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

Abstract

To provide a resist composition having enhanced effects of improved sensitivity, reduced roughness and suppressed film loss, a resist pattern formation method using the resist composition, a compound useful for the resist composition, and an acid generator containing the compound.SOLUTION: A resist composition contains a base material component (A) and an acid generator component (B). The acid generator component (B) contains a compound (B0) represented by general formula (b0). In the formula, Ar1 and Ar2 are aromatic rings. Rf is a trifluoromethyl group or a fluorine atom. L1 and L2 are divalent linking groups. Mm+ represents an m-valence organic cation. m is an integer of 1 or more.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 generator.

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). 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.

[0003] In a chemically amplified resist composition, generally, a resin having a plurality of structural units is used as the base material component in order to improve lithography characteristics and the like. As the acid generator, various types have been proposed so far. For example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, etc. are known.

[0004] In the formation of a resist pattern, the behavior of the acid generated from the acid generator component by exposure is regarded as one factor that greatly affects lithography characteristics. For example, Patent Document 1 discloses a resist composition that employs a sulfonium salt having a specific structure as an acid generator component that generates an acid upon exposure.

Prior Art Documents

Patent Documents

[0005] Patent Document 1 Japanese Patent Application Laid-Open No. 2022-191173 Summary of the Invention Problems to be Solved by the Invention

[0006] With the further progress of lithography technology and the increasing miniaturization of resist patterns, in lithography using, for example, EUV (extreme ultraviolet light) or EB (electron beam), formation of fine patterns with a size of several tens of nm is targeted. As the pattern dimension becomes smaller, higher sensitivity to the exposure light source and all lithography characteristics such as reduction of roughness are required. In addition, with the miniaturization of the resist pattern, during development, particularly in the unexposed portion of the resist film, excessive dissolution in the developer may cause development loss (film reduction), which may become a problem. However, in the conventional resist composition as described in Patent Document 1, further improvement is required in terms of these required characteristics.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition in which the effects of improving sensitivity, reducing roughness, and suppressing film reduction are all enhanced in resist pattern formation, a resist pattern forming method using the resist composition, a compound useful for the resist composition, and an acid generator containing the compound.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition in which the effects of improving sensitivity, reducing roughness, and suppressing film reduction are all enhanced in resist pattern formation, a resist pattern forming method using the resist composition, a compound useful for the resist composition, and an acid generator containing the compound. Means for Solving the Problems

[0009] The present invention includes the following aspects. A first aspect of the present invention is a resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, the resist composition containing a base material component (A) whose solubility in a developer changes due to the action of the acid and an acid generator component (B) that generates an acid upon exposure, wherein the acid generator component (B) includes a compound (B0) represented by the following general formula (b0).

[0010]

Chemical formula

[0011] A second aspect of the present invention is a resist pattern forming method having a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.

[0012] The third aspect of the present invention is a compound represented by the following general formula (b0).

[0013] [Chemical formula] [In the formula, Ar 1 and Ar 2 are each an aromatic ring. R b1 and R b2 are each a substituent other than an iodine atom. R f is a trifluoromethyl group or a fluorine atom. R b3 is a substituent other than a trifluoromethyl group and a fluorine atom. L 1 and L 2 are each a divalent linking group. nb1 and nb2 are each an integer of 1 or more as long as the valence allows. nb3 is an integer of 1 to 4. 3 ≤ nb1 + nb2. nr1 and nr2 are each an integer of 0 or more as long as the valence allows. nr3 is an integer of 0 to 3. When nb3 is an integer of 2 or more, a plurality of R f may be the same or different. When nr1 is an integer of 2 or more, a plurality of R b1 may be the same or different. When nr2 is an integer of 2 or more, a plurality of R b2 may be the same or different. When nr3 is an integer of 2 or more, a plurality of R b3 may be the same or different. M m+ represents an m-valent organic cation. m is an integer of 1 or more.]

[0014] The fourth aspect of the present invention is an acid generator containing the compound according to the third aspect. [Advantages of the Invention]

[0015] According to the present invention, the present invention has been made in view of the above circumstances, and in resist pattern formation, a resist composition in which the effects of improving sensitivity, reducing roughness, and suppressing film loss are all enhanced, a resist pattern formation method using the resist composition, a compound useful for the resist composition, and an acid generator containing the compound can be provided.

Mode for Carrying Out the Invention

[0016] In the present 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. The "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. The "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "structural 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 (-CH 2 -) is substituted with a divalent group. "Exposure" is a concept including all irradiations of radiation.

[0017] The "acid-decomposable group" is a group having acid-decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes 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 (-SO 3 H), 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 some bonds are cleaved by the action of an acid, further decarboxylation occurs, whereby 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 lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thus, when the acid-dissociable group is dissociated by the action of an acid, a polar group having higher polarity than the acid-dissociable group is generated, increasing the polarity. As a result, the polarity of the entire component (A1) increases. By increasing the 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 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 500 or more and less than 4000 are usually used. Hereinafter, when referring to a "low molecular compound", it means a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, when referring to a "resin", "high molecular compound" or "polymer", it means a polymer having a molecular weight of 1000 or more. The molecular weight of the polymer shall be the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography).

[0020] The "derived structural unit" means a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylic ester", the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. The substituent (Rαx ) is an atom or group other than a hydrogen atom. Also, the substituent (R αx ) is a diester of itaconic acid substituted with a substituent containing an ester bond, or an α-hydroxy acrylate ester in which the substituent (R αx ) is substituted with a hydroxyalkyl group or a group obtained by modifying its hydroxyl group. Note that, unless otherwise specified, the α-position carbon atom of the acrylate ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, an acrylate 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 acrylate 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, which may have the hydrogen atom at the α-position 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, which may have the hydrogen atom at the α-position substituted with a substituent, and the like. Note that, 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 those similar to R αx .

[0022] In this specification and the claims, depending on the structure represented by the chemical formula, there may be an asymmetric carbon, 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 changes its solubility in a developer by 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 by the action of an acid, and an acid generator component (B) (hereinafter also referred to as “component (B)”) that generates an acid upon exposure. The acid generator component (B) includes a compound (B0) represented by the general formula (b0) described later (hereinafter also referred to as “component (B0)”). In addition, the resist composition of the present embodiment may further contain other components in addition to the above-described components (A) and (B). Examples of the other components include the following component (D), component (E), component (F), component (S), etc.

[0024] In the resist composition of the present embodiment, component (A) may generate an acid upon exposure. In this case, component (A) becomes a “base material component that generates an acid upon exposure and whose solubility in a developer changes by 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 by the action of the acid, it is preferable that component (A1) described later is a resin that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, structural unit (a5) described later may be used.

[0025] The resist composition of the present embodiment may be a positive resist composition or a negative resist composition. Further, the resist composition of the present 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.

[0026] <Base material component (A)> In the resist composition of the present embodiment, it is preferable to use, as the component (A), a resin component (A1) (hereinafter also referred to as the "(A1) component") whose solubility in a developer changes by 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.

[0027] When a resist film is formed using the resist composition of the present embodiment and selective exposure is performed on the resist film, in the exposed portion of the resist film, an acid is generated from the component (B), and the solubility of the component (A) in the developer changes by 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. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and when the resist composition is negative, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern. As the component (A), other high molecular compounds and / or low molecular compounds may be used in combination with the (A1) component.

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

[0029] ·Regarding the (A1) component The (A1) component is a resin component whose solubility in a developer changes by the action of an acid. As the (A1) component, those having a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid are preferable. The (A1) component may have other structural units as necessary in addition to the structural unit (a1).

[0030] ≪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.

[0031] Examples of the acid-dissociable group include those proposed as the acid-dissociable group of the base resin for chemically amplified resist compositions to date. Specific examples of those proposed as the acid-dissociable group of the base resin for chemically amplified resist compositions 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.

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

[0033] [In the formula, Ra’ [wherein Ra’ 1 , Ra’ 2 is a hydrogen atom or an alkyl group. Ra’ 3 is a hydrocarbon group, and Ra’ 3 may be bonded to either Ra’ 1 , Ra’ 2 to form a ring.]

[0034] In formula (a1-r-1), it is preferable that at least one of Ra’ 1 and Ra’ 2 is a hydrogen atom, and more preferably both are hydrogen atoms. Ra’ 1 or Ra’ 2When it is an alkyl group, examples of the alkyl group include the same groups 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.

[0035] 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.

[0036] The branched alkyl group preferably has 3 to 10 carbon atoms, 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.

[0037] Ra’ 3 When Ra’ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from monocycloalkane is preferred. As the monocycloalkane, those having 3 to 6 carbon atoms are preferred, and specifically, cyclopentane, cyclohexane, etc. are 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. Specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane and the like can be mentioned.

[0038] 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 is substituted with a hetero atom, and the like. 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. Ra’ 3 Specific examples of the aromatic hydrocarbon group in Ra’ 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 (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic 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.). 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.

[0039] Ra’3 The cyclic hydrocarbon group in 3 may have a substituent. Examples of such a 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 substituents alone, or may have one or more of a plurality of types of the above substituents. Examples of the monovalent linear 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; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0040] Ra’ 3 is Ra’ 1 , Ra’ 2 When any of them combines with Ra’ 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 and a tetrahydrofuranyl group.

[0041] 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.

[0042]

Chemical formula

[0043] Ra’ 4 Examples of the hydrocarbon group of Ra’ include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group. Ra’ 4 Examples of the linear or branched alkyl group and cyclic hydrocarbon group (aliphatic hydrocarbon group which is a monocyclic group, aliphatic hydrocarbon group which is a polycyclic group, aromatic hydrocarbon group) in Ra’ are the same as those of the above Ra’ 3 . Ra’ 4The chain or cyclic alkenyl group in [description] preferably has 2 to 10 carbon atoms. Ra’ 5 , Ra’ 6 As the hydrocarbon group of [description], those similar to the above Ra’ 3 can be mentioned.

[0044] 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 mentioned. On the other hand, when Ra’ 4 ~Ra’ 6 are not bonded to each other and are independent hydrocarbon groups, a group represented by the following general formula (a1-r2-4) is preferably mentioned.

[0045]

Chemical formula

[0046] 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.

[0047] Ra’ 10 As the linear alkyl group in Ra’, 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 Ra’, those similar to the above Ra’ 3 can be mentioned.

[0048] Ra’ 10 The alkyl group in Ra’ may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms (such as methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group. Examples of the heteroatom mentioned here include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O) 2 -, -S(=O) 2 -O- and the like.

