causes an ion exchange reaction with the acid generated from the acid generator component and exhibits a quenching effect. By blending such a photoreactive quencher, the diffusion of the acid generated from the acid generator component from the exposed part to the unexposed part of the resist film is controlled, and an improvement in lithography characteristics is achieved.

Prior Art Documents

Patent Document

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] With further progress in lithography technology, expansion of application fields, etc., the miniaturization of patterns is rapidly advancing. Along with this, when manufacturing semiconductor elements, etc., a technology capable of forming a pattern with a fine dimension in a good shape is required. Therefore, it is even more necessary for the resist composition to achieve both high sensitivity and improvement in lithography characteristics such as the uniformity of pattern dimensions.

[0008] The present invention has been made in view of the above circumstances, and in forming a resist pattern, a resist composition having high sensitivity and enhanced lithography characteristics such as the uniformity of pattern dimensions, a resist pattern forming method using the resist composition, and a compound useful as an acid diffusion control agent component used in the resist composition are provided.

Means for Solving the Problems

[0009] In order to solve the above problems, the present invention adopts the following configuration. That is, a first aspect of the present invention is a resist composition that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid, and contains a base material component (A) whose solubility in a developer changes by the action of the acid, and a compound (D0) represented by the following general formula (d0).

[0010]

Chemical Formula

[0011] A second aspect of the present invention is a resist pattern forming method including 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 exposed resist film to form a resist pattern.

[0012] A third aspect of the present invention is a compound represented by the following general formula (d0’).

[0013]

Chemical formula

[0014] A fourth aspect of the present invention is an acid diffusion controller containing the compound according to the third aspect.

Advantages of the Invention

[0015] According to the present invention, in the formation of a resist pattern, a resist composition having high sensitivity and improved lithography characteristics such as pattern dimension uniformity, a resist pattern forming method using the resist composition, and a compound useful as an acid diffusion controller component for the resist composition can be provided.

Embodiments for Carrying Out the Invention

[0016] In this specification and the claims, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group, compound, etc. having no aromaticity. "Alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. "Alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified. "Halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. "Constituent unit" means a monomer unit (monomeric unit) constituting a high molecular compound (resin, polymer, copolymer). When it is described as "may have a substituent", it includes both the case where a hydrogen atom (-H) is substituted with a monovalent group and the case where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept including irradiation with radiation in general.

[0017] The "acid-decomposable group" is a group having acid-decomposability such that at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of the acid-decomposable group whose polarity increases by the action of an acid include groups that decompose by the action of an acid to generate a polar group. Examples of the polar group include a carboxy group, a hydroxy group, an amino group, a sulfo group (-SO3H), etc. More specifically, examples of the acid-decomposable group include a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0018] The "acid-dissociable group" refers to both (i) a group having acid-dissociability such that the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) a group in which, after a part of the bonds are cleaved by the action of an acid and then a decarboxylation reaction occurs, the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thereby, when the acid-dissociable group is dissociated by the action of an acid, a polar group having a higher polarity than the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the whole component (A1) increases. By the increase in polarity, relatively, the solubility in the developer changes. When the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.

[0019] The "base material component" is an organic compound having a film-forming ability. The organic compounds used as the base material component are roughly classified into non-polymers and polymers. As the non-polymer, those having a molecular weight of usually 500 or more and less than 4000 are used (hereinafter referred to as "low molecular compounds"). Hereinafter, when referring to "resin", "high molecular compound" or "polymer", it indicates a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) shall be used.

[0020] The term "derived structural unit" means a structural unit formed by cleavage of a multiple bond between carbon atoms, such as an ethylenic double bond. In the case of "acrylic ester", the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. The substituent (R αx ) that substitutes the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom. Further, it is assumed to include itaconic acid diesters in which the substituent (R αx ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R αx ) is substituted with a hydroxyalkyl group or a group obtained by modifying its hydroxyl group. In addition, unless otherwise specified, the α-position carbon atom of the acrylic ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, an acrylic ester in which the hydrogen atom bonded to the α-position carbon atom is substituted with a substituent may be referred to as an α-substituted acrylic ester.

[0021] The term "derivative" refers to a concept including those in which the hydrogen atom at the α-position of the target compound is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. Examples of those derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound in which the hydrogen atom at the α-position may be substituted with a substituent is substituted with an organic group; those in which a substituent other than a hydroxyl group is bonded to the target compound in which the hydrogen atom at the α-position may be substituted with a substituent, and the like. In addition, unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. Examples of the substituent that substitutes the hydrogen atom at the α-position of hydroxystyrene include the same ones as R αx .

[0022] In this specification and the claims of this patent, depending on the structure represented by the chemical formula, there may be asymmetric carbons and enantiomers or diastereomers may exist. In that case, those isomers are represented by one chemical formula. Those isomers may be used alone or as a mixture.

[0023] (Resist composition) The resist composition of this embodiment generates an acid upon exposure, and the solubility in a developer changes due to the action of the acid. Such a resist composition contains a base material component (A) (hereinafter also referred to as “component (A)”) whose solubility in a developer changes due to the action of an acid, and a compound (D0) represented by the following general formula (d0) (hereinafter also referred to as “component (D0)”).

[0024] In the resist composition of this embodiment, component (A) may generate an acid upon exposure, or an additive component blended separately from component (A) may generate an acid upon exposure. Specifically, the resist composition of this embodiment may further contain an acid generator component (B) (hereinafter referred to as “component (B)”) that generates an acid upon exposure; (2) component (A) may be a component that generates an acid upon exposure; or (3) component (A) may be a component that generates an acid upon exposure and further contains component (B). That is, in the cases of (2) and (3) above, component (A) becomes a “base material component that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid”. When component (A) is a base material component that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, it is preferable that component (A1) described below is a resin that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, structural unit (a5) described below may be used.

[0025] Among the above, the resist composition of this embodiment is preferably the case of (1) or (2). That is, the resist composition of this embodiment preferably contains component (A), component (D0), and component (B), or contains component (A) and component (D0).

[0026] When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, in the exposed portion of the resist film, for example, an acid is generated from the component (B), and the solubility of the component (A) in the developer changes due to the action of the acid. On the other hand, in the unexposed portion of the resist film, the solubility of the component (A) in the developer does not change. Therefore, a difference in solubility in the developer occurs between the exposed portion and the unexposed portion of the resist film. Therefore, when the resist film is developed, when the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and when the resist composition is a negative type, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern.

[0027] The resist composition of this embodiment may be a positive resist composition or a negative resist composition. Further, the resist composition of this embodiment may be for an alkali development process using an alkali developer for the development treatment during resist pattern formation, or may be for a solvent development process using a developer containing an organic solvent (organic-based developer) for the development treatment.

[0028] <Base material component (A)> In the resist composition of this embodiment, as the component (A), it is preferable to use a resin component (A1) (hereinafter also referred to as "(A1) component") whose solubility in the developer changes due to the action of an acid. By using the (A1) component, since the polarity of the base material component changes before and after exposure, good development contrast can be obtained not only in the alkali development process but also in the solvent development process. As a preferable component (A), other high molecular compounds and / or low molecular compounds may be used in combination with the (A1) component.

[0029] In the resist composition of this embodiment, the component (A) may be used alone or in combination of two or more.

[0030] ·Regarding the (A1) component (A1) component is a resin component whose solubility in the developer changes due to the action of an acid. (Component (A1)) preferably has a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid. (Component (A1)) may have other structural units as necessary in addition to the structural unit (a1).

[0031] ≪Structural unit (a1)≫ The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity increases by the action of an acid.

[0032] Specific examples of the acid-decomposable group include a group in which a polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group). Examples of the acid-dissociable group include those proposed as the acid-dissociable group of the base resin for a chemically amplified resist composition. Specific examples of those proposed as the acid-dissociable group of the base resin for a chemically amplified resist composition include the "acetal-type acid-dissociable group", "tertiary alkyl ester-type acid-dissociable group", "tertiary alkyloxycarbonyl acid-dissociable group", and "secondary alkyloxycarbonyl acid-dissociable group" described below.

[0033] Acetal-type acid-dissociable group: Examples of the acid-dissociable group that protects a carboxy group or a hydroxy group among the polar groups include an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as "acetal-type acid-dissociable group").

[0034] [Chemical formula] [In the formula, Ra’ 1 , Ra’ 2 is a hydrogen atom or an alkyl group. Ra’ 3 is a hydrocarbon group, and Ra’ 3 may combine with either Ra’ 1 , Ra’ 2 to form a ring.]

[0035] In formula (a1-r-1), Ra’ 1 and Ra’ 2 Among them, at least one is preferably a hydrogen atom, and more preferably both are hydrogen atoms. Ra’ 1 Or when Ra’ 2 is an alkyl group, examples of the alkyl group include the same ones as the alkyl groups listed as substituents that may be bonded to the carbon atom at the α-position in the description of the above α-substituted acrylic acid ester, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, a linear or branched alkyl group is preferably mentioned. More specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. are mentioned, a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0036] In formula (a1-r-1), Ra’ 3 Examples of the hydrocarbon group of include a linear or branched alkyl group, or a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. are mentioned. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0037] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group, etc. are mentioned, and an isopropyl group is preferred.

[0038] Ra’ 3 When it is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may also be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specifically, cyclopentane, cyclohexane and the like can be mentioned. As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable. As the polycycloalkane, those having 7 to 12 carbon atoms are preferable, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane and the like can be mentioned.

[0039] Ra’ 3 When the cyclic hydrocarbon group of Ra’ becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still 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; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Ra’ 3Specific examples of the aromatic hydrocarbon group in [description] include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (such as biphenyl, fluorene, etc.); a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (such as 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 of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0040] Ra’ 3 The cyclic hydrocarbon group in [description] may have a substituent. Examples of this substituent include -RP1, -RP2-O-RP1, -RP2-CO-RP1, -RP2-CO-ORP1, -RP2-O-CO-RP1, -RP2-OH, -RP2-CN or -RP2-COOH (hereinafter these substituents are also collectively referred to as "Rax5"). Here, R P1 is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 is a single bond, a divalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, some or all of the hydrogen atoms of the linear saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of R P1 and R P2 may be substituted with fluorine atoms. The above-mentioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of a plurality of the above-mentioned substituents. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and the like. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group and the like; 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. Examples of the monovalent aromatic hydrocarbon group having 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, phenanthrene and the like.

[0041] Ra’ 3 is Ra’ 1 or Ra’ 2 When bonding to any of them to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group and the like.

[0042] Tertiary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group for protecting a carboxy group include an acid dissociable group represented by the following general formula (a1-r-2). Among the acid dissociable groups represented by the following formula (a1-r-2), those composed of an alkyl group may be hereinafter referred to as "tertiary alkyl ester type acid dissociable group" for convenience.

[0043]

Chemical formula

[0044] Examples of the hydrocarbon group of Ra’ 4 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group. Examples of the linear or branched alkyl group and the cyclic hydrocarbon group (an aliphatic hydrocarbon group which is a monocyclic group, an aliphatic hydrocarbon group which is a polycyclic group, an aromatic hydrocarbon group) in Ra’ 4 are the same as those of the above Ra’ 3 . The linear or cyclic alkenyl group in Ra’ 4 is preferably an alkenyl group having 2 to 10 carbon atoms. Examples of the hydrocarbon group of Ra’ 5 and Ra’ 6 are the same as those of the above Ra’ 3 .

[0045] When Ra’ 5 and Ra’ 6 are bonded to each other to form a ring, groups represented by the following general formula (a1-r2-1), groups represented by the following general formula (a1-r2-2), and groups represented by the following general formula (a1-r2-3) are preferably exemplified. On the other hand, when Ra’ 4 to Ra’ 6 are not bonded to each other and are independent hydrocarbon groups, groups represented by the following general formula (a1-r2-4) are preferably exemplified.

[0046] [Chemical formula] [In formula (a1-r2-1), Ra’ 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a part of which may be substituted with a halogen atom or a heteroatom-containing group. Ra’ 11 is Ra’ 10represents a group that forms an aliphatic cyclic group together with a bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms of this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent 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 which may have a substituent. In formula (a1-r2-4), Ra’ 12 and Ra’ 13 are each independently 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 which may have a substituent. * represents a bond (the same applies hereinafter).]

[0047] In the above formula (a1-r2-1), Ra’ 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group.

[0048] Ra’ 10 As the linear alkyl group in, it has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra’ 10 As the branched alkyl group in, those similar to the above Ra’ 3 can be mentioned.

[0049] Ra’ 10The alkyl group in may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Further, some of the carbon atoms (such as a methylene group) constituting the alkyl group may be substituted with a heteroatom-containing group. Examples of the heteroatom herein include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, and the like.

[0050] In formula (a1-r2-1), Ra’ 11 (The aliphatic cyclic group formed together with the carbon atom to which Ra’ 10 is bonded) is preferably a group exemplified as the monocyclic group or polycyclic group of Ra’ 3 in formula (a1-r-1), which is an aliphatic hydrocarbon group (alicyclic hydrocarbon group). Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable.

[0051] In formula (a1-r2-2), examples of the cyclic hydrocarbon group formed by Xa together with Ya include a group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) of Ra’ 3 in formula (a1-r-1). The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of this substituent include the same ones as the substituents that the cyclic hydrocarbon group of Ra’ 3 may have. In formula (a1-r2-2), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms for Ra 101 ~Ra 103 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 103Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 2,6 decanyl group, tricyclo[3.3.1.1 3,7 decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecanyl group, adamantyl group and other polycyclic aliphatic saturated hydrocarbon groups. Ra 101 ~Ra 103 Among them, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among them, a hydrogen atom, a methyl group, and an ethyl group are more preferable, and a hydrogen atom is particularly preferable.

[0052] Examples of the substituent of the linear saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the above Ra 101 ~Ra 103 include, for example, the same groups as those of Ra x5 described above.

[0053] Ra 101 ~Ra 103 Examples of the group containing a carbon-carbon double bond formed by two or more of them bonding to each other to form a cyclic structure include cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylideneethenyl group, cyclohexylideneethenyl group and the like. Among these, from the viewpoint of ease of synthesis, cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group are preferable.

[0054] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is preferably the group exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of Ra' 3 in formula (a1-r-1). In formula (a1-r2-3), Ra104 Examples of the aromatic hydrocarbon group in [description] include groups 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, and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0055] 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 hydroxy group, a carboxy 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.

[0056] In formula (a1-r2-4), Ra' 12 and Ra' 13 are each independently a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in Ra' 12 and Ra' 13 are the same as those of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in the above Ra 101 ~Ra 103 Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. When the linear saturated hydrocarbon group represented by the above Ra' 12 and Ra' 13 is substituted, examples of the substituent include the same groups as those of the above Ra x5 for example.

[0057] In formula (a1-r2-4), Ra’ 14 is a hydrocarbon group which may have a substituent. Ra’ 14 Examples of the hydrocarbon group in Ra’ include a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0058] Ra’ 14 The linear alkyl group in Ra’ 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 a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0059] Ra’ 14 The branched alkyl group in Ra’ preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group, etc., and an isopropyl group is preferred.

[0060] Ra’ 14 When Ra’ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may also be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically, examples include cyclopentane, cyclohexane, etc. As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc.

[0061] Ra’ 14 Examples of the aromatic hydrocarbon group in 14 include Ra 104 The same ones as the aromatic hydrocarbon group in 104 can be mentioned. Among them, Ra’ 14 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 naphthalene or anthracene, and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene. Ra’ 14 Examples of the substituent that Ra’ 104 may have include the same ones as the substituent that Ra 104 may have.

[0062] When Ra’ 14 in formula (a1-r2-4) is a naphthyl group, the position bonding to the tertiary carbon atom in the said formula (a1-r2-4) may be either the 1-position or the 2-position of the naphthyl group. When Ra’ 14 in formula (a1-r2-4) is an anthryl group, the position bonding to the tertiary carbon atom in the said formula (a1-r2-4) may be any of the 1-position, 2-position or 9-position of the anthryl group.

[0063] Specific examples of the group represented by the said formula (a1-r2-1) are given below.

[0064]

Chemical formula

[0065]

Chemical formula

[0066]

Chemical formula

[0067] Specific examples of the group represented by the formula (a1-r2-2) are given below.

[0068]

Chem.

[0069]

Chem.

[0070]

Chem.

[0071] Specific examples of the group represented by the formula (a1-r2-3) are given below.

[0072]

Chem.

[0073] Specific examples of the group represented by the formula (a1-r2-4) are given below.

[0074]

Chem.

[0075] Tertiary alkyloxycarbonyl acid-dissociable group: Examples of the acid-dissociable group that protects the hydroxyl group among the polar groups include, for example, the acid-dissociable group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as "tertiary alkyloxycarbonyl acid-dissociable group" for convenience).

[0076]

Chem.

[0077] In formula (a1-r-3), Ra’ 7 ~Ra’ 9 is each preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Further, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0078] Secondary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group for protecting a carboxy group include an acid dissociable group represented by the following general formula (a1-r-4).

[0079] [Chemical formula] [In the formula, Ra’ 10 is a hydrocarbon group. Ra’ 11a and Ra’ 11b are each independently a hydrogen atom, a halogen atom or an alkyl group. Ra’ 12 is a hydrogen atom or a hydrocarbon group. Ra’ 10 and Ra’ 11a or Ra’ 11b and may be bonded to each other to form a ring. Ra’ 11a or Ra’ 11b and Ra’ 12 and may be bonded to each other to form a ring.]

[0080] In the formula, Ra’ 10 and Ra’ 12 Examples of the hydrocarbon group in include the same as those of the above Ra’ 3 . In the formula, Ra’ 11a and Ra’ 11b Examples of the alkyl group in include the same as those of the alkyl group in the above Ra’ 1 . In the formula, Ra’ 10 and Ra’ 12 The hydrocarbon group in, and Ra’11a and Ra’ 11b The alkyl group in 11b may have a substituent. Examples of such a substituent include Ra x5 etc.

[0081] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, and may be an alicyclic ring or an aromatic ring. The alicyclic ring and the aromatic ring may contain heteroatoms.

[0082] Ra’ 10 and Ra’ 11a or Ra’ 11b Among the above, the rings formed by the combination of Ra’ and Ra’ or Ra’ are preferably monocycloalkene, a ring in which some of the carbon atoms of monocycloalkene are substituted with heteroatoms (such as oxygen atoms, sulfur atoms), and monocycloalkadiene. Cycloalkenes having 3 to 6 carbon atoms are preferred, and cyclopentene or cyclohexene is preferred.

[0083] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by the combination of Ra’ and Ra’ or Ra’ may be a fused ring. Specific examples of the fused ring include indane, etc.

[0084] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by the combination of Ra’ and Ra’ or Ra’ may have a substituent. Examples of such a substituent include Ra x5 etc.

[0085] Ra’ 11a or Ra’ 11b and Ra’ 12 may combine with each other to form a ring. The ring may be 10 formed by the combination of Ra’ and Ra’ 11a or Ra’ 11bExamples thereof include those similar to the rings formed by bonding to each other.

[0086] Specific examples of the group represented by the formula (a1-r-4) are given below.

[0087]

Chemical formula

[0088] Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, and a structural unit in which at least a part of the hydrogen atoms in the hydroxyl group of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative is protected with a substituent containing the acid-decomposable group, and a structural unit in which at least a part of the hydrogen atoms in -C(=O)-OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative is protected with a substituent containing the acid-decomposable group.

[0089] Among them, as the structural unit (a1), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent is preferable. Preferable specific examples of such a structural unit (a1) include structural units represented by the following general formulas (a1-1), (a1-2), or (a1-3).

[0090]

Chemical formula

[0091] In the above formulas (a1-1) to (a1-3), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable. As 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 preferable, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable.

[0092] In the above formula (a1-1), Va 1 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0093] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in may be saturated or unsaturated, and is usually preferably saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in the structure.

[0094] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and other alkylalkylene groups. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0095] Examples of the aliphatic hydrocarbon group containing a ring in the above structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, and the like.

[0096] Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in Va is a hydrocarbon group having an aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0097] In the formula (a1-1), Ra 1 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4). Among these, a group represented by the general formula (a1-r2-1) or an acid dissociable group represented by the general formula (a1-r-4) is more preferable.

[0098] In the formula (a1-2), Wa 1 The n a2 +1-valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a group combining a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure. The n a2 +1-valent is preferably divalent to tetravalent, and more preferably divalent or trivalent. In the formula (a1-2), Ra 2 is preferably an acid dissociable group represented by the above general formula (a1-r-1).

[0099] In the formula (a1-3), Ya 001The divalent linking group in [compound name] is not particularly limited, but examples of preferred groups include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Ya 001 Preferably, [linking group] is an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, a combination thereof, or a single bond. The number of carbon atoms in the alkylene group is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 4, and particularly preferably from 1 to 3. Among these, Ya 001 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and still more preferably a single bond.

[0100] In the formula (a1-3), Ya 01 The divalent linking group in [compound name] is not particularly limited, but examples of preferred groups include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Ya 01 Among these, Ya 01 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and still more preferably a single bond.

[0101] In the formula (a1-3), Rax 01 is preferably an acid dissociable group represented by the general formula (a1-r-2) or (a1-r-4) above. Among these, an acid dissociable group represented by the general formula (a1-r-2) is more preferable, and a group represented by the general formula (a1-r2-1) is still more preferable.

[0102] In the formula (a1-3), Rz 01 The alkyl group, halogenated alkyl group, and alkoxy group in are preferably those having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group, halogenated alkyl group, and alkoxy group may be linear or branched. Rz 01 As the halogen atom in, an iodine atom or a bromine atom is preferable. Rz 01 As the halogen atom of the halogenated alkyl group in, a fluorine atom, an iodine atom, or a bromine atom is preferable, and a fluorine atom is more preferable. Rz 01 Is preferably an alkoxy group or a hydroxy group, and more preferably a hydroxy group.

[0103] In the formula (a1-3), q is an integer of 0 to 3. When q is 0, it is a benzene structure, when q is 1, it is a naphthalene structure, when q is 2, it is an anthracene structure, and when q is 3, it is a tetracene structure. In the formula (a1-3), n is an integer of 0 or more, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably 1 or 2. When n is an integer of 2 or more, two or more Rz 01 May be the same as or different from each other. In the formula (a1-3), n ≦ q × 2 + 4. For example, when q is 1 and it is a naphthalene structure, all 6 hydrogen atoms of the naphthalene may be substituted with Rz 01 Also, in the naphthalene, Ya 001 , -Ya 01 -C(=O)-O-Ra 01 Group, and Rz 01 The substitution positions of are not particularly limited.

[0104] Specific examples of the structural unit (a1) are shown below. In the following formulas, R α Represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0105] [Chemistry]

[0106] [Chemistry]

[0107] [Chemistry]

[0108] [Chemistry]

[0109] [Chemistry]

[0110] [Chemistry]

[0111] [Chemistry]

[0112] [Chemistry]

[0113] [Chemistry]

[0114] In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Each Rz independently represents a hydrogen atom, an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group.

[0115] [Chemistry]

[0116] [Chemical]

[0117] [Chemical]

[0118] [Chemical]

[0119] [Chemical]

[0120] The structural unit (a1) contained in the component (A1) may be one kind or two or more kinds. As the structural unit (a1), since the characteristics (sensitivity, shape, etc.) in lithography using an electron beam or EUV can be more easily enhanced, the structural unit represented by the above formula (a1-1) or the structural unit represented by the above formula (a1-3) is more preferable. Among them, since it is suitable for enhancing reactivity in the case of EB or EUV, the acid dissociable groups (Ra 1 , Rax 01 ) are preferably acid dissociable groups represented by the above general formulas (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), respectively, and among them, it is particularly preferable to select those which are cyclic groups.

[0121] Alternatively, as the structural unit (a1), those containing the structural unit represented by the following general formula (a1-1-1) may be used.

[0122] [Chemical] [In the formula, Ra 1" is an acid dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4). * indicates a bond.]

[0123] In the above formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the above formula (a1-1).

[0124] The description of the acid dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4) is as described above. Among them, since it is suitable for enhancing reactivity in EB or EUV, it is preferable to select an acid dissociable group that is a cyclic group.

[0125] The proportion of the structural unit (a1) in the component (A1) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, still more preferably 30 to 70 mol%, and particularly preferably 40 to 70 mol% with respect to the total (100 mol%) of all the structural units constituting the component (A1). By setting the proportion of the structural unit (a1) to be equal to or higher than the lower limit value of the above preferable range, lithography characteristics such as sensitivity, resolution, and roughness improvement are improved. On the other hand, when it is equal to or lower than the upper limit value of the above preferable range, a balance with other structural units can be achieved, and various lithography characteristics become good.

[0126] <<Other Structural Units>> The component (A1) may have other structural units in addition to the above-described structural unit (a1) as necessary. Examples of other structural units include a structural unit represented by the following general formula (a10-1); a structural unit (a2) containing a lactone-containing cyclic group; a structural unit (a5) that generates an acid upon exposure; a structural unit (a8) derived from a compound represented by the following general formula (a8-1), etc.

[0127] Structural unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0128] [Chemical formula] [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. Ya x1 is a single bond or a divalent linking group. Wa x1 is an aromatic hydrocarbon group which may have a substituent. n ax1 is an integer of 1 or more.]

[0129] In the formula (a10-1), R is the same as R in the general formula (a1-1). As 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 preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

[0130] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. In the above chemical formula, the divalent linking group for Ya x1 is not particularly limited, but examples of preferable ones include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

[0131] ·Divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group which may have a substituent may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0132] ··Aliphatic hydrocarbon group The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0133] ···a linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. can be mentioned. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, etc. can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0134] The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, etc.

[0135] ···an aliphatic hydrocarbon group containing a ring in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane and the like can be mentioned.

[0136] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group is more preferable. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is even more preferable. As the halogen atom as the substituent, a fluorine atom is preferable. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Preferred examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0137] ··Aromatic hydrocarbon group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of the group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0138] In the aromatic hydrocarbon group, the hydrogen atoms of the aromatic hydrocarbon group may be substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable. Examples of the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0139] ·Divalent linking group containing a heteroatom: Examples of the divalent linking group containing a heteroatom include -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group, an acyl group, etc.), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y 21 -O-Y22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-O-Y 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -,-Y 21 -O-C(=O)-Y 22 - or -Y 21 -S(=O)2-O-Y 22 -represented by the group [wherein, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m” is an integer of 1 to 3.] etc. are exemplified. When the divalent linking group containing the hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)-, the H thereof may be substituted with a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. General formula -Y 21 -O-Y 22 -,-Y 21 -O-,-Y 21 -C(=O)-O-,-C(=O)-O-Y 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -,-Y 21 -O-C(=O)-Y 22 - or -Y 21 -S(=O)2-O-Y 22 -in, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as described above. Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22As for this, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. The group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 - In the group represented by, m” is an integer of 1 to 3, 1 or 2 is more preferable, and 1 is particularly preferable. That is, the formula -[Y 21 -C(=O)-O] m” -Y 22 - As the group represented by, the group represented by the formula -Y 21 -C(=O)-O-Y 22 - is particularly preferable. Among them, the group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ - is preferable. In the formula, a’ is an integer of 1 to 10, an integer of 1 to 8 is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is further preferable, and 1 is most preferable. b’ is an integer of 1 to 10, an integer of 1 to 8 is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is further preferable, and 1 is most preferable.