[0049] In formula (a1-r2-1), Ra’ 11 (Ra’10 (an aliphatic cyclic group formed together with a carbon atom to which it is bonded) is Ra' in formula (a1-r-1). 3 The group exemplified as an aliphatic hydrocarbon group (alicyclic hydrocarbon group) which is a monocyclic group or a polycyclic group of Ra' in 3 is preferable. Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable.

[0050] 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' in the formula (a1-r-1). 3 The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of this substituent include the same substituents as those that the cyclic hydrocarbon group of Ra' in 3 may have. In formula (a1-r2-2), Ra 3 Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in ~Ra 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. 101 ~Ra 103 Examples of the monovalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms in ~Ra include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 101 decanyl group, a tricyclo[3.3.1.1 103 decanyl group, a tetracyclo[6.2.1.1 2,6 .0 3,7 dodecanyl group, an adamantyl group, and the like. 3,6 .0 2,7 Examples of the monovalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms in ~Ra include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 101 ~Ra 103Among 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, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.

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

[0052] Ra 101 ~Ra 103 Examples of the group containing a carbon-carbon double bond formed by two or more of Ra

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

[0054] Ra in the formula (a1-r2-3)104 Examples of the substituent that may be present include 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.

[0055] 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. Ra’ 12 and Ra’ 13 Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in Ra’ 101 ~Ra 103 are the same as those of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in Ra Ra’ 12 and Ra’ 13 Among them, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group and an ethyl group are even more preferable, and a methyl group is particularly preferable. 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.

[0056] In formula (a1-r2-4), Ra’ 14 is a hydrocarbon group that may have a substituent. Examples of the hydrocarbon group in Ra’ 14 include a linear or branched alkyl group or a cyclic hydrocarbon group.

[0057] Ra’ 14The linear alkyl group in is preferably an alkyl group having 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, and the like. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

[0058] Ra’ 14 The branched-chain alkyl group in is preferably an alkyl group having 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, and the like, and an isopropyl group is preferable.

[0059] Ra’ 14 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from 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 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.

[0060] Ra’ 14 The aromatic hydrocarbon group in is the same as the aromatic hydrocarbon group in Ra 104 Among them, Ra’ 14is 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 those of the substituent that

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

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

[0063]

Chemical formula

[0064]

Chemical formula

[0065]

Chemical formula

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

[0067] [Chemistry]

[0068] [Chemistry]

[0069] [Chemistry]

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

[0071] [Chemistry]

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

[0073] [Chemistry]

[0074] Tertiary alkyloxycarbonyl acid-dissociable group: As the acid-dissociable group for protecting the hydroxyl group among the polar groups, 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) can be mentioned.

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

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

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

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

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

[0080] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a ring. The ring may be polycyclic or monocyclic, and may be an alicyclic ring or an aromatic ring. The alicyclic ring and the aromatic ring may contain heteroatoms.

[0081] Ra’ 10 and Ra’ 11a or Ra’ 11b Among the rings formed by combining with each other, monocycloalkene, a ring in which some of the carbon atoms of monocycloalkene are substituted with heteroatoms (such as oxygen atoms, sulfur atoms), and monocycloalkadiene are preferred, cycloalkenes having 3 to 6 carbon atoms are preferred, and cyclopentene or cyclohexene is preferred.

[0082] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a fused ring. Specific examples of the fused ring include indane and the like.

[0083] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a ring which may have a substituent. Examples of this substituent include Ra described above x5 and the like.

[0084] Ra’ 11a or Ra’ 11b and Ra’ 12 may combine with each other to form a ring. Examples of the ring include those similar to the rings formed by combining Ra’ 10 and Ra’ 11a or Ra’ 11b with each other.

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

[0086] [Chemical formula]

[0087] Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which a hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent, a structural unit derived from acrylamide, 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.

[0088] Among them, as the structural unit (a1), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to the α-position carbon atom 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).

[0089] [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. Va 1 is a divalent hydrocarbon group which may have an ether bond. n a1 is an integer of 0 to 2. Ra 1 is an acid dissociable group represented by the above general formula (a1-r-1), (a1-r-2), or (a1-r-4). Wa 1 is an n a2 + monovalent hydrocarbon group. n a2 is an integer of 1 to 3. Ra2 is an acid dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above. Ya 001 is a single bond or a divalent linking group. Ya 01 is a single bond or a divalent linking group. Rax 01 is an acid dissociable group represented by the general formula (a1-r-1), (a1-r-2) or (a1-r-4) above. Rz 01 is an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group. q is an integer from 0 to 3. n is an integer of 0 or more. However, n ≦ q × 2 + 4.]

[0090] In the above formulas (a1-1) to (a1-3), the alkyl group of R having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. 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.

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

[0092] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in may be saturated or unsaturated, and is usually preferably saturated. More specifically, 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.

[0093] 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, it includes a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc. 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, it includes alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -; alkylmethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2-CH 2 - and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups such as alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0094] 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, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include 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, and more preferably has 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 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 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.

[0095] Va 1 In the formula, the aromatic hydrocarbon group as the divalent hydrocarbon group 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 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 hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group in which one of the hydrogen atoms 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.

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

[0097] In the formula (a1-2), Wa 1 In n a2The monovalent 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. Said n a2 The monovalent is preferably divalent to tetravalent, 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).

[0098] In the formula (a1-3), Ya 001 The divalent linking group in is not particularly limited, and examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 001 is preferably an ester bond [-C(=O)-O-, -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. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 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.

[0099] In the formula (a1-3), Ya 01 The divalent linking group in is not particularly limited, and examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 01Among these, 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 is preferable. 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 even more preferably a single bond.

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

[0101] 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, even 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 The halogen atom in is preferably an iodine atom. Rz 01 The halogen atom of the halogenated alkyl group in is preferably a fluorine atom, an iodine atom, or a bromine atom, and more preferably a fluorine atom. Rz 01 is preferably an alkoxy group or a hydroxy group, and more preferably a hydroxy group.

[0102] 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 0 to 5, more preferably 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 has a naphthalene structure, all 6 hydrogen atoms of the naphthalene may be substituted with hydroxy groups. Also, in the naphthalene, Ya 001 , -Ya 01 -C(=O)-O-Ra 01 groups, and the substitution positions of the hydroxy groups are not particularly limited.

[0103] Specific examples of the constitutional unit (a1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0104]

Chemical formula

[0105]

Chemical formula

[0106]

Chemical formula

[0107]

Chemical formula

[0108]

Chemical formula

[0109]

Chemical formula

[0110] [Chemistry]

[0111] [Chemistry]

[0112] [Chemistry]

[0113] In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Rz represents a hydrogen atom, an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group.

[0114] [Chemistry]

[0115] [Chemistry]

[0116] [Chemistry]

[0117] [Chemistry]

[0118] [Chemistry]

[0119] The constitutional unit (a1) possessed by the component (A1) may be one kind or two or more kinds. As the structural unit (a1), the structural unit represented by the formula (a1-1) or the structural unit represented by the formula (a1-3) is more preferable because the characteristics (sensitivity, shape, etc.) in lithography using an electron beam or EUV can be more easily enhanced. Among them, since it is suitable for enhancing the reactivity in EB or EUV, the acid dissociable group (Ra 1 , Rax 01 ) is preferably an acid dissociable group represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), respectively, and among them, it is particularly preferable to select a cyclic group.

[0120] In the formula (a1-1), n a1 is preferably 0. In the formula (a1-3), Ya 001 is preferably a single bond. n is preferably 1. q is preferably 0 or 1, and more preferably 0. Ya 01 is preferably a single bond.

[0121] From the viewpoint of further enhancing roughness reduction, as the structural unit (a1), the structural unit represented by the formula (a1-3) is preferable. Ra 1 is preferably an acid dissociable group represented by the above general formula (a1-r2-1) or (a1-r-4). Rax 01 is preferably an acid dissociable group represented by the above general formula (a1-r2-1).

[0122] From the viewpoint of further enhancing the effect of improving sensitivity, as the structural unit (a1), the structural unit represented by the formula (a1-1) is preferable. Ra 1 is preferably an acid dissociable group represented by the above general formula (a1-r2-1) or (a1-r-4), and more preferably an acid dissociable group represented by the above general formula (a1-r-4). Rax 01is preferably an acid dissociable group represented by the general formula (a1-r2-1) described above.

[0123] From the viewpoint of further enhancing the effect of suppressing film reduction, as the constitutional unit (a1), the constitutional unit represented by the formula (a1-1) is preferable. Ra 1 is preferably an acid dissociable group represented by the general formula (a1-r2-1) or (a1-r-4) described above, and more preferably an acid dissociable group represented by the general formula (a1-r2-1) described above. Rax 01 is preferably an acid dissociable group represented by the general formula (a1-r2-1) described above.

[0124] Alternatively, as the constitutional unit (a1), those containing the constitutional unit represented by the following general formula (a1-1-1) may also be used.

[0125] [Chemical formula] [In the formula, Ra 1 ” is an acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4). * indicates a bond.]

[0126] In the formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the formula (a1-1).

[0127] The description of the acid dissociable group represented by the 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.

[0128] (A1) The proportion of the structural unit (a1) in the component 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% based on the total of all the structural units (100 mol%) constituting the (A1) component. By setting the proportion of the structural unit (a1) to be equal to or higher than the lower limit value of the above-mentioned preferred range, lithography characteristics such as sensitivity, resolution, and CDU improvement are improved. On the other hand, when it is equal to or lower than the upper limit value of the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithography characteristics become good.

[0129] ≪Other structural units≫ (A1) The component may have other structural units in addition to the above-mentioned structural unit (a1) as necessary. Examples of other structural units include, for example, the structural unit (a10) represented by the general formula (a10-1) described later; the structural unit (a2) containing a lactone-containing cyclic group; the structural unit (a5) that generates an acid upon exposure; the structural unit (a6) having acid diffusion control properties; the structural unit (a8) derived from a compound represented by the general formula (a8-1) described later, and the like.

[0130] Structural unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0131]

Chemical formula

[0132] 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 from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferable.

[0133] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in is not particularly limited, but 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.

[0134] · 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.

[0135] ·· 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.

[0136] ··· 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 preferable. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4-), pentamethylene group [-(CH 2 ) 5 -), etc. 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, -CH(CH 3 ), -CH(CH 2 CH 3 ), -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 ), -C(CH 3 )(CH 2 CH 2 CH 3 ), -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 ), -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2Examples of the alkylalkylene group include an alkyltetramethylene group such as - etc. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0137] 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, and the like.

[0138] ··· 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, etc. are 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, etc. are mentioned.

[0139] 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 a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom. Examples of the substituent containing a heteroatom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferable.

[0140] ·· 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, even 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; 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, a thiophene ring, and the like. 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 a 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 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 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.

[0141] 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, and the like. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0142] ·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 or an acyl group.), -S-, -S(=O) 2 -, -S(=O) 2 -O-, 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 -represented groups [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.] and the like. When the divalent linking group containing a heteroatom 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-Y22 - 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 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. The group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 - In, m” is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 - is particularly preferably a group represented by the formula -Y 21 -C(=O)-O-Y 22 -. Among them, the group represented by the formula -(CH 2 ) a’ -C(=O)-O-(CH 2 ) b’ - is preferred. In the formula, a’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0143] Ya x1Examples thereof include 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, with a single bond or an ester bond [-C(=O)-O-, -O-C(=O)-] being more preferred.

[0144] In the formula (a10-1), Wa x1 is an aromatic hydrocarbon group which may have a substituent. Examples of the aromatic hydrocarbon group in Wa x1 include a group obtained by removing (n ax1 +1) hydrogen atoms from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, 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. Further, examples of the aromatic hydrocarbon group in Wa x1 include a group obtained by removing (n ax1 +1) hydrogen atoms from an aromatic compound (such as biphenyl or fluorene) containing an aromatic ring which may have two or more substituents. Among the above, Wa x1 is preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, more preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene or naphthalene, and still more preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene.

[0145] Wa x1The aromatic hydrocarbon group in [description] may or may not have a substituent. Examples of the substituent include, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, etc. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent are Ya x1 Those similar to those listed as the substituent of the cyclic aliphatic hydrocarbon group in [description] can be mentioned. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, even more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. Wa x1 The aromatic hydrocarbon group in [description] preferably has no substituent.

[0146] 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, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0147] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0148]

Chemical formula

[0149]

Chemical formula

[0150]

Chemical formula

[0151] (A1) component may have one or more structural units (a10). (A1) component may or may not have the structural unit (a10), but preferably has the structural unit (a10). When the (A1) component has the structural unit (a10), the proportion of the structural unit (a10) in the (A1) component 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 of all structural units constituting the (A1) component (100 mol%). By setting the proportion of the structural unit (a10) to be equal to or higher than the lower limit value, the sensitivity is more easily increased. On the other hand, by setting it to be equal to or lower than the upper limit value, it becomes easier to balance with other structural units.

[0152] Structural unit (a2): (A1) component may or may not have a structural unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to the structural unit (a1)). The lactone-containing cyclic group of the structural 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 structural unit (a2), for example, 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 result in good lithography characteristics and the like.

[0153] 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 when it further has other ring structures, 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 structural 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.

[0154]

Chemical formula

[0155] In the general formulas (a2-r-1) to (a2-r-7), Ra’ 21 As the alkyl group in, 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 and the like can 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, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, a group in which the alkyl group mentioned as the alkyl group in the above Ra’ 21 is linked to an oxygen atom (-O-) can be mentioned. Ra’ 21 As the halogen atom in, a fluorine atom is preferable. Ra’ 21 As the halogenated alkyl group in, a group in which part or all of the hydrogen atoms of the alkyl group in the above Ra’ 21 are substituted with the halogen atom can be mentioned. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0156] Ra’ 21In “-COOR” and “-OC(=O)R”, each R” is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group for R” may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R” is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 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 bicycloalkane, tricycloalkane, tetracycloalkane, etc. can be exemplified. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, etc.; 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 for 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 for Ra’ preferably has 1 to 6 carbon atoms. Specifically, it includes a group in which at least one hydrogen atom of the alkyl group in Ra’ 21 is substituted with a hydroxyl group.

[0157] Ra’ 21 Among the above, each is preferably independently a hydrogen atom or a cyano group.

[0158] 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. For example, -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 -, -CH 2 -S-CH 2 - etc. are mentioned. 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.

[0159] Specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0160]

Chemical formula

[0161]

Chemical formula

[0162] As the constitutional unit (a2), among others, a constitutional unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent is preferable. Such a constitutional unit (a2) is preferably a constitutional unit represented by the following general formula (a2-1).

[0163]

Chemical formula

[0164] 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.

[0165] In the formula (a2-1), Ya 21 The divalent linking group in is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. are preferably exemplified. Ya 21 The divalent linking group in Ya x1 is the same as the divalent linking group in Ya

[0166] 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.

[0167] In the formula (a2-1), Ya 21 is a single bond, and La 21 is preferably -COO- or -OCO-.

[0168] 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 above general formulas (a2-r-1) to (a2-r-7), respectively.

[0169] (A1) component may have one or more than two kinds of structural units (a2). (A1) component may or may not have the structural unit (a2). When (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%, still more preferably 1 to 10 mol% with respect to the total of all structural units (100 mol%) 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 taken, and various lithography characteristics become good.

[0170] Structural unit (a5): (A1) component may or may not have the structural unit (a5) that generates an acid upon exposure. Known structural units can be used for the structural unit (a5). By having the structural unit (a5), the acid generated upon exposure is likely to be uniformly distributed in the resist film. By having the structural unit (a5), the acid generated upon exposure is likely to be uniformly distributed in the resist film. Examples of the structural unit (a5) include structural units containing the structure described in the following (B) component. For example, structural units containing the structure represented by any of the following general formulas (b-1) to (b-3) can be mentioned. Examples of the structural unit (a5) preferably include structural units represented by the following general formula (a5-1).

[0171] [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 50 is a divalent linking group or a single bond. Ra 50 is a divalent hydrocarbon group which may have a substituent. n a5 is an integer of 0 to 2. La 51is a divalent linking group. Ya 5 is a divalent linking group which may have a hetero atom, or a single bond. Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. n5 is an integer of 1 to 4. m is an integer of 1 or more, and M’ m+ is an m-valent onium cation. ]

[0172] {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 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 part 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 them, a fluorine atom is particularly preferable as the halogen atom in the halogenated alkyl group. 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.

[0173] In the formula (a5-1), La 50 is a divalent linking group or a single bond. La 50 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 of them is the above Ya x1It is 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 . Among these, La 50 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, La 5 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)-].

[0174] In the formula (a5-1), Ra 50 is a divalent hydrocarbon group which may have a substituent. Ra 50 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0175] ··Ra 50 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 a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0176] ···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. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH2 ) 3 -), tetramethylene group [-(CH 2 ) 4 -), pentamethylene group [-(CH 2 ) 5 -), etc. can be mentioned. The branched-chain 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-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -CH(CH 3 ), -CH(CH 2 CH 3 ), -C(CH 3 ) 2 -), -C(CH 3 )(CH 2 CH 3 ), -C(CH 3 )(CH 2 CH 2 CH 3 ), -C(CH 2 CH 3 ) 2 -), etc. alkylmethylene groups; -CH(CH 3 )CH 2 -), -CH(CH 3 )CH(CH 3 ), -C(CH 3 ) 2 CH 2 -), -CH(CH 2 CH 3 )CH 2 -), -C(CH 2 CH 3 ) 2 -CH 2 -), etc. alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -), -CH 2 CH(CH 3 )CH 2 -), etc. alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -), -CH 2CH(CH 3 )CH 2 CH 2 - alkyl alkylene groups such as alkyl tetramethylene groups like - etc. are exemplified. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0177] The above-mentioned 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, and the like.

[0178] ··· 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 hetero atom 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 above-mentioned linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 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. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specifically, cyclopentane, cyclohexane, etc. are exemplified. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms 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, etc. are exemplified.

[0179] 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 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 halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is 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. 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. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferable.

[0180] ··Ra 50 The aromatic hydrocarbon group in 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 it 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 carbon atoms in the substituents. Specifically, as the aromatic ring, 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 can be mentioned. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specifically, as the aromatic heterocyclic ring, a pyridine ring, a thiophene ring, and the like can be mentioned. Specifically, as the aromatic hydrocarbon group, 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 (for example, biphenyl, fluorene, etc.); a group in which one hydrogen atom of a 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 (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), and the like can be mentioned. 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.

[0181] 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, 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, and a tert-butyl group are most preferable. Examples of the alkoxy group, halogen atom, and alkyl halide group as the substituent include those exemplified as the substituent that replaces the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0182] In the formula (a5-1), n a5 is an integer of 0 to 2. Among these, Ra 50 is preferably an aliphatic hydrocarbon group containing a ring in the structure, more preferably a cyclic aliphatic hydrocarbon group that may contain a substituent containing a hetero atom in the ring structure, and still more preferably an alicyclic hydrocarbon group that may have a substituent and is a polycyclic group or a monocyclic group. Alternatively, among these, Ra 50 is preferably an aromatic hydrocarbon group.

[0183] n a5 When it is 2, the two Ra 50 may both be alicyclic hydrocarbon groups that may have a substituent, may both be aromatic hydrocarbon groups, or may be a combination of an alicyclic hydrocarbon group that may have a substituent and an aromatic hydrocarbon group.

[0184] In the formula (a5-1), La 51 is a divalent linking group. La 51 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 (-SO 2 -) 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) 50 is bonded to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0185] [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.]

[0186] 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.

[0187] 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' 102 Specific examples of the alkylene group include a methylene group [-CH 2 -]; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2-alkylmethylene groups such as; ethylene group [-CH 2 CH 2 -]; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -alkyl ethylene groups such as; trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2 -]; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -alkyl trimethylene groups such as; tetramethylene group [-CH 2 CH 2 CH 2 CH 2 -]; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -alkyl tetramethylene groups such as; pentamethylene group [-CH 2 CH 2 CH 2 CH 2 CH 2 -] and the like. Also, some of the methylene groups in the alkylene group in V' 101 or V' 102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra' 3 in the formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

[0188] La 51 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably the linking groups represented by the above formulas (L-al-1) to (L-al-5) and (L-al-8), and still more preferably the linking group represented by (L-al-3) or (L-al-8).

[0189] In the formula (a5-1), Ya 5 is a divalent linking group which may have a heteroatom or a single bond. Ya 5 The divalent linking group in Ya is not particularly limited, and preferably includes a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Ya 5 Regarding the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom in Ya, 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 x1 Among the above, Ya 5 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0190] In the formula (a5-1), Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. Ra 51 and Ra 52 The fluorinated alkyl group in Ra and Ra 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 3 - bonded to the carbon atom adjacent to SO 51 and Ra 52 is preferably a fluorine atom from the viewpoint of acid strength.

[0191] In the formula (a5-1), n5 is an integer of 1 to 4, and 1, 2 or 3 is preferable.

[0192] {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.