[0140] Ya x1 As for this, a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof is preferable, and a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-] is more preferable.

[0141] In the formula (a10-1) above, Wa x1 is an aromatic hydrocarbon group which may have a substituent. Wa x1 As the aromatic hydrocarbon group in, from an aromatic ring which may have a substituent (n ax1Examples of the group excluding (+1) hydrogen atoms include those where the aromatic ring herein is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still 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 heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Also, Wa x1 Examples of the aromatic hydrocarbon group in include groups excluding (n ax1 +1) hydrogen atoms from aromatic compounds containing an aromatic ring which may have two or more substituents (for example, biphenyl, fluorene, etc.). Among the above, Wa x1 is preferably a group excluding (n ax1 +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, more preferably a group excluding (n ax1 +1) hydrogen atoms from benzene or naphthalene, and still more preferably a group excluding (n ax1 +1) hydrogen atoms from benzene.

[0142] Wa x1 The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, etc. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent are the same as those listed as the substituent of the cyclic aliphatic hydrocarbon group in Ya x1 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, still more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. Wa x1The aromatic hydrocarbon group in [it] preferably has no substituent.

[0143] In the formula (a10-1), n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0144] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0145] [Chemical formula]

[0146] [Chemical formula]

[0147] [Chemical formula]

[0148] The structural unit (a10) contained in the component (A1) may be one kind or two or more kinds. The component (A1) may or may not have the structural unit (a10), but preferably has the structural unit (a10). When the component (A1) has the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, still more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol% with respect to the total (100 mol%) of all the structural units constituting the component (A1). By setting the proportion of the structural unit (a10) to be not less than the lower limit value, the sensitivity is more likely to be enhanced. On the other hand, by setting it to be not more than the upper limit value, it becomes easier to balance with other structural units.

[0149] Constituent unit (a2): (A1) The component may have a constituent unit (a2) containing a lactone-containing cyclic group (however, excluding those corresponding to the constituent unit (a1)). The lactone-containing cyclic group of the constituent unit (a2) is effective in enhancing the adhesion of the resist film to the substrate when the (A1) component is used for forming the resist film. Further, by having the constituent unit (a2), lithography characteristics and the like become good due to effects such as appropriately adjusting the acid diffusion length, enhancing the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0150] The "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. Counting the lactone ring as the first ring, in the case of only the lactone ring, it is a monocyclic group, and in the case of having another ring structure, regardless of the structure, it is called a polycyclic group. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. As the lactone-containing cyclic group in the constituent unit (a2), any group can be used without particular limitation. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be mentioned.

[0151] [Chemical formula] [In the formula, Ra’ 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR”, -OC(=O)R”, a hydroxyalkyl group or a cyano group; R” is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A” is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom, n’ is an integer of 0 to 2, and m’ is 0 or 1. * indicates a bond (the same applies hereinafter).]

[0152] In the general formulas (a2-r-1) to (a2-r-7), Ra’ 21As the alkyl group in [description], an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, etc. may be mentioned. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Ra’ 21 As the alkoxy group in [description], an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, the group in which the alkyl group mentioned as the Ra’ 21 in [description] and an oxygen atom (-O-) are linked may be mentioned. Ra’ 21 As the halogen atom in [description], a fluorine atom is preferable. Ra’ 21 As the alkyl halide group in [description], the group in which a part or all of the hydrogen atoms of the alkyl group in the Ra’ 21 in [description] are substituted with the halogen atom may be mentioned. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0153] Ra’ 21 In -COOR” and -OC(=O)R” in [description], R” is each a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. As the alkyl group in R”, it may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R” is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When “R” is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane can be exemplified. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tetracyclododecane, etc. can be mentioned. Examples of the lactone-containing cyclic group in R” include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7) respectively. Ra’ 21 The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, and specifically, a group in which at least one hydrogen atom of the alkyl group in the above Ra’ 21 is substituted with a hydroxyl group can be mentioned.

[0154] Ra’ 21 Among the above, each is preferably independently a hydrogen atom or a cyano group.

[0155] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A” is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropyl group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed at the terminal or between carbon atoms of the alkylene group, and examples thereof include -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. As A”, an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

[0156] Specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0157]

Chemical formula

[0158]

Chemical formula

[0159] As the constitutional unit (a2), among others, a constitutional unit derived from an acrylate ester in which a hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent is preferable. Such a constitutional unit (a2) is preferably a constitutional unit represented by the following general formula (a2-1).

[0160]

Chemical formula

[0161] In the formula (a2-1), R is the same as described above. As 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 preferable, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferable.

[0162] In the formula (a2-1), Ya 21 The divalent linking group in is not particularly limited, but examples thereof preferably include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. The divalent linking group in Ya 21 is the same as the divalent linking group in Ya x1 in the general formula (a10-1) above.

[0163] Ya 21 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0164] In the formula (a2-1), Ya 21 is a single bond, and La 21 is preferably -COO- or -OCO-.

[0165] In the formula (a2-1), Ra 21 is a lactone-containing cyclic group. Ra 21 The lactone-containing cyclic groups in are preferably the groups represented by the general formulas (a2-r-1) to (a2-r-7) described above, respectively.

[0166] (A1) component may have one or more types of structural units (a2). (A1) component may or may not have the structural unit (a2). When the (A1) component has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 1 to 10 mol% with respect to the total (100 mol%) of all the structural units constituting the (A1) component. When the proportion of the structural unit (a2) is equal to or higher than the preferable lower limit value, the effect of containing the structural unit (a2) can be sufficiently obtained due to the above-described effect. When it is equal to or lower than the upper limit value, the balance with other structural units can be achieved, and various lithography characteristics become good.

[0167] Structural unit (a5): In the present embodiment, the structural unit (a5) is a structural unit that generates an acid upon exposure, and a known one can be used. By having the structural unit (a5), the acid generated upon exposure is likely to be uniformly distributed in the resist film. As the structural unit (a5), for example, the structural unit represented by the following general formula (a5-1) is preferably exemplified.

[0168] [Chemical formula] [In the formula, R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. La 1 is a divalent linking group or a single bond. Ra 050 is a divalent hydrocarbon group which may have a substituent. n a5 is an integer of 0 to 2. La 0 is a divalent linking group. Ya 0 is a divalent linking group which may have a hetero atom, or a single bond. Ra 051 and Ra 052 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. n0 is an integer of 1 to 4. m is an integer of 1 or more, and M’m+ is an m-valent onium cation.

[0169] {Anion part} In the formula (a5-1), R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. R m The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among the halogen atoms in the halogenated alkyl group, a fluorine atom is particularly preferable. R m 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. From the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable.

[0170] In the formula (a5-1), La 1 is a divalent linking group or a single bond. La 1 The divalent linking group in La is not particularly limited, but a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom are preferably mentioned. Each is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified as the divalent linking group in the above Ya x1 Among them, La Among the above, as La 1 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group or a combination thereof, or a single bond. Among these, La1 is more preferably an ester bond [-C(=O)-O-, -O-C(=O)-] or a single bond, and even more preferably an ester bond [-C(=O)-O-, -O-C(=O)-].

[0171] In the formula (a5-1), Ra 050 is a divalent hydrocarbon group which may have a substituent. Ra 050 The divalent hydrocarbon group in Ra may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0172] ··Ra 050 The aliphatic hydrocarbon group in The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in the structure.

[0173] ···linear or branched aliphatic hydrocarbon group 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. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically includes a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group 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. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0174] The above-mentioned linear or branched-chain aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like.

[0175] ···an aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched-chain aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched-chain aliphatic hydrocarbon group, and the like can be mentioned. Examples of the above-mentioned linear or branched-chain aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from monocycloalkane is preferred. As the monocycloalkane, those having 3 to 6 carbon atoms are preferred, and specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane and the like can be mentioned.

[0176] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are most preferred. As the alkoxy group 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. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom. As the substituent containing a heteroatom, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferred.

[0177] ··Ra 050Aromatic hydrocarbon group herein The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specifically, as the aromatic ring, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc. may be mentioned. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specifically, as the aromatic heterocycle, a pyridine ring, a thiophene ring, etc. may be mentioned. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0178] In the aromatic hydrocarbon group, the hydrogen atoms possessed by the aromatic hydrocarbon group may be substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are most preferable. As the alkoxy group, halogen atom, and halogenated alkyl group as the substituent, those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group can be mentioned.

[0179] In the formula (a5-1), n a5 is an integer of 0 to 2. Among the above, Ra 050 is preferably an aliphatic hydrocarbon group containing a ring in the structure, more preferably a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure, and still more preferably an alicyclic hydrocarbon group which may have a substituent and is a polycyclic group or a monocyclic group. Alternatively, among the above, Ra 050 is preferably an aromatic hydrocarbon group.

[0180] n a5 When n is 2, the two Ra's 050 may both be alicyclic hydrocarbon groups which may have substituents, may both be aromatic hydrocarbon groups, or may be a combination of an alicyclic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group.

[0181] In the formula (a5-1), La 0 is a divalent linking group. La 0 Examples of the divalent linking group in La include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-O-C(=O)-O-); combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, etc. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of such divalent linking groups include linking groups represented by the following general formulas (L-al-1) to (L-al-8). In the following general formulas (L-al-1) to (L-al-8), Ra in the above formula (a5-1) 050 is bonded to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0182] [Chemical formula] [In the formula, V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0183] The divalent saturated hydrocarbon group in V' 102 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.

[0184] The alkylene group in V' 101 and V' 102 may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred. V' 101 and V' 102As the alkylene group in [it], specifically, a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-; a pentamethylene group [-CH2CH2CH2CH2CH2-] and the like can be mentioned. Also, V’ 101 or V’ 102 In [it], 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 the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra’ in the above formula (a1-r-1) 3 A divalent group obtained by further removing one hydrogen atom is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.

[0185] La 0 As [it], a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, the linking groups represented by the above formulas (L-al-1) to (L-al-5), (L-al-8) are more preferable, and the linking group represented by (L-al-3) or (L-al-8) is still more preferable.

[0186] In the above formula (a5-1), Ya 0 is a divalent linking group which may have a hetero atom, or a single bond. Ya 0The divalent linking group in [the relevant context] is not particularly limited, but examples thereof preferably include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Ya 0 Regarding the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom in [the relevant context], they are the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom exemplified as the divalent linking group in the above Ya x1 in [the relevant context]. Among the above, Ya 0 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0187] In the formula (a5-1), Ra 051 and Ra 052 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. Ra 051 and Ra 052 The fluorinated alkyl group in [the relevant context] is preferably a linear or branched fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a trifluoromethyl group. In the formula (a5-1), at least one of Ra - bonded to the carbon atom adjacent to SO3 051 and Ra 052 is preferably a fluorine atom from the viewpoint of acid strength.

[0188] In the formula (a5-1), n0 is an integer of 1 to 4, and 1, 2 or 3 is preferred.

[0189] {Cation part} In the formula (a5-1), M’ m+ represents an m-valent onium cation. Among these, M’ m+ is preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more.

[0190] Preferred cation part ((M’ m+ )) 1 / m) Examples thereof include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0191]

Chemical formula

[0192] In the above general formulas (ca-1) to (ca-3), the aryl group in R 201 ~R 207 includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable. R 201 ~R 207 The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in is preferably having 2 to 10 carbon atoms. R 201 ~R 207 , and R 210Examples of the substituent that may be possessed include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, a group represented by each of the following general formulas (ca-r-1) to (ca-r-7), and the like.

[0193] [Chemical formula] [In the formula, R’ 201 is each independently a hydrogen atom, a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.]

[0194] Cyclic group which may have a substituent: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0195] R’ 201 The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R’ 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which a part of the carbon atoms constituting these aromatic rings is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. R’ 201Specific examples of the aromatic hydrocarbon group in [X] include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (e.g., arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0196] R’ 201 The cyclic aliphatic hydrocarbon group in [X] includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, etc. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, as the polycycloalkane, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0197] Among them, R’201 As the cyclic aliphatic hydrocarbon group in 201 , a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, a group obtained by removing one hydrogen atom from polycycloalkane is more preferable, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

[0198] 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, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-] etc. may be mentioned. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- etc. may be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0199] Also, R’ 201The cyclic hydrocarbon group in [description] may contain heteroatoms such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the aforementioned 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) described later, and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16) are exemplified.

[0200]

Chemical formula

[0201] R’ 201 Examples of the substituent in the cyclic group of [description] include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. As the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are most preferable. As the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, 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 preferable, and a methoxy group and an ethoxy group are most preferable. As the halogen atom as a substituent, a fluorine atom is preferable. Examples of the halogenated alkyl group as a substituent include an alkyl group having 1 to 5 carbon atoms, for example, a group in which some or all of the hydrogen atoms of a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc. are substituted with the halogen atom. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0202] Optionally substituted chain alkyl group: R’ 201 The chain alkyl group of [description] 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, for example, 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, 4-methylpentyl group, etc. can be mentioned.