[0193] Preferred cation parts ((M’ m+ )) 1 / m include organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0194]

Chemical formula

[0195] In the above general formulas (ca-1) to (ca-3), examples of the aryl group in R 201 ~R 207 include unsubstituted aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable. R 201 ~R207 As the alkyl group in 207 , a linear or cyclic alkyl group having 1 to 30 carbon atoms is preferred. R 201 ~R 207 As the alkenyl group in 207 , it preferably has 2 to 10 carbon atoms. R 201 ~R 207 and the substituent that R 210 may have includes, 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 the following general formulas (ca-r-1) to (ca-r-7), etc.

[0196]

Chemical formula

[0197] 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. Also, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0198] R’ 201 The aromatic hydrocarbon group in 201 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’ 201Specific examples of the aromatic ring of the aromatic hydrocarbon group in [context] 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 heteroatom. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R’ 201 Specific examples of the aromatic hydrocarbon group in [context] 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 hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, 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 (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0199] R’ 201 The cyclic aliphatic hydrocarbon group in [context] 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 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 polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable, and as the polycycloalkane, those having 7 to 30 carbon atoms are preferable. 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 preferable.

[0200] Among them, as the cyclic aliphatic hydrocarbon group in R’ 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.

[0201] 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 [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -] and the like can be mentioned. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 - and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups such as alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0202] Also, R’ 201The cyclic hydrocarbon group in [substance] may contain a heteroatom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), -SO-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 included. 2 Examples of the cyclic group of - include cyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0203]

Chemical formula

[0204] R’ 201 Examples of the substituent in the cyclic group of R’ 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 a group 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, and a tert-butyl group, are substituted with the halogen atom. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH 2 -) constituting the cyclic hydrocarbon group.

[0205] The chain-like alkyl group may have a substituent: R’ 201 The chain-like alkyl group of R’ 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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); -SO 2 -containing cyclic groups represented by the following general formulas (b5-r-1) to (b5-r-4) etc. are preferable.

[0210] 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-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )(wherein 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 ring formed 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 and the like.

[0211] 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.

[0212] 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 -SO 2 -containing cyclic group which may have a substituent. R 210 Examples of the aryl group in R R 210 include unsubstituted aryl groups having 6 to 20 carbon atoms, preferably a phenyl group and a naphthyl group. R 210 Examples of the alkyl group in R R 210 include linear or cyclic alkyl groups, preferably those having 1 to 30 carbon atoms. R 210 The alkenyl group in R R 210 preferably has 2 to 10 carbon atoms. R 210 In R 2 any -SO 2 -containing cyclic group can be used without particular limitation. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) can be mentioned. A "-SO 2 -containing polycyclic group" is preferred, and a group represented by the general formula (b5-r-1) is more preferred.

[0213]

Chemical formula

[0214] 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, 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.

[0215] 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.

[0216] Specific examples of the groups respectively represented by the following general formulas (b5-r-1) to (b5-r-4) are given below. “Ac” in the formula represents an acetyl group.

[0217]

Chemical formula

[0218]

Chemical formula

[0219]

Chemical formula

[0220] Specific examples of the preferred cation represented by the formula (ca-1) include cations respectively represented by the following chemical formulas.

[0221]

Chemical formula

[0222]

Chemical formula

[0223]

Chem.

[0224]

Chem.

[0225]

Chem.

[0226]

Chem.

[0227]

Chem.

[0228] Specific examples of the preferred cation represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0229] 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.

[0230]

Chem.

[0231] The cationic part ((M’ m+ ) 1 / m ) in the formula (a5-1) is preferably a sulfonium cation, more preferably a cation represented by the formula (ca-1) to (ca-3), still more preferably a cation represented by the formula (ca-1), and particularly preferably a cation represented by the formula (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, a cation selected from the group consisting of cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) is particularly preferred.

[0232] Preferred specific examples of the structural unit (a5) are shown below. In the following formula, 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).

[0233]

Chemical formula

[0234]

Chemical formula

[0235]

Chemical formula

[0236] The structural unit (a5) contained in the component (A1) may be one kind or two or more kinds. When the component (A1) has the constitutional unit (a5), the proportion of the constitutional unit (a5) in the component (A1) is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, still more preferably 15 to 20 mol% with respect to the total (100 mol%) of all the constitutional units constituting the component (A1). When the proportion of the constitutional unit (a5) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity and improved resolution. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other constitutional units.

[0237] Constitutional unit (a6): The constitutional unit (a6) is a constitutional unit having acid diffusion controllability. The component (A1) may or may not have the constitutional unit (a6). Known constitutional units can be used as the constitutional unit (a6). Examples of the constitutional unit (a6) include constitutional units containing the structures described in the components (D1) and (D2) described below. For example, constitutional units containing the structures represented by any of the general formulas (d1-1) to (d1-3) described below can be mentioned.

[0238] The component (A1) may have one or more kinds of the constitutional unit (a6). When the component (A1) has the constitutional unit (a6), the proportion of the constitutional unit (a6) in the component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 10 mol% with respect to the total (100 mol%) of all the constitutional units constituting the component (A1). When the proportion of the constitutional unit (a6) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other constitutional units.

[0239] Constitutional unit (a8): The constitutional unit (a8) is a constitutional unit derived from a compound represented by the following general formula (a8-1). The component (A1) may or may not have the constitutional unit (a8).

[0240] [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 and 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. ]

[0241] W 2 In the polymerizable group-containing group of, the "polymerizable group" means a group that enables a compound having a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a multiple bond between carbon atoms such as an ethylenic double bond.

[0242] The polymerizable group-containing group may be a group composed only of a polymerizable group, or a group composed of a polymerizable group and another group other than the polymerizable group. Examples of the other group 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.

[0243] Ya x2 and W 2 The condensed ring formed by and is W2 The polymerizable group of the moiety and Ya x2 The condensed ring formed with W 2 The other group other than the polymerizable group of the moiety and Ya x2 The condensed ring formed with W is mentioned. Ya x2 And W 2 The condensed ring formed with W may have a substituent.

[0244] Specific examples of the structural unit (a8) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0245]

Chemical formula

[0246] Among the above examples, the structural unit (a8) is preferably at least one selected from the group consisting of the 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 the structural units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0247] The structural unit (a8) contained in the (A1) component may be one kind or two or more kinds. 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 (100 mol%) of all the structural units constituting the (A1) component.

[0248] The (A1) component contained in the resist composition may be used alone or in combination of two or more.

[0249] Examples of the component (A1) include a polymer compound having a constitutional unit (a1) and a constitutional unit (a10). The component (A1) is preferably a polymer compound composed of only the constitutional unit (a1) and the constitutional unit (a10).

[0250] In the polymer compound composed of the constitutional unit (a1) and the constitutional unit (a10), the proportion of the constitutional unit (a1) is more preferably 10 to 75 mol%, further preferably 30 to 70 mol%, and still further preferably 40 to 70 mol% with respect to the total (100 mol%) of all the constitutional units constituting the polymer compound. The proportion of the constitutional unit (a10) in the polymer compound is preferably 25 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 30 to 60 mol%, and particularly preferably 20 to 50 mol% with respect to the total (100 mol%) of all the constitutional units constituting the polymer compound.

[0251] Such a component (A1) can be produced by dissolving the monomers that induce each constitutional unit in a polymerization solvent, adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601, etc.) thereto, and performing polymerization. Alternatively, such a component (A1) can be produced by dissolving the monomer that induces the constitutional unit (a1) and the monomers that induce arbitrary constitutional units (e.g., the constitutional unit (a10), the constitutional unit (a5), etc.) in a polymerization solvent, adding the radical polymerization initiator as described above thereto, performing polymerization, and then performing a deprotection reaction. During the polymerization, for example, a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination. Thus, 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: non-uniform irregularities on the sidewall of the line). 3 ) 2 It is also possible to introduce a -C(CF 3 ) 2 -OH group at the end.

[0252] (A1) component's weight average molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography (GPC)) is not particularly limited, preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and even more preferably from 5,000 to 30,000. When the Mw of the (A1) component is below the preferable upper limit of this range, there is sufficient solubility in the resist solvent for use as a resist. When it is above the preferable lower limit of this range, the dry etching resistance and the cross-sectional shape of the resist pattern 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.

[0253] ·Regarding the (A2) component The resist composition of this embodiment may also use, as the (A) component, a base material component (hereinafter referred to as "(A2) component") that does not correspond to the (A1) component and whose solubility in the developer changes by the action of an acid. As the (A2) component, it is not particularly limited, and it may be arbitrarily selected from a number of conventionally known base material components for chemically amplified resist compositions. (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.

[0254] The ratio of the (A1) component in the (A) 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 CDU improvement is likely to be formed.

[0255] 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.

[0256] <Acid generator component (B)> The resist composition of this embodiment contains an acid generator component (B) that generates an acid upon exposure.

[0257] ·Regarding the component (B0) The acid generator component (B) includes a compound (B0) (component (B0)) represented by the following general formula (b0).

[0258] [Chemical formula] [In the formula, Ar 1 and Ar 2 are each an aromatic ring. R b1 and R b2 are each a substituent other than an iodine atom. R f is a trifluoromethyl group or a fluorine atom. R b3 is a substituent other than a trifluoromethyl group and a fluorine atom. L 1 and L 2 are each a divalent linking group. nb1 and nb2 are each an integer of 1 or more as long as the valence allows. nb3 is an integer of 1 to 4. 3 ≤ nb1 + nb2. nr1 and nr2 are each an integer of 0 or more as long as the valence allows. nr3 is an integer of 0 to 3. When nb3 is an integer of 2 or more, the plurality of R f may be the same or different. When nr1 is an integer of 2 or more, the plurality of R b1 may be the same or different. When nr2 is an integer of 2 or more, the plurality of R b2 may be the same or different. When nr3 is an integer of 2 or more, the plurality of R b3 may be the same or different. M m+ represents an m-valent organic cation. m is an integer of 1 or more. ]

[0259] ((Anion part of component (B0)) In the formula (b0), Ar 1The aromatic ring in [the relevant context] is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and it 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. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene. Ar 1 Preferably, it is a benzene ring, a naphthalene ring, or an anthracene ring, more preferably a benzene ring or a naphthalene ring, and still more preferably a benzene ring. Ar 2 The aromatic ring in [a certain context related to Ar] includes the same ones as the aromatic ring in . 1 The aromatic ring in [a certain context related to Ar] includes the same ones as the aromatic ring in . Ar 2 Preferably, it is a benzene ring, a naphthalene ring, or an anthracene ring, more preferably a benzene ring or a naphthalene ring, and still more preferably a benzene ring.

[0260] In the formula (b0), nb1 is preferably 2 or more. For example, nb1 may be 4 or less, or 3 or less. nb1 is preferably 1 to 4, and more preferably 2. In the formula (b0), nb2 is preferably 2 or more, and more preferably 3 or more. For example, nb2 may be 5 or less, 4 or less, or 3 or less. nb2 is preferably 1 to 5, and more preferably 3.

[0261] In the formula (b0), nb1 + nb2 is preferably an integer of 4 or more, and more preferably an integer of 5 or more. The relationship between nb1 and nb2 is preferably nb1 ≤ nb2, and more preferably nb1 < nb2.

[0262] In the formula (b0), R b1Examples thereof include an alkyl group, an alkoxy group, a halogen atom other than an iodine atom, a halogenated alkyl group, a hydroxyl group, and the like. As the alkyl group, 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, an alkoxy group having 1 to 5 carbon atoms is preferable, and 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. Examples of the halogenated alkyl group include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. In the formula (b0), R b2 Examples of R b1 include the same groups as those of R.

[0263] nr1 and nr2 are each not particularly limited as long as the valence allows, and may be 0.

[0264] In the formula (b0), L 1 Examples of the divalent linking group in include, but are not particularly limited to, a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

[0265] ·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.

[0266] ··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 the structure.

[0267] ···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 [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc. may 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, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 )2 -CH 2 - and other alkylethylene groups such as -CH(CH 3 )CH 2 CH 2 -; -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -; -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups such as these may be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0268] 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, and the like.

[0269] ··· 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 hetero atom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal 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 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 polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from polycycloalkane is preferable, and 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.

[0270] 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, a tert-butyl group are 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, a tert-butoxy group are more preferable, and a methoxy group, an ethoxy group are 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 a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. 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. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferable.

[0271] ·· 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 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. 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 (for example, biphenyl, fluorene, etc.); a group in which one hydrogen atom of a 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 (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 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.

[0272] In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. 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, 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.

[0273] · 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 or an acyl group), -S-, -S(=O) 2 -, -S(=O) 2 -O-, 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 -, -C(=O)-O-Y 21 -C(=O)-O- or -Y 21 -S(=O) 2 -O-Y 22 -represented groups [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.] and the like. When the divalent linking group containing a heteroatom 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 -Among them, 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 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula -[Y 21 -C(=O)-O] m” -Y 22 -In the group represented by, m” is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. 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 preferred. Among them, the formula -(CH 2 ) a’ -C(=O)-O-(CH 2 ) b’The group represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0274] Among these, L 1 as 1 -C(=O)-O- 0 , 1 -O-C(=O)- 0 , 1 -Y 21 -C(=O)-O- 0 , 1 -C(=O)-O-Y 21 - 0 , 1 -[Y 21 -C(=O)-O][ m” -Y 22 - 0 , 1 -C(=O)-O-Y 21 -C(=O)-O- 0 , or, 1 -Y 21 -O-C(=O)-Y 22 - 0 is preferred, 1 -C(=O)-O- 0 , or, 1 -O-C(=O)- 0 is more preferred. In the formula, 1 is a bond to Ar 1 . 0 is a bond to a benzene ring having R f .

[0275] L 2 as 1 includes the same ones as the divalent linking groups described above in L L 2 as 2 -C(=O)-O- 1 , 2 -O-C(=O)- 1 ,2 -Y 21 -C(=O)-O-* 1 、* 2 -C(=O)-O-Y 21 -* 1 、* 2 -[Y 21 -C(=O)-O] m” -Y 22 -* 1 、* 2 -Y 21 -O-C(=O)-Y 22 -* 1 、* 2 -Y 21 -O-Y 22 -* 1 、* 2 -Y 21 -O-* 1 、 or, * 2 -C(=O)-NH-* 1 is preferred, * 2 -C(=O)-O-* 1 、* 2 -O-C(=O)-* 1 、 or, * 2 -CH 2 -O-* 1 is more preferred, * 2 -C(=O)-O-* 1 、 or, * 2 -O-C(=O)-* 1 is even more preferred. In the formula, * 1 is a bond to Ar 1 is a bond to Ar 2 is a bond to Ar 2 is a bond to Ar

[0276] R f is preferably a fluorine atom. nb3 is preferably an integer of 2 to 4, more preferably 3 or 4, and even more preferably 4. 1 ≦ nb3 + nr3 ≦ 4. nr3 is not particularly limited as long as the valence allows, but it may be 0.

[0277] In the formula (b0), R b3Examples thereof include an alkyl group, an alkoxy group, a halogen atom other than a fluorine atom, a halogenated alkyl group other than a trifluoromethyl group, a hydroxyl group, and the like. Examples of the alkyl group and the alkoxy group include those described above for R b1 and R b2 above. Examples of the halogenated alkyl group include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom (excluding the trifluoromethyl group).

[0278] The anionic part of the component (B0) is preferably an anion represented by the following general formula (b0-an).

[0279] [Chemical formula] [In the formula, R b1 , R b2 , R b3 , R f , nb3, nr3, L 1 and L 2 are the same as R b1 , R b2 , R b3 , R f , nb3, nr3, L 1 and L 2 in the formula (b0), respectively. nb10 and nb20 are each an integer of 1 or more. 3 ≤ nb10 + nb20. nr10 and nr20 are each an integer of 0 or more. When nr10 is an integer of 2 or more, the plurality of R b1 may be the same or different. When nr20 is an integer of 2 or more, the plurality of R b2 may be the same or different. qb1 is an integer from 0 to 3. nb10 + nr10 ≤ qb1 × 2 + 4. qb2 is an integer from 0 to 3. nb20 + nr20 ≤ qb2 × 2 + 5.]

[0280] In the formula (b0 - an), nb10 is preferably 2 or more. nb10 may be, for example, 4 or less, or may be 3 or less. nb10 is preferably 1 or more and 4 or less, and more preferably 2. In the formula (b0 - an), nb20 is preferably 2 or more, and more preferably 3 or more. nb20 may be, for example, 5 or less, or may be 4 or less, or may be 3 or less. nb20 is preferably 1 or more and 5 or less, and more preferably 3.

[0281] In the formula (b0 - an), nb10 + nb20 is preferably an integer of 4 or more, and more preferably an integer of 5 or more. The relationship between nb10 and nb20 is preferably nb10 ≤ nb20, and more preferably nb10 < nb20.

[0282] Specific examples of the anionic part of the component (B0) are shown below.

[0283]

Chemical formula

[0284]

Chemical formula

[0285]

Chemical formula

[0286]

Chemical formula

[0287] Examples of the anionic part of the (B0) component include anions represented by chemical formulas (b0-an-1) to (b0-an-34), and anions represented by chemical formulas (b0-an-3), (b0-an-20), (b0-an-25), (b0-an-27), and (b0-an-34) are preferred. Alternatively, anions represented by chemical formulas (b0-an-9), (b0-an-18), (b0-an-19), (b0-an-20), (b0-an-26), or (b0-an-27) are preferred, and anions represented by chemical formula (b0-an-20) or (b0-an-27) are more preferred.

[0288] ((Cation part of the (B0) component)) In the above formula (b0), M m+ is preferably a cation represented by the general formulas (ca-1) to (ca-3), and an organic cation represented by the general formula (ca-1) is more preferred. Among them, from the viewpoints of sensitivity and LWR improvement, the cation in M m+ is preferably a cation represented by the general formula (ca-1), and among them, at least one of R 201 ~R 203 is preferably an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group, and more preferably at least one of R 201 ~R 203 is an aryl group having a fluorine atom.

[0289] Alternatively, from the viewpoints of improving sensitivity and reducing roughness, the organic cation in M m+ is more preferably an organic cation represented by the following general formula (b0-ca).

[0290]

Chemical formula

[0291] Rc f1 、Rc f2 and Rc f3are preferably each independently a fluorine atom.

[0292] In the above formula (b0-ca), examples of the substituent other than a trifluoromethyl group or a fluorine atom include a halogen atom other than a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0293] From the viewpoint of improving sensitivity and reducing roughness, 1≦m 01 +m 02 +m 03 ≦6, and 2≦m 01 +m 02 +m 03 More preferably, m 01 +m 02 +m 03 It is even more preferable that it is ≦4. m 01 , m 02 and m 03 are each preferably independently 1 or 2.

[0294] In the above formula (b0-ca), Rc f1 , Rc f2 and Rc f3 At least one of these is preferably present at the ortho- or meta-position to the sulfur atom in the formula.

[0295] As the cationic moiety represented by the formula (b0-ca), the cations represented by the formulas (ca-1-44), (ca-1-71) to (ca-1-77), (ca-1-80) or (ca-1-81) are preferable, the cations represented by the formulas (ca-1-72) to (ca-1-75) are more preferable, and the cation represented by the formula (ca-1-74) is even more preferable.

[0296] Specific examples of the component (B0) are given below.

[0297] [ka]

[0298] [Chem.]

[0299] In the resist composition of this embodiment, the component (B0) may be used alone or in combination of two or more. In the resist composition of this embodiment, the content of the component (B0) is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and still more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (B0) is equal to or higher than the lower limit value of the above preferred range, in resist pattern formation, the effects of improving sensitivity, reducing roughness, and suppressing film loss are all likely to be enhanced. On the other hand, when the content of the component (B0) is equal to or lower than the upper limit value of the above preferred range, it is easy to maintain good sensitivity.

[0300] ·Regarding the component (B1) The component (B) may contain an acid generator component (B1) other than the component (B0) (hereinafter also referred to as the "component (B1)"). The component (B1) 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 and poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, and many others. The form of the component (B) may be in the form of a compound, may be incorporated into the component (A1) as the above structural unit (a5), or may be in both of these forms.

[0301] Examples of the onium salt-based acid generator 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").

[0302] Examples of the onium salt-based acid generator 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").

[0303] [Chemical formula] [In the formula, R 101 and R 104 ~R 108 are each independently 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. R 104 and R 105 may be bonded to each other to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 is a divalent linking group containing an oxygen atom or a single bond. V 101 ~V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group. However, Y 101 and V 101 do not simultaneously become a single bond. L 101 ~L 102 are each independently a single bond or an oxygen atom. L 103 ~L 105 are each independently a single bond, -CO- or -SO 2 -. m is an integer of 1 or more, and M' m+ is an m-valent onium cation.]

[0304] {Anion part} · Anions in the component (b-1) In formula (b-1), R 101 is 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.

[0305] 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 is preferably saturated.

[0306] 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 101 Specific examples of the aromatic ring of 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, etc. R 101 Specific examples of the aromatic hydrocarbon group in 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 hydrogen atom 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.