[0203] The chain alkenyl group which may have a substituent: R’ 201 The chain alkenyl group of R’ may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include vinyl group, propenyl group (allyl group), butenyl group, etc. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. Among the above, the linear alkenyl group is preferred as the chain alkenyl group, and the vinyl group and propenyl group are more preferred, and the vinyl group is particularly preferred.

[0204] R’ 201 Examples of the substituent in the chain alkyl group or alkenyl group of R’ include alkoxy group, halogen atom, halogenated alkyl group, hydroxyl group, carbonyl group, nitro group, amino group, and the cyclic group in the above R’ 201 etc.

[0205] R’ 201The cyclic group which may have a substituent, the chain-like alkyl group which may have a substituent, or the chain-like alkenyl group which may have a substituent, in addition to those described above, as the cyclic group which may have a substituent or the chain-like alkyl group which may have a substituent, those similar to the acid dissociable group represented by the above formula (a1-r-2) are also included.

[0206] Among them, R’ 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; a lactone-containing cyclic group represented by the above general formulas (a2-r-1) to (a2-r-7); a -SO2-containing cyclic group represented by the following general formulas (b5-r-1) to (b5-r-4), etc. are preferable.

[0207] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R N )(wherein the R N is an alkyl group having 1 to 5 carbon atoms).). As the ring formed, it is preferable that one ring containing the sulfur atom in the formula in its ring skeleton is a 3- to 10-membered ring including the sulfur atom, and particularly preferably a 5- to 7-membered ring. 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 thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, etc.

[0208] R 208 ~R 209Each 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. When it is an alkyl group, they may be bonded to each other to form a ring.

[0209] R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO2-containing cyclic group which may have a substituent. R 210 Examples of the aryl group in R include unsubstituted aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 210 Examples of the alkyl group in R include linear or cyclic alkyl groups, preferably those having 1 to 30 carbon atoms. R 210 The alkenyl group in R preferably has 2 to 10 carbon atoms. R 210 The -SO2-containing cyclic group in R is not particularly limited and any one can be used. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) are exemplified, a "-SO2-containing polycyclic group" is preferred, and a group represented by the general formula (b5-r-1) is more preferred.

[0210]

Chemical formula

[0211] In the 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. As B”, an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is even more preferable.

[0212] In the general formulas (b5-r-1) to (b5-r-4), Rb’ 51 is each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR”, -OC(=O)R”, a hydroxyalkyl group or a cyano group, and among them, each is preferably independently a hydrogen atom or a cyano group.

[0213] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. “Ac” in the formula represents an acetyl group.

[0214]

Chemical formula

[0215]

Chemical formula

[0216]

Chemical formula

[0217] Specific examples of the suitable cation represented by the formula (ca-1) include cations represented by the following chemical formulas respectively.

[0218]

Chemical formula

[0219]

Chemical formula

[0220] [Chemical formula] [In the formula, g1, g2, and g3 represent the number of repetitions, 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.]

[0221] [Chemical formula]

[0222] [Chemical formula]

[0223] [Chemical formula] [In the formula, R” 201 is a hydrogen atom or a substituent, and examples of the substituent are the same as those listed as the substituents that R 201 ~R 207 , and R 210 ~R 212 may have.]

[0224] [Chemical formula]

[0225] Specific examples of the preferred cation represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0226] Specific examples of the preferred cation represented by the formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively.

[0227] [Chemical formula]

[0228] The cationic part ((M’ m+ ) 1 / m ) in the formula (a5-1) is preferably a sulfonium cation, more preferably the cations represented by the formulas (ca-1) to (ca-3), still more preferably the cation represented by the formula (ca-1), and particularly preferably the cations represented by the formulas (ca-1-1) to (ca-1-84). From the viewpoint of particularly high sensitivity, as the preferred cation represented by the formula (ca-1), those having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent are preferred. For example, cations selected from the group consisting of the cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferred.

[0229] Specific preferred examples of the structural unit (a5) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. m and M’ m+ are the same as m and M’ m+ in the above general formula (a5-1).

[0230]

Chemical formula

[0231]

Chemical formula

[0232]

Chemical formula

[0233] The structural unit (a5) contained in the component (A1) may be one kind or two or more kinds. When the component (A1) has the structural unit (a5), the proportion of the structural unit (a5) in the component (A1) is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, and even more preferably 15 to 20 mol% with respect to the total of all the structural units constituting the component (A1) (100 mol%). When the proportion of the structural unit (a5) is equal to or higher than the lower limit of the above-mentioned preferred range, it becomes easier to achieve further increased sensitivity and improved resolution. On the other hand, when it is equal to or lower than the upper limit of the above-mentioned preferred range, it becomes easier to balance with other structural units.

[0234] Structural unit (a8): The structural unit (a8) is a structural unit derived from a compound represented by the following general formula (a8-1).

[0235] [Chemical formula] [In the formula, W 2 is a polymerizable group-containing group. Ya x2 is a single bond or an (n ax2 +1)-valent linking group. Ya x2 and W 2 may form a condensed ring. R 1 is a fluorinated alkyl group having 1 to 12 carbon atoms. R 2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom. R 2 and Ya x2 may be bonded to each other to form a ring structure. n ax2 is an integer of 1 to 3.]

[0236] W 2 In the polymerizable group-containing group of, the "polymerizable group" is a group that enables a compound having a polymerizable group to polymerize by radical polymerization or the like, and refers to a group containing a multiple bond between carbon atoms such as an ethylenic double bond.

[0237] As the polymerizable group-containing group, it may be a group composed only of polymerizable groups, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of the other groups other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like. Examples of the polymerizable group-containing group include, for example, a group represented by the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 -. In this chemical formula, R X11 , R X12 and R X13 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 is a single bond or a divalent linking group.

[0238] Examples of the condensed ring formed by Ya x2 and W 2 include a condensed ring formed by the polymerizable group at the W 2 site and Ya x2 , and a condensed ring formed by a group other than the polymerizable group at the W 2 site and Ya x2 . The condensed ring formed by Ya x2 and W 2 may have a substituent.

[0239] Specific examples of the constitutional unit (a8) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0240]

Chemical formula

[0241] Among the above examples, the structural unit (a8) is preferably at least one selected from the group consisting of structural units represented by 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 structural units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0242] (A1) component may have one or more than two kinds of the structural unit (a8). The (A1) component may or may not have the structural unit (a8). The proportion of the structural unit (a8) in the (A1) component is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, based on the total of all structural units (100 mol%) constituting the (A1) component.

[0243] The (A1) component contained in the resist composition may be used alone or in combination of two or more.

[0244] Examples of the (A1) component include a polymer compound containing a repeating structure of the structural unit (a1) and the structural unit (a10), a polymer compound containing a repeating structure of the structural unit (a1), the structural unit (a10), and the structural unit (a5), and the like.

[0245] In the polymer compound having a repeating structure of the structural unit (a1) and the structural unit (a10), the proportion of the structural unit (a1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, based on the total of all structural units (100 mol%) constituting the polymer compound. Also, the proportion of the structural unit (a10) in the polymer compound is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, based on the total of all structural units (100 mol%) constituting the polymer compound.

[0246] In a polymer compound having a repeating structure of a structural unit (a1), a structural unit (a10), and a structural unit (a5), the proportion of the structural unit (a1) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound. Also, the proportion of the structural unit (a10) in the polymer compound is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound. Also, the proportion of the structural unit (a5) in the polymer compound is preferably more than 0 mol% and 20 mol% or less, more preferably 5 to 20 mol%, and even more preferably 5 to 15 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound.

[0247] Such component (A1) can be produced by dissolving monomers that induce each structural unit in a polymerization solvent, and adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (e.g., V-601, etc.) thereto and performing polymerization. Alternatively, such component (A1) can be produced by dissolving a monomer that induces the structural unit (a1) and a monomer that induces an arbitrary structural unit (e.g., a monomer that induces the structural unit (a10), etc.) in a polymerization solvent, adding the radical polymerization initiator as described above thereto and performing polymerization, and then performing a deprotection reaction. In addition, during polymerization, for example, 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 end. In this way, a copolymer into which a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is introduced is effective for reducing development defects and LER (line edge roughness: uneven irregularities on the line sidewall).

[0248] (A1) component's weight-average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, and even more preferably from 4,000 to 15,000. When the Mw of the (A1) component is below the preferred upper limit of this range, there is sufficient solubility in the resist solvent for use as a resist. When it is above the preferred lower limit of this range, the dry etching resistance and the resist pattern cross-sectional shape are good. (A1) component's dispersity (Mw / Mn) is not particularly limited, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0. Here, Mn represents the number-average molecular weight.

[0249] ·Regarding the (A2) component The resist composition of this embodiment may use, as the (A) component, a base material component (hereinafter referred to as the "(A2) component") that does not correspond to the (A1) component and whose solubility in the developer changes by the action of an acid in combination. (A2) component is not particularly limited and may be arbitrarily selected from a number of conventionally known ones as a base material component for a chemically amplified resist composition and used. (A2) component may be used alone as one kind of high molecular compound or low molecular compound, or may be used in combination of two or more kinds.

[0250] (A) component's ratio of the (A1) component is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of the (A) component. When the ratio is 25% by mass or more, a resist pattern excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement is likely to be formed.

[0251] In the resist composition of this embodiment, the content of the (A) component may be adjusted according to the resist film thickness to be formed, etc.

[0252] <Compound (D0)> Compound (D0) is a compound represented by the following general formula (d0), and has one or more halogen atoms and acetal groups (R 02 -O-R 01 -O-) each. By containing the (D0) component, the resist composition of the present embodiment has better lithography characteristics such as sensitivity and uniformity of pattern dimensions in the formation of a resist pattern.

[0253] [Chemical formula] [In the formula, R ar is an aromatic ring which may have a substituent. R 01 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R 02 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R 03 is a halogen atom. j is an integer of 1 or more as long as the valence permits. When j is an integer of 2 or more, a plurality of groups represented by R 02 -O-R 01 -O- may be the same or different from each other. k is an integer of 1 or more as long as the valence permits. When k is an integer of 2 or more, a plurality of R 03 may be the same or different from each other. Y d0 is a divalent linking group or a single bond. m is an integer of 1 or more, and M m+ represents an m-valent organic cation.]

[0254] {(Anion part of the (D0) component)} In the above formula (d0), the aromatic ring in R ar is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still 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; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

[0255] The aromatic ring in the above R ar may or may not have a substituent other than R 03 (halogen atom) and R 02 -O-R 01 -O-. Examples of the substituent include a linear alkyl group, an alkoxy group, a halogenated alkyl group, a nitro group, a hydroxy group, and the like. As the linear alkyl group as the substituent, a linear alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is most preferable. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. The aromatic ring in R ar preferably has no substituent.

[0256] The above R 01 is a chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. The chain-like saturated hydrocarbon group has 1 to 10 carbon atoms, and among them, 1 to 5 carbon atoms are preferable, 1 to 3 carbon atoms are more preferable, 1 to 2 carbon atoms are still more preferable, and 2 carbon atoms are particularly preferable. R 01Examples of the linear saturated hydrocarbon group in [compound name] include linear alkylene groups. R 01 Examples of the linear alkylene group in [compound name] include, for example, a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. R 01 The saturated hydrocarbon group in [compound name] is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Among them, from the viewpoints of ease of synthesis and acid diffusion control, a monovalent linear saturated hydrocarbon group having 1 to 5 carbon atoms is preferable, a methylene group and an ethylene group are more preferable, and an ethylene group is even more preferable.

[0257] R 02 R is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. The linear saturated hydrocarbon group has 1 to 10 carbon atoms. Among them, 1 to 5 carbon atoms are preferable, 1 to 3 carbon atoms are more preferable, 1 to 2 carbon atoms are even more preferable, and 1 carbon atom is particularly preferable. R 02 Examples of the linear saturated hydrocarbon group in [compound name] include linear alkyl groups. R 02 Examples of the linear alkyl group in [compound name] include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like. R 02 The saturated hydrocarbon group in [compound name] is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Among them, from the viewpoints of ease of synthesis and acid diffusion control, a monovalent linear saturated hydrocarbon group having 1 to 5 carbon atoms is preferable. Among them, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable.

[0258] In the formula (d0), R 03 is a halogen atom. R 03Examples of the halogen atom as the substituent include an iodine atom, a fluorine atom, a chlorine atom, and a bromine atom. Among them, from the viewpoints of high sensitivity and lithography characteristics, an iodine atom and a fluorine atom are preferable, and particularly from the viewpoint of high sensitivity, an iodine atom is more preferable.

[0259] In the formula (d0), j is an integer of 0 or more as long as the valence allows. When j is an integer of 2 or more, a plurality of R 02 -O-R 01 The groups represented by -O- may be the same or different from each other. In the formula (d0), k is an integer of 1 or more as long as the valence allows.

[0260] In the formula (d0), Y d0 is a divalent linking group or a single bond. Y d0 Examples of the divalent linking group in Y include, for example, a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a heteroatom. The same as the description of the divalent linking group (a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom) in Ya in the above formula (a10-1) can be mentioned. x1 The same as the description of the divalent linking group (a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom) in Ya in the above formula (a10-1) can be mentioned. As the divalent hydrocarbon group which may have a substituent, a linear or branched alkylene group is preferable. The number of carbon atoms of the alkylene group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2. As the divalent linking group containing a heteroatom, an ester bond [-C(=O)-O-, -O-C(=O)-] and an ether bond (-O-) are preferable. Y d0 Y is more preferably a linear or branched alkylene group, a combination of a linear or branched alkylene group and an ester bond [-C(=O)-O-, -O-C(=O)-], a combination of a linear or branched alkylene group and an ether bond (-O-), or a single bond, still more preferably a linear or branched alkylene group or a single bond, and particularly preferably a single bond.

[0261] As the component (D0), a compound (D0-0) represented by the following general formula (d0-0) is preferable.

[0262] [Chemical formula] [In the formula, n is an integer from 0 to 2. R 01 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R 02 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R 030 is a halogen atom. j0 is an integer from 1 to 8. When j0 is an integer of 2 or more, a plurality of R 02 -O-R 01 -O- represented groups may be the same or different from each other. k0 is an integer from 1 to 8. When k0 is an integer of 2 or more, a plurality of R 030 may be the same or different from each other. However, 2 ≦ j0 + k0 ≦ 5 + 2 × n. m is an integer of 1 or more, and M m+ represents an m-valent organic cation. ]

[0263] In the formula (d0-0), R 01 , R 02 , m, M m+ are the same as R 01 , R 02 , m, M m+ in the formula (d0). In the formula (d0’), R 030 is a halogen atom. Examples of the halogen atom as the substituent in R 030 include an iodine atom, a fluorine atom, a chlorine atom, and a bromine atom. Among them, from the viewpoints of high sensitivity and lithography characteristics, an iodine atom and a fluorine atom are preferable, and particularly, from the viewpoint of high sensitivity, an iodine atom is more preferable.

[0264] In the formula (d0-0), n is an integer from 0 to 2, preferably 0 or 1, and more preferably 0. In the formula (d0-0), j0 is an integer from 1 to 8, preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1. When j0 is an integer of 2 or more, a plurality of R 02 -O-R 01 The groups represented by -O- may be the same or different from each other. In the formula (d0-0), k0 is an integer from 1 to 8, preferably an integer from 1 to 4, and from the viewpoint of achieving both high sensitivity and lithography characteristics, an integer from 1 to 3 is more preferable. In particular, from the viewpoint of high sensitivity, 2 or 3 is even more preferable, and from the viewpoint of lithography characteristics, 1 or 2 is even more preferable. When k0 is an integer of 2 or more, a plurality of R 030 may be the same or different from each other.

[0265] Specific examples of the anionic part of the (D0) component are shown below.

[0266]

Chemical formula

[0267] The anionic part of the (D0) component is preferably selected from the group consisting of anions represented by the above chemical formulas (d0-an-1) to (d0-an-13). Among these, the anionic part of the (D0) component is preferably selected from the group consisting of anions represented by the above chemical formulas (d0-an-1) to (d0-an-4), (d0-an-6) to (d0-an-11), and (d0-an-13) because the sensitivity is more likely to be improved. More preferably, it is selected from the group consisting of anions represented by the above chemical formulas (d0-an-8) and (d0-an-9). Alternatively, since the lithography characteristics can be easily enhanced, the anion part of the (D0) component is preferably selected from the group consisting of anions represented by the above chemical formulas (d0-an-1) to (d0-an-13), and more preferably selected from the group consisting of anions represented by the above chemical formulas (d0-an-1) to (d0-an-4), (d0-an-6) to (d0-an-8), and (d0-an-12).

[0268] {(Cation part of the (D0) component)} In the above formula (d0), M m+ represents an m-valent organic cation. m is an integer of 1 or more. M m+ As the organic cation in, an onium cation is preferable, and among these, a sulfonium cation and an iodonium cation are more preferable.

[0269] M m+ As the organic cation of, at least one selected from the group consisting of cations represented by the above general formulas (ca-1) to (ca-3) is preferable, and among these, the cation represented by the above general formula (ca-1) is more preferable. Specifically, cations represented by the above formulas (ca-1-1) to (ca-1-84) are exemplified. From the viewpoint of particularly high sensitivity, as the preferable cation represented by the above formula (ca-1), those having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent are preferable. For example, cations selected from the group consisting of cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferable.

[0270] Specific examples of the (D0) component are given below, but are not limited thereto.

[0271]

Chemical formula

[0272]

Chemical formula

[0273]

Chem.

[0274] (Component (D0)) is preferably selected from the group consisting of compounds represented by the above chemical formulas (D0-1) to (D0-17). Alternatively, among the above, since the sensitivity of (Component (D0)) is more likely to be improved, those selected from the group consisting of compounds represented by the above chemical formulas (D0-8), (D0-9) and (D0-14) are more preferable. Alternatively, among the above, since the lithography characteristics of (Component (D0)) are more likely to be enhanced, those selected from the group consisting of compounds represented by the above chemical formulas (D0-1) to (D0-4), (D0-6) to (D0-8) and (D0-12) are more preferable, and from the viewpoint of compatibility with high sensitivity, the compound represented by the chemical formula (D0-8) is even more preferable.

[0275] In the resist composition of the present embodiment, (Component (D0)) may be used alone or in combination of two or more. In the resist composition of the present embodiment, the content of (Component (D0)) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 10 parts by mass with respect to 100 parts by mass of (Component (A)). When the content of (Component (D0)) is equal to or higher than the lower limit value of the above preferable range, in the formation of a resist pattern, it has high sensitivity and lithography characteristics such as the uniformity of pattern dimensions are better. On the other hand, when the content of (Component (D0)) is equal to or lower than the upper limit value of the above preferable range, it is easy to maintain good sensitivity and the solubility in the developer is also easy to improve.

[0276] <Other components> In addition to the above-described component (A) and component (D0), the resist composition of this embodiment may further contain other components. Examples of the other components include the following component (B), component (D) (excluding component (D0)), component (E), component (F), component (S), and the like.

[0277] ≪Acid Generator Component (B)≫ The resist composition of this embodiment preferably further contains an acid generator component (B) (excluding the compound (D0)) that generates an acid upon exposure. Component (B) is not particularly limited, and those proposed as acid generators for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyldiazomethanes, poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, and many others.

[0278] Examples of the onium salt-based acid generators include a compound represented by the following general formula (b-1) (hereinafter also referred to as "(b-1) component"), a compound represented by general formula (b-2) (hereinafter also referred to as "(b-2) component"), or a compound represented by general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0279]

Chemical Formula

[0280] {Anion part} ·Anion in the component (b-1) In the formula (b-1), R 101 is an optionally substituted cyclic group, an optionally substituted chain-like alkyl group, or an optionally substituted chain-like alkenyl group.

[0281] Optionally substituted cyclic group: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Further, the aliphatic hydrocarbon group is preferably saturated.

[0282] R 101 The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R 101Specific examples of the aromatic ring of the aromatic hydrocarbon group include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. R 101 Specific examples of the aromatic hydrocarbon group include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0283] R 101 The cyclic aliphatic hydrocarbon group includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, as the polycycloalkane, adamantane, norbornane, isobornane, tricyclo[5.2.1.02,6 Polysicycloalkanes having a polycyclic skeleton of a crosslinked ring system such as decane and tetracyclododecane; polysicycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton are more preferable.

[0284] Among them, R 101 As the cyclic aliphatic hydrocarbon group in, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polysicycloalkane is preferable, a group obtained by removing one hydrogen atom from polysicycloalkane is more preferable, an adamantyl group and a norbornyl group are further preferable, and an adamantyl group is particularly preferable.

[0285] 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 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. may be mentioned. The branched aliphatic hydrocarbon group, which may be bonded to an alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0286] Also, R 101 The cyclic hydrocarbon group in may contain a heteroatom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the above 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) can be mentioned. In the formula, * represents a bond that binds to Y 101 in formula (b-1).

[0287] R 101 Examples of the substituent in the cyclic group of include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. As the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred. As the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferred. As the halogen atom as a substituent, a fluorine atom, a bromine atom, or an iodine atom is preferable. As the halogenated alkyl group as a substituent, there may be mentioned groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc., are substituted with the above halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) constituting a cyclic hydrocarbon group.

[0288] R 101 The cyclic hydrocarbon group in may be a condensed cyclic group including a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include those in which one or more aromatic rings are condensed to a polycycloalkane having a bridged ring system polycyclic skeleton. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed cyclic group, a group including a condensed ring in which two or three aromatic rings are condensed to a bicycloalkane is preferable, and a group including a condensed ring in which two or three aromatic rings are condensed to bicyclo[2.2.2]octane is more preferable. R 101 Specific examples of the condensed cyclic group in include those represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents a bond that binds to Y in formula (b-1). 101 represents a bond that binds to Y in formula (b-1).

[0289]

Chemical formula

[0290] R 101 Examples of the substituent that the condensed cyclic group in may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, etc. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the condensed cyclic group are as described above for R 101Those similar to those listed as the substituents of the cyclic group in [are listed]. Examples of the aromatic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from an aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), etc. Examples of the alicyclic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane and cyclohexane; a group obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane 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), etc.

[0291] A chain alkyl group which may have a substituent: R 101 The chain alkyl group of [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-chain 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, for example, 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, 4-methylpentyl group, etc. can be mentioned.

[0292] A chain alkenyl group which may have a substituent: R 101 As the chain alkenyl group of, it may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, still more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butenyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like. Among the above, as the chain alkenyl group, a linear alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0293] R 101 Examples of the substituent in the chain alkyl group or alkenyl group of include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in the above R 101 and the like.

[0294] In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 When is a divalent linking group containing an oxygen atom, the Y 101 may contain atoms other than the oxygen atom. Examples of the atoms other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom and the like. Examples of the divalent linking group containing an oxygen atom include the linking groups respectively represented by the above general formulas (y-al-1) to (y-al-8).

[0295] In formula (b-1), V 101 is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and the fluorinated alkylene group in V 101 preferably have 1 to 4 carbon atoms. Among them, V 101is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0296] In formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

[0297] Specific examples of the anion moiety represented by the formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) can be mentioned.

[0298]

Chemical formula

[0299] R” 101 、R” 102 and R” 103 The aliphatic cyclic group which may have substituents of 101 is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in R 101 in the formula (b-1). Examples of the substituent include the same substituents as those which may substitute the cyclic aliphatic hydrocarbon group in R 101 in the formula (b-1).

[0300] R” 101 and R” 103 The aromatic cyclic group which may have substituents of 101 is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R 101 in the formula (b-1). Examples of the substituent include the same substituents as those which may substitute the aromatic hydrocarbon group in R 101 in the formula (b-1).

[0301] R” 101 The linear alkyl group which may have substituents of 101 is preferably a group exemplified as the linear alkyl group in R 101 in the formula (b-1). R” 103 The linear alkenyl group which may have substituents of 101 is preferably a group exemplified as the linear alkenyl group in R 101 in the formula (b-1).

[0302] · Anion in the component (b-2) In the formula (b-2), R 104 , R 105 are each 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 is R 101 in the formula (b-1) respectively.However, R 104 , R 105 may be bonded to each other to form a ring. R 104 , R 105 is preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. 104 , R 105 The number of carbon atoms in the chain alkyl group of R is preferably as small as possible within the above range of carbon atoms, for reasons such as good solubility in a resist solvent. 104 , R 105 In the chain alkyl group, the more hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes, and the more the transparency to high-energy light of 250 nm or less and electron beams improves, which is preferable. The ratio of fluorine atoms in the chain alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 each independently represents a single bond, an alkylene group, or a fluorinated alkylene group, and each represents V in formula (b-1). 101 The same can be mentioned. In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0303] Anion in component (b-3) In formula (b-3), R 106 ~R 108 each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each represents R 101The same ones can be mentioned. In formula (b-3), L 103 ~L 105 is each independently a single bond, -CO- or -SO2-.

[0304] Among the above, as the anion part of the component (B), the anion in the component (b-1) is preferable.

[0305] {Cation part} In the above formulas (b-1), (b-2), and (b-3), M' m+ represents an m-valent onium cation. Among these, a sulfonium cation and an iodonium cation are preferable. m is an integer of 1 or more.

[0306] Preferred cation parts ((M' m+ )) 1 / m ) are preferably the same as the cations respectively represented by the above general formulas (ca-1) to (ca-3). The cation represented by the general formula (ca-1) is more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are even more preferable.

[0307] In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more. When the resist composition contains the component (B), in the resist composition, the content of the component (B) is preferably less than 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the component (A). By setting the content of the component (B) within the above preferable range, pattern formation can be sufficiently performed. In addition, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability as a resist composition is good, which is preferable.

[0308] ≪Base component (D) (excluding the component (D0))≫ In addition to the component (D0), the resist composition of the present embodiment may contain a base component (hereinafter also referred to as "(D) component (excluding the component (D0))") that traps the acid generated by exposure (that is, controls the diffusion of the acid). The (D) component (excluding the component (D0)) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition.

[0309] Examples of the (D) component other than the component (D0) include a photo-dissociable base (D1) that decomposes upon exposure and loses acid diffusion controllability (hereinafter referred to as "(D1) component"), and a nitrogen-containing organic compound (D2) that does not correspond to the (D1) component (hereinafter referred to as "(D2) component"). Among these, the photo-dissociable base ((D1) component) is preferred because it is easy to enhance high sensitivity, in-plane uniformity of pattern dimensions (CDU), fine resolution, etc. The compounds exemplified as the (D1) component described later may be used as the above-mentioned acid generator component ((B) component) in combination with other compounds in some cases.