[0307] R 101The cyclic aliphatic hydrocarbon group in [ID] includes aliphatic hydrocarbon groups containing a ring in the structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. 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, and the like. 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.

[0308] Among them, the cyclic aliphatic hydrocarbon group in R 101 is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0309] 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 preferred. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc. may be mentioned. The branched-chain aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still 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, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 - and other alkylethylene groups; -CH(CH3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups such as those mentioned above. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0310] Also, the cyclic hydrocarbon group in R 101 may contain a hetero atom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO 2 -containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16) are exemplified.

[0311] R 101 Examples of the substituent in the cyclic group of include, for example, 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. As the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, and most preferably a methoxy group and an ethoxy group. As the halogen atom as a substituent, a fluorine atom, a bromine atom, and an iodine atom are preferable. Examples of the halogenated alkyl group as a substituent include 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, or a tert-butyl group, are substituted with the halogen atom. The carbonyl group as a substituent is a group that substitutes a methylene group (—CH 2 —) constituting the cyclic hydrocarbon group.

[0312] R 101 The cyclic hydrocarbon group in R 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. Specific examples of the condensed cyclic group in R 101 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

[0313]

Chemical formula

[0314] R 101 Examples of the substituent that the condensed cyclic group in R may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the condensed cyclic group are the same as those exemplified as the substituent of the cyclic group in R 101 above. Examples of the aromatic hydrocarbon group as a substituent of the condensed ring 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 a substituent of the condensed ring group include a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, a group obtained by removing one hydrogen atom from a polycycloalkane such as tetracyclododecane; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7); -SO 2 -containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4); heterocyclic groups represented by the formulas (r-hr-7) to (r-hr-16), etc.

[0315] Optionally substituted chain alkyl group: R 101 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched-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.

[0316] Optionally substituted chain alkenyl group: R 101 The chain alkenyl group of R may be linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butenyl group, etc. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. Among them, the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.

[0317] R 101 Examples of the substituent in the chain alkyl group or alkenyl group of R 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.

[0318] In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 When Y is a divalent linking group containing an oxygen atom, 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, etc. Examples of the divalent linking group containing an oxygen atom include the linking groups respectively represented by the above general formulas (L-al-1) to (L-al-8). In the following general formulas (L-al-1) to (L-al-8), the one that binds to R in the above formula (b-1) 101 is V' 101 in the following general formulas (L-al-1) to (L-al-8).

[0319] In formula (b-1), V 101 is a single bond, an alkylene group or a fluorinated alkylene group. Among them, V 101is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0320] 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, and more preferably a fluorine atom.

[0321] Specific examples of the anion part 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.

[0322] [Chemical formula] [In the formula, R” 101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6) respectively, a condensed cyclic group represented by the formula (r-br-1) or (r-br-2), a chain alkyl group which may have a substituent or an aromatic cyclic group which may have a substituent. R” 102 is an aliphatic cyclic group which may have a substituent, a condensed cyclic group represented by the formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7) respectively, or a -SO 2 -containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4) respectively. R” 103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V” 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v” is each independently an integer of 0 to 3, q” is each independently an integer of 0 to 20, and n” is 0 or 1.]

[0323] R” 101 、R” 102 and R” 103 The aliphatic cyclic group which may have a substituent of 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).

[0324] R” 101 and R” 103 The aromatic cyclic group which may have a substituent of 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).

[0325] R” 101 The linear alkyl group which may have a substituent of 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 a substituent of is preferably a group exemplified as the linear alkenyl group in R 101 in the formula (b-1).

[0326] · The anion in the component (b-2) In the formula (b-2), R 104 、R 105 are each independently a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and each is R in the formula (b-1)101 The same applies. However, R 104 , R 105 may be bonded to each other to form a ring. R 104 , R 105 is preferably a linear or branched alkyl group or a linear or branched fluorinated alkyl group which may have a substituent, and more preferably a linear or branched alkyl group. The number of carbon atoms of the linear alkyl group is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 3. For R 104 , R 105 , the smaller the number of carbon atoms of the linear alkyl group within the above range of the number of carbon atoms, the more preferable because of good solubility in the resist solvent. Further, in the linear alkyl group of R 104 , R 105 , the larger the number of hydrogen atoms substituted by fluorine atoms, the stronger the acid strength, and the more preferable because the transparency to high-energy light or electron beams of 250 nm or less is improved. The ratio of fluorine atoms in the linear alkyl group, that is, 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 by fluorine atoms. In formula (b-2), V 102 , V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and are the same as those of V 101 in formula (b-1), respectively. In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0327] · Anion in component (b-3) In formula (b-3), R 106 to R 108 are each independently a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and are the same as those of R101 The same ones can be cited. In formula (b-3), L 103 ~L 105 are each independently a single bond, -CO- or -SO 2 -.

[0328] Among the above, as the anion part of the component (B), the anion in the component (b-1) is preferable, and the anion represented by the formula (an-1) is more preferable.

[0329] {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.

[0330] As the cation part of the component (B), a sulfonium cation is preferable, the cations respectively represented by the formulas (ca-1) to (ca-3) are more preferable, the cation represented by the formula (ca-1) is still more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are particularly preferable.

[0331] In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more. In the resist composition, the content of the component (B) is preferably less than 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 43 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, 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.

[0332] The resist composition of the present embodiment may further contain other components in addition to the above-described components (A) and (B). Examples of the other components include the component (D), the component (E), the component (F), the component (S), etc. shown below.

[0333] <Base component (D)> In addition to the component (A) and the component (B), the resist composition of this embodiment may contain a base component ((D) component) that traps the acid generated by exposure (that is, controls the diffusion of the acid). The (D) component acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. Examples of the (D) component include a photo-dissociable base (D1) that decomposes upon exposure and loses acid diffusion controllability (hereinafter referred to as the "(D1) component"), and a nitrogen-containing organic compound (D2) that does not correspond to the (D1) component (hereinafter referred to as the "(D2) component"). Among these, the photo-dissociable base ((D1) component) is preferred because it is easy to enhance all of the characteristics of high sensitivity, reduction of roughness, and suppression of the occurrence of coating defects. The form of containing the (D1) component and the (D2) component may be in the form of a compound, may be in the form incorporated into the (A1) component as the above-described structural unit (a6), or may be in both of these forms. The compounds exemplified as the (D1) component described later may be used as the above-described acid generator component ((B) component) in combination with other compounds in some cases.

[0334] ·Regarding the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability, and one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as the "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter referred to as the "(d1-2) component"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as the "(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.

[0335]

Chemical formula

[0336] {(component (d1-1))} ·· Anion part In the formula (d1-1), Rd 1 is 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, and examples thereof are the same as those of the above R' 201 . Among these, as Rd 1 , an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent 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, as the substituent, a linking group represented by the above formulas (L-al-1) to (L-al-5) is preferable. When the aromatic hydrocarbon group, aliphatic cyclic group, or chain-like alkyl group in Rd 1 has a linking group represented by the above general formulas (L-al-1) to (L-al-7) as a substituent, in the above general formulas (L-al-1) to (L-al-7), the V' in the general formula (L-al-1) to (L-al-7) is bonded to the carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain-like alkyl group in Rd 1 in the formula (d3-1).101 It is as follows. As the aromatic hydrocarbon group, 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) are preferably exemplified. As the aliphatic cyclic group, it is more preferably 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, and tetracyclododecane. As the linear alkyl group, the number of carbon atoms is preferably 1 to 10. Specifically, 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 can be mentioned.

[0337] When the linear alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0338] The following shows preferred specific examples of the anionic part of the component (d1-1).

[0339]

Chemical formula

[0340] ···Cationic part In formula (d1-1), M m+ is an m-valent organic cation. M m+Examples of the organic cation include the same cations as those represented by the general formulas (ca-1) to (ca-3) respectively, with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the formulas (ca-1-1) to (ca-1-84) being even more preferred. The component (d1-1) may be used alone or in combination of two or more.

[0341] {(Component (d1-2))} ··Anion part In the formula (d1-2), Rd 2 is a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and examples thereof are the same as those of the above R'. 201 However, it is assumed that the carbon atom adjacent to the S atom in Rd 2 is not bonded to a fluorine atom (not fluorine-substituted). Thereby, the anion of the component (d1-2) becomes a moderately weak acid anion, and the quenching ability as the component (D) is improved. As Rd 2 it is preferably a linear 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.

[0342] The linear alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. (which may have a substituent); and more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0343] The hydrocarbon group of Rd 2 may have a substituent, and examples of the substituent are the same as those of Rd in the formula (d1-1). 1 ​The same substituents as those which may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain-like alkyl group) in [are mentioned].

[0344] The following shows preferable specific examples of the anion part of the component (d1-2).

[0345]

Chemical formula

[0346] ·· Cation part In formula (d1-2), M m+ is an m-valent organic cation, which is the same as M m+ in the above formula (d1-1). The component (d1-2) may be used alone or in combination of two or more.

[0347] {(d1-3) component} ·· Anion part In formula (d1-3), Rd 3 is 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, and the same as the above R' 201 is mentioned, and it is preferably a cyclic group, a chain-like alkyl group, or a chain-like alkenyl group containing a fluorine atom. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of the above Rd 1 is more preferable.

[0348] In formula (d1-3), Rd 4 is 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, and the same as the above R' 201 is mentioned. Among them, it is preferably an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group which may have a substituent. Rd 4The alkyl group in Rd is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically includes 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. 4 Part of the hydrogen atoms of the alkyl group in 4 may be substituted with a hydroxyl group, a cyano group or the like. Rd 4 The alkoxy group in Rd is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Among them, a methoxy group and an ethoxy group are preferred.

[0349] Rd 4 The alkenyl group in Rd is the same as the alkenyl group in the above R'. 201 Examples thereof include a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

[0350] Rd 4 The cyclic group in Rd is the same as the cyclic group in the above R'. 201 Examples thereof include 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 2,6 decane, tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group. When Rd 4 is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in good lithography characteristics. Also, when Rd 4 is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition has excellent light absorption efficiency and good sensitivity and lithography characteristics.

[0351] 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 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.

[0352] Preferred specific examples of the anion part of the component (d1-3) are shown below.

[0353]

Chemical formula

[0354]

Chemical formula

[0355] ·· Cation part In the formula (d1-3), M m+ is an m-valent organic cation, which is the same as M in the above formula (d1-1). m+ is the same. The component (d1-3) may be used alone or in combination of two or more.

[0356] The component (D1) may use only any one of the above components (d1-1) to (d1-3), or may use a combination of two or more. 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 15 parts by mass, and even more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the component (A).