[0310] ·Regarding the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability. One or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component") are preferred. The (d1-1) to (d1-3) components do not act as a quencher because they decompose in the exposed portion of the resist film and lose acid diffusion controllability (basicity), and act as a quencher in the unexposed portion of the resist film.

[0311] [Chemical formula] [In the formula, Rd 1 ~Rd 4is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. However, Rd in formula (d1-2) 2 is such that a fluorine atom is not bonded to the carbon atom adjacent to the S atom in 1 Yd is a single bond or a divalent linking group. m is an integer of 1 or more, and M m+ are each independently an m-valent cation. ]

[0312] {(d1-1) component} ·· Anion part In formula (d1-1), Rd 1 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof are the same as those of the above R’ 201 . Among these, as Rd 1 , a cyclic aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkyl group which may have a substituent is preferable. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by the above general formulas (a2-r-1) to (a2-r-8), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is included as a substituent, it may be via an alkylene group, and in this case, the linking group represented by the above formulas (y-al-1) to (y-al-5) is preferable as the substituent. In addition, when the cyclic aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 has a linking group represented by the above general formulas (y-al-1) to (y-al-7) as a substituent, in the above general formulas (y-al-1) to (y-al-7), the V’ 1 in the above general formulas (y-al-1) to (y-al-7) is bonded to the carbon atom constituting the cyclic aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 101 in formula (d3-1). Examples of the aromatic hydrocarbon group preferably include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and another ring structure). Examples of the alicyclic group preferably include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, or tetracyclododecane. The linear alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; branched-chain alkyl groups such as 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.

[0313] When the linear alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the fluorinated alkyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. The fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of the atoms other than fluorine atoms include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0314] Preferred specific examples of the anionic part of the component (d1-1) are shown below.

[0315]

Chemical formula

[0316] ···Cationic part In formula (d1-1), M m+ is an m-valent cation. M m+As the cation, those similar to the cations respectively represented by the general formulas (ca-1) to (ca-3) are preferably exemplified, the cation represented by the general formula (ca-1) is more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are even more preferable. The component (d1-1) may be used alone or in combination of two or more.

[0317] {(d1-2) component} ·· Anion part In the formula (d1-2), Rd 2 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and those similar to the above R’ 201 are exemplified. However, it is assumed that a fluorine atom is not bonded (not fluorine-substituted) to the carbon atom adjacent to the S atom in Rd 2 . Thereby, the anion of the component (d1-2) becomes an appropriate weak acid anion, and the quenching ability as the component (D) is improved. Rd 2 is preferably a chain alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.

[0318] The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. from which one or more hydrogen atoms have been removed (which may have a substituent); and more preferably a group from which one or more hydrogen atoms have been removed from camphor.

[0319] The hydrocarbon group of Rd 2 may have a substituent, and as the substituent, Rd of the formula (d1-1) 1Examples of the substituents that the hydrocarbon group (aromatic hydrocarbon group, alicyclic group, or linear alkyl group) may have are the same as those described above.

[0320] Preferred specific examples of the anionic part of the component (d1-2) are shown below.

[0321] [Chemical formula]

[0322] ···Cationic part In formula (d1-2), M m+ is an m-valent cation, which is the same as M m+ in the formula (d1-1). The component (d1-2) may be used alone or in combination of two or more.

[0323] {(d1-3) component} ···Anionic part In formula (d1-3), Rd 3 is an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group, and examples thereof are the same as those of R’ 201 , and it is preferably a cyclic group, a linear alkyl group, or a linear alkenyl group containing a fluorine atom. Among them, a fluorinated alkyl group is preferred, and those similar to the fluorinated alkyl group of Rd 1 are more preferred.

[0324] In formula (d1-3), Rd 4 is an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group, and examples thereof are the same as those of R’ 201 . Among them, it is preferably an optionally substituted alkyl group, alkoxy group, alkenyl group, or cyclic group. Rd 4The alkyl group in 4 may have a part of the hydrogen atoms of the alkyl group substituted with a hydroxyl group, a cyano group or the like. Rd 4 The alkoxy group in

[0325] Rd 4 The alkenyl group in 201 is the same as the alkenyl group in the above R’

[0326] Rd 4 The cyclic group in 201 is the same as the cyclic group in the above R’ 2,6 and preferably includes an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 4 decane, tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group. Rd 4 When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in good lithography characteristics. Also, Rd

[0327] In formula (d1-3), Yd1 is a single bond or a divalent linking group. Yd 1 The divalent linking group in is not particularly limited, and examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, a divalent linking group containing a heteroatom, and the like. Each of these is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom, which were mentioned in the description of the divalent linking group in Ya in the above formula (a2-1). 21 Examples thereof include the same ones as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom, which were mentioned in the description of the divalent linking group in. Yd 1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0328] Specific preferred examples of the anionic part of the component (d1-3) are shown below.

[0329]

Chemical formula

[0330]

Chemical formula

[0331] ···Cationic part In the formula (d1-3), M m+ is an m-valent cation, which is the same as M in the above formula (d1-1). m+ and (d1-3) component may be used alone or in combination of two or more.

[0332] (D1) component may use only any one of the above (d1-1) to (d1-3) components, or may use two or more in combination. When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[0333] The component (D1) preferably contains the component (d1-1). Among the whole component (D1), the content of the component (d1-1) is preferably 50% by mass or more, preferably 70% by mass or more, still more preferably 90% by mass or more, and the component (D1) may consist only of the compound (d1-1) component.

[0334] Manufacturing method of the component (D1): The manufacturing methods of the above-mentioned components (d1-1) and (d1-2) are not particularly limited and can be manufactured by known methods. In addition, the manufacturing method of the component (d1-3) is not particularly limited and is manufactured, for example, in the same manner as the method described in US2012-0149916 Gazette.

[0335] ·Regarding the component (D2) As the component (D), a nitrogen-containing organic compound component that does not correspond to the above-mentioned component (D1) (hereinafter referred to as the "component (D2)") may be contained. The component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not correspond to the component (D1), and any known one can be arbitrarily used. Among them, aliphatic amines are preferable, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferable. An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. Examples of the aliphatic amine include amines (alkylamines or alkyl alcohol amines) or cyclic amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or a 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 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

[0336] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. As for aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specific 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.

[0337] Examples of 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., and triethanolamine triacetate is preferred.

[0338] Also, as the component (D2), an aromatic amine may be used. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, 2,6-di-tert-butylpyridine, etc.

[0339] The component (D2) may be used alone or in combination of two or more. When the resist composition contains the component (D2), in the resist composition, the content of the component (D2) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting the range as above, the resist pattern shape, standing time stability, etc. are improved.

[0340] Among the whole component (D), the proportion of the component (D0) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 95% by mass or more. The proportion of the component (D0) in the whole component (D) may be 100% by mass.

[0341] ≪At least one compound (E) selected from the group consisting of organic carboxylic acids, oxoacids of phosphorus and their derivatives≫ In the resist composition of the present embodiment, for the purpose of preventing sensitivity deterioration and improving resist pattern shape, standing stability over time, etc., as optional components, an organic carboxylic acid and at least one compound (E) selected from the group consisting of oxo acids of phosphorus and their derivatives (hereinafter referred to as "(E) component") can be contained. Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. Among them, salicylic acid is preferred. Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid, etc. Among them, phosphonic acid is particularly preferred.

[0342] In the resist composition of the present embodiment, the (E) component may be used alone or in combination of two or more. When the resist composition contains the (E) component, the content of the (E) component is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the (A) component. By setting the content within the above range, lithography characteristics can be further improved.

[0343] ≪Fluorine additive component (F)≫ The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "(F) component") as a hydrophobic resin. The (F) component is used to impart water repellency to the resist film, and by using it as a resin different from the (A) component, lithography characteristics can be improved. As the (F) component, for example, fluorine-containing polymer compounds described in JP-A Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 can be used. (F) More specifically as the component, a polymer having a structural unit (f1) represented by the following general formula (f1-1) can be mentioned. As this polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1); a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1) is preferable, and a copolymer of the structural unit (f1) and the structural unit (a1) is more preferable. Here, as the structural unit (a1) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate and a structural unit derived from 1-methyl-1-adamantyl (meth) acrylate are preferable, and a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate is more preferable.

[0344]

Chemical formula

[0345] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as above. As R, a hydrogen atom or a methyl group is preferable. In formula (f1-1), Rf 102 and Rf 103 As the halogen atom, a fluorine atom is preferable. Rf 102 and Rf 103 As the alkyl group having 1 to 5 carbon atoms, the same ones as the alkyl group having 1 to 5 carbon atoms of the above R can be mentioned, and a methyl group or an ethyl group is preferable. Rf 102 and Rf103 As the alkyl halide group having 1 to 5 carbon atoms, specifically, a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms can be mentioned. As the halogen atom, a fluorine atom is preferable. Among them, Rf 102 and Rf 103 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom. In formula (f1-1), nf 1 is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

[0346] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, and particularly preferably having 1 to 10 carbon atoms. Further, in the hydrocarbon group containing a fluorine atom, 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 preferably 60% or more are fluorinated because the hydrophobicity of the resist film during immersion exposure increases. Among them, as Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF2-CF3.

[0347] (F) component's weight average molecular weight (Mw) (in terms of polystyrene conversion standard by gel permeation chromatography) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 10,000 to 30,000. When it is below the upper limit value of this range, there is sufficient solubility in the resist solvent for use as a resist, and when it is above the lower limit value of this range, the water repellency of the resist film is good. (F) component's dispersity (Mw / Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.

[0348] In the resist composition of this embodiment, the (F) component may be used alone or in combination of two or more. When the resist composition contains the (F) component, the content of the (F) component is preferably from 0.5 to 10 parts by mass, more preferably from 1 to 10 parts by mass, based on 100 parts by mass of the (A) component.

[0349] ≪Organic solvent component (S)≫ The resist composition of this embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component"). In the resist composition of this embodiment, the (S) component may be used alone or as a mixed solvent of two or more. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0350] Also, as the (S) component, a mixed solvent of PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent. 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, as the mixing ratio, the mass ratio of the former to the latter is preferably from 70:30 to 95:5. (S) The amount used is not particularly limited and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. Generally, the (S) component 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.

[0351] For the resist composition of this embodiment, after dissolving the above resist material in the (S) component, impurities and the like may be removed using a polyimide porous membrane, a polyamideimide porous membrane, or the like. For example, filtration of the resist composition may be performed using a filter made of a polyimide porous membrane, a filter made of a polyamideimide porous membrane, a filter made of a polyimide porous membrane and a polyamideimide porous membrane, or the like. Examples of the polyimide porous membrane and the polyamideimide porous membrane include those described in JP-A-2016-155121.

[0352] The resist composition of this embodiment described above contains a compound (D0) ((D0) component) represented by the general formula (d0). The anion part of the (D0) component is an aromatic ring (R 02 -O-R 01 -O-) containing a halogen atom and an acetal group (a group represented by ar ). This (D0) component has an aromatic ring (R ar ) containing a halogen atom, so it has excellent light absorption efficiency in exposure such as EUV, and also has a large molecular size, enhancing the effect of suppressing acid diffusion generated by exposure. In addition, the anion part of this (D0) component further has an acetal group on the aromatic ring (R ar ) containing a halogen atom, so the hydrophilicity does not become too high, and when forming a resist pattern, an interaction easily occurs between the acetal group bonded to the aromatic ring (R ar ) and the acid generated by exposure in the resist film. Due to these synergistic effects, in the formation of a resist pattern, the diffusion of the acid generated by exposure is further suppressed in the resist composition of this embodiment. Therefore, according to the resist composition of the present embodiment, in the formation of a resist pattern, it has high sensitivity and improved lithography characteristics such as the uniformity of pattern dimensions.

[0353] (Resist Pattern Forming Method) The resist pattern forming method according to the second aspect of the present invention includes a step of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern. As an embodiment of such a resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

[0354] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film. Next, selective exposure is performed on the resist film, for example, by exposure through a mask (mask pattern) having a predetermined pattern formed thereon or by direct irradiation with an electron beam without passing through a mask pattern using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus. After that, a baking (post-exposure bake (PEB)) treatment is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds. Next, the resist film is developed. In the case of an alkali development process, an alkali developer is used, and in the case of a solvent development process, a developer containing an organic solvent (organic-based developer) is used.

[0355] After the development process, preferably a rinsing process is performed. In the case of an alkali development process, water rinsing using pure water is preferred, and in the case of a solvent development process, it is preferable to use a rinsing solution containing an organic solvent. In the case of a solvent development process, after the development process or the rinse process, a process of removing the developer or the rinse solution adhering to the pattern with a supercritical fluid may be performed. After the development process or the rinse process, drying is performed. In some cases, a baking process (post-bake) may be performed after the development process.

[0356] The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for electronic components, or a substrate on which a predetermined wiring pattern is formed, etc. can be mentioned. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, aluminum, or a glass substrate, etc. can be mentioned. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0357] The wavelength used for exposure is not particularly limited, and exposure can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The resist pattern forming method of the present embodiment is a method useful in the form of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam) in the step of exposing the resist film.

[0358] The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion exposure (Liquid Immersion Lithography). Liquid immersion exposure is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is filled with a solvent (liquid immersion medium) having a refractive index larger than that of air in advance, and exposure (immersion exposure) is performed in that state. As the liquid immersion medium, a solvent having a refractive index larger than that of air and smaller than that of the resist film to be exposed is preferable. For example, water, a fluorine-based inert liquid, a silicon-based solvent, a hydrocarbon-based solvent, etc. can be mentioned. Among these, water is preferably used as the liquid immersion medium.