[0357] The component (D1) preferably contains the above component (d1-1). Of the whole component (D1), the content of the component (d1-1) is preferably 50% by mass or more, preferably 70% by mass or more, and even more preferably 90% by mass or more. The component (D1) may consist only of the compound (d1-1) component.

[0358] Production method of the component (D1): The production methods of the above components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Also, the production method of the component (d1-3) is not particularly limited and is produced, for example, in the same manner as the method described in US2012-0149916. As an example of the base component ((D) component) that traps the acid generated by exposure, the compound of the component (D1) was shown, but the compound of the component (D1) may be used as the component (B). For example, in the resist composition of the present embodiment, a compound of the component (D1) is used as the component (B), and as the component (D), a compound that generates an acid having a lower acidity than the acid generated by exposure of the compound of the component (D1) may be used. Further, in the resist composition of the present embodiment, a compound of the component (D1) is used as the component (B), and as the component (D), the component (D2) described later may be used.

[0359] ·Regarding the component (D2) As the component (D), a nitrogen-containing organic compound component that does not correspond to the above component (D1) (hereinafter referred to as the "component (D2)") may be contained. (Component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not correspond to component (D1), and any known one can be arbitrarily used. Among them, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are particularly preferred.) An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.) As the aliphatic amine, at least one hydrogen atom of ammonia NH 3 is replaced by an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms (alkylamine or alkyl alcohol amine), or a cyclic amine.) Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.)

[0360] Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).) Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.) As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc. can be mentioned.

[0361] As other aliphatic amines, 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. can be mentioned, and triethanolamine triacetate is preferable.

[0362] Also, as the component (D2), an aromatic amine may be used. As the aromatic amine, 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. can be mentioned.

[0363] 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 it within the above range, the resist pattern shape, standing storage stability over time, etc. are improved.

[0364] <At least one compound (E) selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus and its derivatives> In the resist composition of the present embodiment, for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, stability over time during standing, 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.

[0365] 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, the lithography characteristics can be further improved.

[0366] <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, the lithography characteristics can be improved. As the (F) component, for example, the fluorine-containing polymer compounds described in JP-A No. 2010-002870, JP-A No. 2010-032994, JP-A No. 2010-277043, JP-A No. 2011-13569, and JP-A No. 2011-128226 can be used. (F) More specifically as the component, polymers 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.

[0367] [Chemical formula] [In the formula, R is the same as described above, Rf 102 and Rf 103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 may be the same or different. nf 1 is an integer of 0 to 5, and Rf 101 is an organic group containing a fluorine atom.]

[0368] In the formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. As R, a hydrogen atom or a methyl group is preferable. In the 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 R above 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.

[0369] 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. In addition, 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, Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, a trifluoromethyl group, -CH 2 -CF 3 、-CH 2 -CF 2 -CF 3 、-CH(CF 3 ) 2 、-CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CF 2 -CF 2 -CF 2 -CF3 is particularly preferred.

[0370] (F) component's weight-average molecular weight (Mw) (in terms of polystyrene conversion standard by gel permeation chromatography) is preferably 1000 to 50000, more preferably 5000 to 40000, and most preferably 10000 to 30000. When it is below the upper limit 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 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0371] 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 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the (A) component.

[0372] <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.

[0373] Also, as the (S) component, a mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, etc. (S) component preferably includes a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably 70:30 to 95:5. (S) The amount of the component used is not particularly limited, and it 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.

[0374] After dissolving the above resist material in the (S) component, the resist composition of this embodiment may be subjected to removal of impurities or the like using a polyimide porous membrane, a polyamideimide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a 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.

[0375] The resist composition of this embodiment described above contains a compound (B0) represented by the general formula (b0). The compound (B0) has a benzene ring in which a hydrogen atom is substituted with a trifluoromethyl group or a fluorine atom and a structure of an iodine-containing aromatic ring. By containing the compound (B0), a resist composition having enhanced effects of improving sensitivity, reducing roughness, and suppressing film loss is realized. The reason for such an effect is presumed as follows. The compound (B0) has a structure of an iodine-containing aromatic ring, thereby improving sensitivity. In addition, since the compound (B0) has the above-described benzene ring and aromatic ring structures, the molecular weight increases and the glass transition temperature rises, so that the diffusion of the compound (B0) is suppressed and the effect of reducing roughness is enhanced. Furthermore, since the compound (B0) has the structures of the benzene ring and the aromatic ring described above, its hydrophobicity is enhanced, so that the effect of suppressing film loss in the unexposed areas by water rinsing is enhanced. It is presumed that when the above-described respective actions work synergistically, the effects of improving the sensitivity, reducing the roughness, and suppressing film loss of the resist composition are all enhanced.

[0376] (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.

[0377] 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 by exposure through a mask (mask pattern) having a predetermined pattern formed thereon or by direct irradiation with an electron beam without using a mask pattern, using an exposure apparatus such as an electron beam drawing 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.

[0378] After the development process, preferably a rinsing process is performed. In the case of an alkaline development process, water rinsing using pure water is preferable, 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 rinsing process, a process of removing the developer or the rinsing solution adhering to the pattern with a supercritical fluid may be performed. After the development process or the rinsing process, drying is performed. Further, in some cases, a baking process (post-bake) may be performed after the development process.

[0379] The support is not particularly limited, and conventionally known ones can be used. For example, substrates for electronic components, those with a predetermined wiring pattern formed thereon, etc. can be mentioned. More specifically, silicon wafers, metal substrates such as copper, chromium, iron, aluminum, and glass substrates can be mentioned. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0380] The wavelength used for exposure is not particularly limited, and it can be performed using radiation such as ArF excimer laser, KrF excimer laser, F 2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The resist pattern forming method of this embodiment is particularly useful for a method of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam) in the step of exposing the resist film.

[0381] 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 immersion medium, a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed is preferable. Examples thereof include water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is preferably used as the immersion medium.

[0382] Examples of the alkaline developer used for development in the alkaline development process include an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH). The organic solvent contained in the organic developer used for development in the solvent development process may be any one that can dissolve the component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents can be mentioned.

[0383]

[0384] Examples of the nitrile-based solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0385] ​Known additives can be incorporated into the organic developer as necessary. Examples of such additives include surfactants. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

[0386] The development process can be carried out by known development methods. For example, a method of immersing the support in the developer for a certain period of time (dip method), a method of raising the developer on the surface of the support 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 surface of the support (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dispense method), etc. can be mentioned.

[0387] 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 in 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. They may also be used in mixture with organic solvents other than those described above and water.

[0388] 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 surface of the support (spray method), etc.

[0389] According to the resist pattern forming method of the present embodiment described above, since the above-described resist composition is used, when forming a resist pattern, the effects of improving sensitivity, reducing roughness, and suppressing film loss can be enhanced.

[0390] In the resist composition of the above-described embodiment and the various materials used in the pattern forming method of the above-described embodiment (for example, resist solvent, developer, rinse liquid, composition for forming an antireflection film, composition for forming a top coat, 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 still 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).

[0391] (Compound) The compound according to the third aspect of the present invention is a compound represented by the following general formula (b0) (hereinafter, also referred to as "compound (B0)").

[0392] [Chemical formula] [In the formula, Ar 1 and Ar 2 are each an aromatic ring. R b1 and R b2 are each a substituent other than an iodine atom. R f is a trifluoromethyl group or a fluorine atom. R b3 is a substituent other than a trifluoromethyl group and a fluorine atom. L 1 and L 2 are each a divalent linking group. nb1 and nb2 are each an integer of 1 or more as long as the valence allows. nb3 is an integer of 1 to 4. 3 ≤ nb1 + nb2. nr1 and nr2 are each an integer of 0 or more as long as the valence allows. nr3 is an integer of 0 to 3. When nb3 is an integer of 2 or more, a plurality of R fMay be the same or different. When nr1 is an integer of 2 or more, a plurality of R b1 May be the same or different. When nr2 is an integer of 2 or more, a plurality of R b2 May be the same or different. When nr3 is an integer of 2 or more, a plurality of R b3 May be the same or different. M m+ Represents an m-valent organic cation. m is an integer of 1 or more.]

[0393] <Method for producing a compound> Compound (B0) can be produced by appropriately combining known methods as in the <Compound synthesis example> shown in [Examples] described later. Compound (B0) can be produced, for example, by an esterification reaction or a salt exchange reaction.

[0394] (Acid generator) The acid generator according to the fourth aspect of the present invention contains the compound (B0). The acid generator of this embodiment can be used in the production of the resist composition according to the first aspect. By incorporating the acid generator of this embodiment into the resist composition, the effects of improving sensitivity, reducing roughness, and suppressing film loss can be enhanced.

Examples

[0395] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples.

[0396] <Compound synthesis example> Compounds represented by chemical formulas (B0)-1 to (B0)-9 were each produced by the synthesis methods shown below.

[0397] [Synthesis Example 1: Synthesis of Compound (B0)-1] (B-m01) (Sodium 4-hydroxy-2,3,5,6-tetrafluorobenzenesulfonate) (53.6 g) was dissolved in water (536 g), and a solution of benzyltrimethylammonium chloride (48.3 g) dissolved in water (483 g) was added dropwise thereto over 5 minutes. After the solution was stirred for 2 hours, the precipitated solid was collected by filtration and washed twice with water (161 g). The obtained solid was dried under reduced pressure overnight to obtain 60.1 g of (B-pre1) (yield 76%).

[0398] (B-pre1) (40.0 g), (B-m11) (3,5-diiodosalicylic acid) (47.3 g), and DMAP (0.62 g) were dissolved in dichloromethane (400 g), and DIC (15.3 g) was added dropwise thereto over 15 minutes under ice cooling. After the mixture was stirred at room temperature for 6 hours, the precipitated solid was filtered off. After the filtrate was concentrated under reduced pressure, crystallization was performed multiple times using methanol / t-butyl methyl ether to obtain 37.3 g of (B-pre2) (yield 48%)

[0399] NMR measurement was performed on the obtained compound (B-pre1), and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 3.05 (s, CH 3 , 9H), 4.55 (s, CH 2 , 2H), 7.51 - 7.55 (m, Ar-H, 5H), 11.51 (brd, OH, 1H) 19 F-NMR (DMSO-d 6 , 376 MHz): δ (ppm) = -141.7 (d, 2F), -162.1 (d, 2F)

[0400] (Bpre-2) (37.0 g), (B-m21) (4-iodobenzoic acid) (14.4 g), and DMAP (0.29 g) were dissolved in dichloromethane (370 g), and DIC (7.30 g) was added dropwise thereto over 15 minutes under ice cooling. After the mixture was stirred at room temperature for 3 hours, the precipitated solid was filtered off. After the filtrate was concentrated under reduced pressure, the obtained solid was crystallized multiple times using methanol / t-butyl methyl ether to obtain 25.0 g of (B-pre3) (yield 52%)

[0401] NMR measurement was performed on the obtained compound (B-pre2), and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 3.05 (s, CH 3 , 9H), 4.55 (s, CH 2 , 2H), 7.51 - 7.55 (m, Ar-H, 5H), 8.28 (d, Ar-H, 1H), 8.45 (d, Ar-H, 1H), 10.63 (brd, OH, 1H)

[0402] (B-pre3) (25.0 g) and (B-s1) (triphenylsulfonium bromide) (9.47 g) were dissolved in dichloromethane (150 g). Water (100 g) was added, and the mixture was stirred at room temperature for 1 hour for a salt exchange reaction, after which the aqueous layer was removed. The organic layer was repeatedly washed with water and then concentrated under reduced pressure and dried under reduced pressure to obtain 27.0 g of compound (B0)-1 (yield 97%).