[0359] As the alkaline developer used for development in the alkaline development process, for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) can be mentioned. As the organic solvent contained in the organic developer used for development in the solvent development process, any one can be used as long as it can dissolve the component (A) (component (A) before exposure), and it can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents can be mentioned.

[0360] Examples of the ester solvent 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.

[0361] Examples of the nitrile solvent include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like.

[0362] Known additives can be blended into the organic developer as necessary. Examples of the additive include surfactants.

[0363] The development process can be carried out by known development methods. For example, a method of immersing the support in a developer for a certain period of time (dip method), a method of raising the developer on the support surface by surface tension and allowing it to stand still for a certain period of time (paddle method), a method of spraying the developer on the support surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dispense method), etc. can be mentioned.

[0364] As the organic solvent contained in the rinse liquid used for the rinse treatment after the development process in the solvent development process, for example, among the organic solvents mentioned as the organic solvents used for the organic developer, those that are difficult to dissolve the resist pattern can be appropriately selected and used. Usually, 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 alone or in combination of two or more. Also, they may be used in mixture with organic solvents other than the above and water.

[0365] The rinse treatment (cleaning treatment) using the rinse liquid can be carried out by known rinse methods. Examples of the method of this rinse treatment include a method of continuously discharging the rinse liquid on a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid on the support surface (spray method), etc.

[0366] According to the resist pattern forming method of the present embodiment described above, since the above-described resist composition is used, high sensitivity can be achieved when forming the resist pattern, and a resist pattern with good shape can be formed with lithography characteristics such as dimensional uniformity enhanced.

[0367] In the resist composition of the above-described embodiment and various materials used in the resist pattern forming method of the above-described embodiment (for example, resist solvents, developers, rinse liquids, compositions for forming antireflection films, compositions for forming top coats, etc.), it is preferable that they do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, components containing sulfur atoms or phosphorus atoms, etc. Here, 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. As the content of impurities contained in these materials, 200 ppb or less is preferable, 1 ppb or less is more preferable, 100 ppt (parts per trillion) or less is even more preferable, 10 ppt or less is particularly preferable, and it is most preferable that they are substantially not contained (below the detection limit of the measuring device).

[0368] (Compound represented by general formula (d0)) The compound according to the third aspect of the present invention is a compound (compound (D0')) represented by the following general formula (d0').

[0369] [Chemical formula] [In the formula, R ar is an aromatic ring which may have a substituent. R 01 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R 02 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R 03 is a halogen atom. j is an integer of 1 or more as long as the valence permits. When j is an integer of 2 or more, a plurality of groups represented by R 02 -O-R 01 -O- may be the same or different from each other. k is an integer of 1 or more as long as the valence permits. When k is an integer of 2 or more, a plurality of R 03 may be the same or different from each other. Y d0 is a divalent linking group or a single bond. X + represents a counter cation.]

[0370] The compound represented by the above general formula (d0’) (compound (D0’)) has the same anion part as the (D0’) component in the resist composition according to the first aspect of the present invention described above, and the cation part is a counter cation, and examples thereof include an organic cation or a metal cation. X + Examples of the organic cation in X include, for example, an organic ammonium cation and an onium cation, and preferably include a primary to quaternary ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, and an iodonium cation. X + Examples of the metal cation in X include an alkali metal ion, an alkaline earth metal ion, a rubidium ion, a strontium ion, a yttrium ion, and the like.

[0371] As the compound of this embodiment, a compound represented by the following general formula (d0’-0) is preferably mentioned.

[0372] [Chemical formula] [In the formula, n is an integer of 0 to 2. R 01 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R 02 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R 030 is a halogen atom. j0 is an integer of 1 to 8. When j0 is an integer of 2 or more, a plurality of R 02 -O-R 01 -O- groups represented may be the same or different from each other. k0 is an integer of 1 to 8. When k0 is an integer of 2 or more, a plurality of R 030 may be the same or different from each other. However, 2 ≦ j0 + k0 ≦ 5 + 2 × n. m is an integer of 1 or more, and X + represents a counter cation.]

[0373] The compound represented by the above general formula (d0’-0) (compound (D0’-0)) has the same anion part as the compound (D0-0) in the resist composition according to the first aspect of the present invention described above, and the cation part is X in the above formula (d0’). + is the same as. Specific examples of the compound of this embodiment include compounds in which the anion part is an anion represented by the above chemical formulas (d0-an-1) to (d0-an-13), respectively.

[0374] Specific examples of the compound of this embodiment further preferably include compounds represented by the above chemical formulas (D0-1) to (D0-17), respectively.

[0375] [Method for producing the compound represented by the general formula (d0’)] (The component (D0’) can be produced using a known production method. As an embodiment of the production method of the component (D0’), a production method including the following first to third steps can be mentioned.

[0376] First step: In the first step, as raw materials corresponding to the target compound, a compound (d0’-10) represented by the following general formula (d0’-10) and a compound (S0-10) represented by the following general formula (S0-10) are reacted to obtain a compound (D0’pre-1) represented by the following general formula (d0’pre-1) as an intermediate for the target compound.

[0377] [Chemical formula] [In the formula, R ar is an aromatic ring which may have a substituent. R 01 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R 02 is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R 03 is a halogen atom. j is an integer of 1 or more as long as the valence permits. When j is an integer of 2 or more, a plurality of R 02 -O-R 01The groups represented by -O- may be the same or different from each other. k is an integer of 1 or more as long as the valence permits. When k is an integer of 2 or more, a plurality of R 03 may be the same or different from each other. Y d0 is a divalent linking group or a single bond. R 04 is a halide having an alkoxy group.]

[0378] In the formula (d0'-10), R ar , R 01 ~R 03 , j, k and Y d0 are the same as the explanations for R ar , R 01 ~R 03 , j, k and Y d0 in the formula (d0). In the formula (S0-10), as the alkoxy group in R 04 , an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group are more preferable, and a methoxy group and an ethoxy group are even more preferable. In the formula (S0-10), as the halide in R 04 , fluoride, chloride, bromide, iodide are preferable, and chloride is more preferable.

[0379] In the first step, as the solvent used for the reaction of the compound (d0'-10) and the compound (S0-10), for example, dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide and the like can be mentioned. In the first step, the reaction temperature is, for example, 0 to 50 °C, and the reaction time is, for example, 10 minutes or more and 24 hours or less.

[0380] Second step: In the second step, by reacting the compound (D0’pre-1) represented by the following general formula (d0’pre-1) with sodium hydroxide, the compound (D0’pre-2) represented by the following general formula (d0’pre-2) is obtained as an intermediate for the target compound.

[0381]

Chemical formula

[0382] In the second step, examples of the solvent used for the reaction between the compound (D0’pre-1) and the compound (S0-10) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N’-dimethylacetamide, dimethyl sulfoxide, and the like. In the second step, the reaction temperature is, for example, 0 to 50 °C, and the reaction time is, for example, 10 minutes or more and 24 hours or less.

[0383] Third step: In the third step, the compound (D0’pre-2) is reacted with the salt-exchanging compound (S0) represented by the following general formula (S0) to obtain the target compound (D0’) represented by the following general formula (d0’).

[0384]

Chemical formula

[0385] In the above formula (S0), X + is a counter cation, and examples include organic cations. Examples of the organic cation in X+ include organic ammonium cations and onium cations, and preferably include primary to quaternary ammonium cations, pyridinium cations, sulfonium cations, phosphonium cations, and iodonium cations. X - Examples of the counter anion in include halogen ions such as bromide ions and chloride ions; BF4 - , AsF6 - , SbF6 - , PF6 - , ClO4 - and the like. Among these, X - preferably has a halogen ion, and more preferably a bromide ion (Br - ).

[0386] In the third step, the reaction between the compound (D0pre-2) and the compound (S0) is carried out in a solvent such as water, dichloromethane, acetonitrile, or chloroform. The solvent here may be an organic solvent or a mixed solvent of an organic solvent and water. Examples of the organic solvent include ketone solvents such as cyclohexanone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether, t-butyl methyl ether, and diisopropyl ether; halogen solvents such as tetrahydrofuran, 1,3-dioxolane, dichloromethane, 1,2-dichloroethane, and chloroform; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, propionitrile, acetonitrile, or a mixed solvent thereof. In the third step, the reaction temperature is, for example, 0 to 100°C, and the reaction time is, for example, 10 minutes or more and 24 hours or less.

[0387] After the salt exchange reaction is completed, the compound in the reaction solution may be isolated and purified. For isolation and purification, conventionally known methods can be used. For example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be appropriately combined and used. The structure of the compound obtained as described above is 1H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19 It can be identified by general organic analytical methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystallography. As the raw materials, reagents, etc. used in each step, commercially available ones may be used, or synthesized ones may be used.

[0388] The compound of the present embodiment described above is a compound suitable as a base component for a resist composition according to the first aspect of the present invention described above. Further, the compound of the present embodiment can be used as an acid diffusion controller according to the fourth aspect described later.

[0389] (Acid diffusion controller) The acid diffusion controller according to the fourth aspect of the present invention contains the compounds (compound (D0'), compound (D0'-0)) according to the third aspect described above. The acid diffusion controller of the present embodiment is particularly suitable as a base component for a resist composition according to the first aspect described above. Such an acid diffusion controller is useful as an acid diffusion controller for a chemically amplified resist composition. Since the compounds according to the third aspect described above each have a halogen atom and an acetal group in the anion part, they cause an ion exchange reaction with the acid generated from the acid generator component and exhibit a quenching effect. By using such an acid diffusion controller in a chemically amplified resist composition, lithography characteristics such as sensitivity and pattern dimension uniformity are further improved in resist pattern formation. By using such an acid diffusion controller, in particular, in resist pattern formation using an EB or EUV light source, lithography characteristics such as sensitivity and pattern dimension uniformity are further improved.

Examples

[0390] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples.

[0391] <Production Example of Compound> [Production Example 1: Synthesis of Compound (D0-1)] 25.0 g of compound (d0-1-1), 20.8 g of 2-chloroethyl methyl ether, 20.5 g of potassium carbonate, and 250 g of N,N-dimethylformamide were placed in a three-necked flask and reacted at room temperature for 5 hours. Then, 250 g of dichloromethane and 250 g of ultrapure water were added for extraction, and the aqueous layer was removed. Thereafter, the organic layer was washed 3 times with 250 g of ultrapure water. The organic layer was concentrated to dryness using a rotary evaporator to obtain compound (d0-1-2) (34.3 g).

[0392] 30.0 g of compound (d0-1-2), 120 g of tetrahydrofuran, and 120 g of 5% aqueous sodium hydroxide solution were placed in a three-necked flask, stirred at room temperature for 2 hours, and then the aqueous layer was removed. Then, 200 g of 3% aqueous hydrochloric acid solution was added and stirred for 2 hours, followed by extraction with 200 g of dichloromethane, and the aqueous layer was removed. Thereafter, the organic layer was washed 3 times with 200 g of ultrapure water. The organic layer was concentrated to dryness using a rotary evaporator to obtain compound (d0-1-3) (24.2 g).

[0393]

Chemical Structure

[0394] 20.0 g of compound (d0-1-3), 25.5 g of sulfonium salt (S-1), 100 g of dichloromethane, and 120 g of 5% aqueous tetramethylammonium hydroxide (TMAH) solution were placed in a three-necked flask and reacted at room temperature for 30 minutes. After completion of the reaction, the aqueous layer was removed, and the organic layer was washed 5 times with 100 g of ultrapure water. This organic layer was concentrated to dryness using a rotary evaporator to obtain compound (D0-1) (32.8 g).

Chemical Structure

[0395] NMR measurement was performed on the obtained compound (D0-1), and its structure was identified from the following results. 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.74 - 7.90 (m, 15H), 7.25 - 7.64 (m, 3H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0396] [Production Example 2: Synthesis of Compound (D0-2)] The target compound (D0-2) was obtained in the same manner as in Production Example 1, except that the following compound (d0-2-1) was used instead of compound (d0-1-1).

[0397]

Chemical Structure

[0398] NMR measurement was performed on the obtained compound (D0-2), and its structure was identified from the following results. 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.05 - 8.19 (m, 2H), 7.74 - 7.90 (m, 15H), 6.92 (d, 1H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0399] [Production Example 3: Synthesis of Compound (D0-3)] The target compound (D0-3) was obtained in the same manner as in Production Example 1, except that the following compound (d0-3-1) was used instead of compound (d0-1-1).

[0400]

Chemical Structure

[0401] NMR measurement was performed on the obtained compound (D0-3), and its structure was identified from the following results. 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.74 - 7.90 (m, 15H), 7.53 - 7.64 (m, 3H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0402] [Production Example 4: Synthesis of Compound (D0-4)] The target compound (D0-4) was obtained in the same manner as in Production Example 1, except that the following compound (d0-4-1) was used instead of compound (d0-1-1).

[0403] [Chemical Formula]

[0404] NMR measurement was performed on the obtained compound (D0-4), and its structure was identified from the following results. 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.03 - 8.05 (m, 1H), 7.74 - 7.90 (m, 16H), 6.97 - 6.99 (m, 1H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0405] [Production Example 5: Synthesis of Compound (D0-5)] The target compound (D0-5) was obtained in the same manner as in Production Example 1, except that the following compound (d0-5-1) was used instead of compound (d0-1-1).

[0406] [Chemical Formula]

[0407] NMR measurement was performed on the obtained compound (D0-5), and its structure was identified from the following results. 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.72 - 7.90 (m, 16H), 7.03 - 7.07 (m, 2H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0408] [Production Example 6: Synthesis of Compound (D0-6)] The target compound (D0-6) was obtained in the same manner as in Production Example 1, except that the following compound (d0-6-1) was used instead of compound (d0-1-1).

[0409]

Chemical Formula

[0410] NMR measurement was performed on the obtained compound (D0-6), and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.74 - 7.96 (m, 16H), 7.12 - 7.30 (m, 2H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0411] [Production Example 7: Synthesis of Compound (D0-7)] The target compound (D0-7) was obtained in the same manner as in Production Example 1, except that the following compound (d0-7-1) was used instead of compound (d0-1-1).

[0412]

Chemical Formula

[0413] NMR measurement was performed on the obtained compound (D0-7), and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.19 (d, H), 7.74 - 7.90 (m, 16H), 6.92 - 6.99 (m, 1H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0414] [Production Example 8: Synthesis of Compound (D0-8)] The target compound (D0-8) was obtained in the same manner as in Production Example 1, except that the following compound (d0-8-1) was used instead of the compound (d0-1-1).

[0415] [Chemical Formula]

[0416] NMR measurement was performed on the obtained compound (D0-8), and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.18 - 8.30 (m, 2H), 7.74 - 7.90 (m, 15H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0417] [Production Example 9: Synthesis of Compound (D0-9)] The target compound (D0-9) was obtained in the same manner as in Production Example 1, except that the following compound (d0-9-1) was used instead of the compound (d0-1-1).

[0418] [Chemical Formula]

[0419] NMR measurement was performed on the obtained compound (D0-9), and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.07 (s, 1H), 7.74 - 7.90 (m, 15H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0420] [Production Example 10: Synthesis of Compound (D0-10)] The target compound (D0-10) was obtained in the same manner as in Production Example 1, except that chloromethyl methyl ether was used instead of 2-chloroethyl methyl ether.

[0421] [Chemical Formula]

[0422] For the obtained compound (D0-10), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.64 - 7.90 (m, 16H), 7.25 - 7.40 (m, 2H), 6.02 (s, 2H), 3.30 (s, 3H)

[0423] [Production Example 11: Synthesis of Compound (D0-11)] The target compound (D0-11) was obtained in the same manner as in Production Example 1 except that 2-chloroethyl ethyl ether was used instead of 2-chloroethyl methyl ether.

[0424] [Chemical formula]

[0425] For the obtained compound (D0-11), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.64 - 7.90 (m, 16H), 7.25 - 7.40 (m, 2H), 4.31 (t, 2H), 3.77 - 3.85 (m, 2H), 3.46 - 3.51 (m, 2H), 1.05 - 1.12 (m, 3H)

[0426] [Production Example 12: Synthesis of Compound (D0-12)] The target compound (D0-12) was obtained in the same manner as in Production Example 1 except that the following compound (d0-12-1) was used instead of compound (d0-1-1).

[0427] [Chemical formula]

[0428] For the obtained compound (D0-12), NMR measurement was carried out and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.22 (d, 1H), 7.74 - 7.90 (m, 15H), 7.40 (d, 1H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0429] [Production Example 13: Synthesis of Compound (D0-13)] The target compound (D0-13) was obtained in the same manner as in Production Example 1, except that the following compound (d0-13-1) was used instead of compound (d0-1-1).

[0430]

Chemical formula

[0431] For the obtained compound (D0-13), NMR measurement was carried out and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 7.74 - 7.90 (m, 15H), 6.80 (s, 2H), 4.31 (t, 4H), 3.77 (t, 4H), 3.40 (s, 6H)

[0432] [Production Examples 14 to 17: Synthesis of Compounds (D0-14) to (D0-17)] The target compounds (D0-14), (D0-15), (D0-16), and (D0-17) were obtained in the same manner as in Production Example 8, except that the cation moiety in the sulfonium salt (S-1) was changed to the following sulfonium cations (S-ca-1), (S-ca-2), (S-ca-3), and (S-ca-4).

[0433]

Chemical formula

[0434] [Chemical formula]

[0435] For the obtained compound (D0-14), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.18 - 8.30 (m, 2H), 7.77 - 7.98 (m, 11H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0436] For the obtained compound (D0-15), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.18 - 8.30 (m, 2H), 7.25 - 7.64 (m, 12H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0437] For the obtained compound (D0-16), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.50 (d, 2H), 8.37 (d, 2H), 8.18 - 8.30 (m, 2H), 7.93 (t, 2H), 7.25 - 7.75 (m, 7H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0438] For the obtained compound (D0-17), NMR measurement was carried out, and its structure was identified from the following results. 1 1H-NMR (400 MHz, DMSO-d6): δ (ppm) = 8.18 - 8.30 (m, 2H), 6.75 - 6.81 (m, 9H), 4.31 (t, 2H), 3.77 (t, 2H), 3.40 (s, 3H)

[0439] <Preparation of resist composition> (Examples 1 to 23, Comparative Examples 1 to 6) The respective components shown in Tables 1 to 2 were mixed and dissolved to prepare the resist compositions of each example.

[0440]

Table 1

[0441]

Table 2

[0442] In Tables 1 to 2, each abbreviation has the following meaning respectively. The numerical values in [ ] are the blending amounts (parts by mass).

[0443] (A)-1: A polymer compound represented by the following chemical formula (A1)-1. Regarding the polymer compound (A1)-1, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5100, and the molecular weight dispersity (Mw / Mn) was 1.71. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 60 / 40.

[0444] (A)-2: A polymer compound represented by the following chemical formula (A1)-2. Regarding the polymer compound (A1)-2, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 4900, and the molecular weight dispersity (Mw / Mn) was 1.74. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 60 / 40.

[0445] (A)-3: A polymer compound represented by the following chemical formula (A1)-3. Regarding the polymer compound (A1)-3, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5200, and the molecular weight dispersity (Mw / Mn) was 1.72. 13The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0446] (A)-4: A polymer compound represented by the following chemical formula (A1)-4. Regarding the polymer compound (A1)-4, the weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 4800, and the molecular weight dispersity (Mw / Mn) was 1.68. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0447] (A)-5: A polymer compound represented by the following chemical formula (A1)-5. Regarding the polymer compound (A1)-5, the weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5100, and the molecular weight dispersity (Mw / Mn) was 1.70. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was l / m = 60 / 40.

[0448] (A)-6: A polymer compound represented by the following chemical formula (A1)-6. Regarding the polymer compound (A1)-6, the weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 12900, and the molecular weight dispersity (Mw / Mn) was 1.76. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was l / m / n = 50 / 35 / 15.

[0449]

Chemical formula

[0450] (B)-1: An acid generator composed of the following compound (B1-1). (B)-2: An acid generator composed of the following compound (B1-2).

[0451] [Chemical]

[0452] (D)-1: An acid diffusion controller composed of the above compound (D0-1). (D)-2: An acid diffusion controller composed of the above compound (D0-2). (D)-3: An acid diffusion controller composed of the above compound (D0-3). (D)-4: An acid diffusion controller composed of the above compound (D0-4). (D)-5: An acid diffusion controller composed of the above compound (D0-5). (D)-6: An acid diffusion controller composed of the above compound (D0-6). (D)-7: An acid diffusion controller composed of the above compound (D0-7). (D)-8: An acid diffusion controller composed of the above compound (D0-8). (D)-9: An acid diffusion controller composed of the above compound (D0-9). (D)-10: An acid diffusion controller composed of the above compound (D0-10). (D)-11: An acid diffusion controller composed of the above compound (D0-11). (D)-12: An acid diffusion controller composed of the above compound (D0-12). (D)-13: An acid diffusion controller composed of the above compound (D0-13). (D)-14: An acid diffusion controller composed of the above compound (D0-14). (D)-15: An acid diffusion controller composed of the above compound (D0-15). (D)-16: An acid diffusion controller composed of the above compound (D0-16). (D)-17: An acid diffusion controller composed of the above compound (D0-17).

[0453] (D)-18: An acid diffusion controller composed of the following compound (D1-1). (D)-19: An acid diffusion controller composed of the following compound (D1-2). (D)-20: An acid diffusion controller composed of the following compound (D1-3). (D)-21: An acid diffusion control agent comprising the following compound (D1-4). (D)-22: An acid diffusion control agent comprising the following compound (D1-5). (D)-23: An acid diffusion control agent comprising the following compound (D1-6).

[0454]

Chemical formula

[0455] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0456] <Formation of resist pattern> Step of forming a resist film: On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), the resist composition was applied using a spinner, and pre-baked (PAB) at a temperature of 110 °C for 60 seconds on a hot plate and dried to form a resist film with a thickness of 50 nm.

[0457] Step of exposing the resist film: Next, using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), drawing (exposure) was performed on the resist film at an acceleration voltage of 100 kV with a target size of a contact hole pattern (CH pattern) with a pitch width of 64 nm / hole diameter of 32 nm. Thereafter, post-exposure bake (PEB) treatment was performed at 100 °C for 60 seconds.

[0458] Step of developing the exposed resist film: Next, at 23 °C, alkali development was performed for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, water rinsing was performed for 15 seconds using pure water. As a result, a CH pattern with a pitch width of 64 nm / hole diameter of 32 nm was formed.

[0459] [Evaluation of Optimal Exposure Dose (Eop)] The optimal exposure dose Eop (μC / cm 2 ) at which the CH pattern of the target size is formed by the above <formation of resist pattern> was determined. The results are shown in Table 3 as "Eop (μC / cm 2 )".

[0460] [Evaluation of In-Plane Uniformity (CDU) of Pattern Dimensions] Regarding the CH pattern formed by the above <formation of resist pattern>, it was observed from above the CH pattern using a length-measuring SEM (scanning electron microscope, acceleration voltage 500 V, product name: CG5000, manufactured by Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. The same measurement was performed on 10 different CH patterns. Then, the triple value (3σ) of the standard deviation (σ) calculated from the measurement results was determined. The results are shown in Table 3 as "CDU (nm)". The 3σ obtained in this way means that the smaller the value, the higher the dimensional (CD) uniformity of the plurality of holes formed in the resist film.

[0461] [Table 3]

[0462] From the results shown in Table 3, it was confirmed that the resist compositions of Examples 1 to 23 to which the present invention was applied were highly sensitive and had good lithography characteristics such as the uniformity of pattern dimensions as compared with the resist compositions of Comparative Examples 1 to 6.

Claims

1. A resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, a base material component (A) whose solubility in a developer changes due to the action of the acid, a compound (D0) represented by the following general formula (d0), and contains the above, a resist composition. 【Chemical Formula 1】 [In the formula, R ａｒ is an aromatic ring which may have a substituent. R ０１ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R ０２ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R ０３ is a halogen atom. j is an integer of 1 or more as long as the valence permits. When j is an integer of 2 or more, a plurality of R ０２ -O-R ０１ -O- groups represented by may be the same or different from each other. k is an integer of 1 or more as long as the valence permits. When k is an integer of 2 or more, a plurality of R ０３ may be the same or different from each other. Y ｄ０ is a divalent linking group or a single bond. m is an integer of 1 or more, and M ｍ＋ represents an m-valent organic cation. ]

2. The resist composition according to claim 1, wherein the compound (D0) is a compound represented by the following general formula (d0-0). 【Chemical Formula 2】 [In the formula, n is an integer of 0 to 2. R ０１ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R ０２ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R ０３０ is a halogen atom. j0 is an integer of 1 to 8. When j0 is an integer of 2 or more, a plurality of R ０２ -O-R ０１The groups represented by -O- may be the same or different from each other. k0 is an integer of 1 to 8. When k0 is an integer of 2 or more, a plurality of R ０３０ may be the same or different from each other. However, 2 ≦ j0 + k0 ≦ 5 + 2×n. m is an integer of 1 or more, and M ｍ＋ represents an m-valent organic cation. ]

3. Furthermore, a resist composition according to claim 1, which contains an acid generator component that generates an acid upon exposure (however, excluding the compound (D0)).

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

5. A compound represented by the following general formula (d0'). 【Chemical Formula 3】 [In the formula, R ａｒ is an aromatic ring which may have a substituent. R ０１ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R ０２ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R ０３ is a halogen atom. j is an integer of 1 or more as long as the valence allows. When j is an integer of 2 or more, a plurality of, R ０２ -O-R ０１ -O- represented groups may be the same or different from each other. k is an integer of 1 or more as long as the valence allows. When k is an integer of 2 or more, a plurality of R ０３ may be the same or different from each other. Y ｄ０ is a divalent linking group or a single bond. X ＋ represents a counter cation. ]

6. The compound according to claim 5, which is a compound represented by the following general formula (d0'-0). 【Chemical Formula 4】 [wherein, n is an integer of 0 to 2. R ０１ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms. R ０２ is a linear saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a hydrogen atom. R ０３０ is a halogen atom. j0 is an integer of 1 to 8. When j0 is an integer of 2 or more, a plurality of R ０２ -O-R ０１ -O- groups represented may be the same or different from each other. k0 is an integer of 1 to 8. When k0 is an integer of 2 or more, a plurality of R ０３０ may be the same or different from each other. However, 2 ≦ j0 + k0 ≦ 5 + 2×n. X ＋ represents a counter cation. ]

7. An acid diffusion controller containing the compound according to Claim 5 or 6.

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