[0403] NMR measurement was performed on the obtained compound (B-pre3), and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 3.05 (s, CH 3 , 9H), 4.55 (s, CH 2 , 2H), 7.51 - 7.55 (m, Ar-H, 5H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0404] [Chemical formula]

[0405] For the obtained compound (B0)-1, NMR measurement was carried out and its structure was identified based on the following data. 1 1H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 7.74 - 7.90 (m, Ar-H, 15H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0406] [Synthesis Example 2: Synthesis of Compound (B0)-2] Compound (B0)-2 was obtained in the same manner as in Synthesis Example 1, except that (B-m21) was changed to (B-m22).

[0407] [Chemical formula]

[0408] For the obtained compound (B0)-2, NMR measurement was carried out and its structure was identified based on the following data. 1 1H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 7.74 - 7.90 (m, Ar-H, 15H), 8.04 (d, Ar-H, 1H), 8.28 (d, Ar-H, 1H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0409] [Synthesis Example 3: Synthesis of Compound (B0)-3] Compound (B0)-3 was obtained in the same manner as in Synthesis Example 1, except that (B-m11) was changed to (B-m12) and (B-m21) was changed to (B-m23).

[0410] [Chemical formula]

[0411] For the obtained compound (B0)-3, NMR measurement was carried out, and its structure was identified based on the following data. 1 H-NMR(DMSO-d 6 , 400 MHz): δ(ppm) = 7.74 - 7.90 (m, Ar-H, 15H), 7.92 - 7.95 (m, Ar-H, 4H), 8.23 (s, Ar-H, 1H)

[0412] [Synthesis Example 4: Synthesis of Compound (B0)-4] (B-pre2) (23.0 g) was dissolved in DMF (138 g), and potassium carbonate (6.49 g) and 4-iodobenzyl bromide (12.8 g) were sequentially added. After the mixture was stirred at room temperature for 5 hours, water (138 g) was added. The precipitated solid was washed twice with water (46 g), and then crystallized multiple times using methanol / t-butyl methyl ether to obtain 26.4 g of (B-pre4) (yield 86%). Using (B-s1), (B-pre4) was subjected to the same salt exchange reaction as in Synthesis Example 1 to obtain (B0)-4.

[0413]

Chemical formula

[0414] For the obtained compound (B0)-4, NMR measurement was carried out, and its structure was identified based on the following data. 1 H-NMR(DMSO-d 6 , 400 MHz): δ(ppm) = 5.16 (s, CH 2 , 2H), 7.05 (d, Ar-H, 2H), 7.60 (d, Ar-H, 2H), 7.74 - 7.90 (m, Ar-H, 15H), 8.27 (d, Ar-H, 1H), 8.51 (d, Ar-H, 1H)

[0415] For the obtained compound (B-pre4), NMR measurement was carried out, and its structure was identified based on the following data. 1 H-NMR(DMSO-d 6, 400 MHz): δ (ppm) = 3.05 (s, CH 3 , 9H), 4.55 (s, CH 2 , 2H), 7.51 - 7.55 (m, Ar - H, 5H), 5.16 (s, CH 2 , 2H), 7.05 (d, Ar - H, 2H), 7.60 (d, Ar - H, 2H), 8.27 (d, Ar - H, 1H), 8.51 (d, Ar - H, 1H)

[0416] [Synthesis Example 5: Synthesis of Compound (B0)-5] (B - m01) was changed to (B - m02), (B - m11) was changed to (B - m13), and (B - m21) was changed to (B - m24). Otherwise, in the same manner as in Synthesis Example 1, Compound (B0)-5 was obtained.

[0417]

Chemical Structure

[0418] For the obtained Compound (B0)-5, NMR measurement was carried out, and its structure was identified based on the following data. 1 H - NMR (DMSO - d 6 , 400 MHz): δ (ppm) = 7.74 - 7.90 (m, Ar - H, 15H), 8.08 (d, Ar - H, 2H), 8.34 (d, Ar - H, 1H), 8.58 (d, Ar - H, 1H)

[0419] [Synthesis Example 6: Synthesis of Compound (B0)-6] (B - s1) was changed to (B - s2). Otherwise, in the same manner as in Synthesis Example 1, Compound (B0)-6 was obtained.

[0420]

Chemical Structure

[0421] For the obtained Compound (B0)-6, NMR measurement was carried out, and its structure was identified based on the following data. 1 H - NMR (DMSO - d 6, 400 MHz): δ (ppm) = 7.74 - 8.11 (m, Ar-H, 17H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0422] [Synthesis Example 7: Synthesis of Compound (B0)-7] Compound (B0)-7 was obtained in the same manner as in Synthesis Example 1, except that (B-s1) was changed to (B-s3).

[0423] [Chemical Formula]

[0424] NMR measurement was performed on the obtained compound (B0)-7, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 7.63 - 7.77 (m, Ar-H, 12H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0425] [Synthesis Example 8: Synthesis of Compound (B0)-8] Compound (B0)-8 was obtained in the same manner as in Synthesis Example 1, except that (B-s1) was changed to (B-s4).

[0426] [Chemical Formula]

[0427] NMR measurement was performed on the obtained compound (B0)-8, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 7.53 - 7.74 (m, Ar-H, 11H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0428] [Synthesis Example 9: Synthesis of Compound (B0)-9] Compound (B0)-9 was obtained in the same manner as in Synthesis Example 1, except that (B-s1) was changed to (B-s5).

[0429]

Chemical formula

[0430] NMR measurement was performed on the obtained compound (B0)-9, and its structure was identified based on the following data. 1 1H-NMR (DMSO-d 6 , 400 MHz): δ (ppm) = 7.36 - 7.54 (m, Ar-H, 9H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0431] <Preparation of resist composition> (Examples 1 to 13, Comparative Examples 1 to 4) The components shown in Table 1 were mixed and dissolved to prepare the resist compositions of each example, respectively.

[0432]

Table 1

[0433] In Table 1, each abbreviation has the following meaning. The numerical values in [ ] are the blending amounts (parts by mass). (A)-1 to (A)-4: The following polymer compounds (A1-1) to (A1-4).

[0434]

Chemical formula

[0435] A2, A7, A5 (A)-1: The above polymer compound (A1-1). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6600, and the molecular weight dispersity (Mw / Mn) was 1.53. The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was m / n = 50 / 50. (A)-2: The polymer compound (A1-2). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6400, and the molecular weight distribution (Mw / Mn) was 1.49. The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was m / n = 50 / 50. (A)-3: The polymer compound (A1-3). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 7000, and the molecular weight distribution (Mw / Mn) was 1.59. The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was m / n = 50 / 50. (A)-4: The polymer compound (A1-4). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6700, and the molecular weight distribution (Mw / Mn) was 1.52. The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by 13C-NMR was m / n = 50 / 50.

[0436] (B0)-1 to (B0)-9: Acid generators each composed of the compounds (B0)-1 to (B0)-9, respectively.

[0437] (B1)-1: Acid generator composed of the following compound (B1)-1. (B1)-2: Acid generator composed of the following compound (B1)-2. (B1)-3: Acid generator composed of the following compound (B1)-3. (B1)-4: Acid generator composed of the following compound (B1)-4.

[0438]

Chemical formula

[0439] The compounds (B1)-1 to (B1)-4 were synthesized. For (B1)-1, NMR measurement was performed, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 、400 MHz): δ (ppm) = 7.74 - 7.90 (m, Ar-H, 15H), 7.62 - 7.76 (m, Ar-H, 4H), 7.82 (dd, Ar-H, 1H), 8.02 (d, Ar-H, 1H), 8.16 (dd, Ar-H, 2H)

[0440] (B1)-2 was subjected to NMR measurement, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 、400 MHz): δ (ppm) = 7.56 (d, Ar-H, 2H), 7.74 - 7.90 (m, Ar-H, 15H), 8.04 (d, Ar-H, 1H), 8.06 (d, Ar-H, 2H), 8.28 (d, Ar-H, 1H)

[0441] (B1)-3 was subjected to NMR measurement, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 、400 MHz): δ (ppm) = 5.44 (m, CH 2 , 2H), 7.74 - 7.90 (m, Ar-H, 15H), 7.92 - 7.95 (m, Ar-H, 4H), 8.34 (d, Ar-H, 1H), 8.58 (d, Ar-H, 1H)

[0442] (B1)-4 was subjected to NMR measurement, and its structure was identified based on the following data. 1 H-NMR (DMSO-d 6 、400 MHz): δ (ppm) = 7.15 (d, Ar-H, 1H), 7.74 - 7.90 (m, Ar-H, 15H), 7.92 - 7.95 (m, Ar-H, 4H), 8.09 (dd, Ar-H, 1H), 8.59 (d, Ar-H, 1H)

[0443] (D)-1: An acid diffusion controller comprising a compound represented by the following chemical formula (D1-1). (D)-2: An acid diffusion controller comprising a compound represented by the following chemical formula (D1-2). (S)-1: Propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio) mixed solvent.

[0444]

Chemical formula

[0445] <Formation of resist pattern> On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), each resist composition was applied using a spinner, and prebaked (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 35 nm. Next, using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), exposure (lithography) was performed on the resist film at an acceleration voltage of 100 kV with a target size of a 1:1 line and space pattern (hereinafter referred to as "LS pattern") with a line width of 50 nm, and then post-exposure bake (PEB) treatment was performed at 100 °C for 60 seconds. Subsequently, at 23 °C, using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), alkali development was performed for 60 seconds, and then water rinsing treatment was performed for 15 seconds using pure water. As a result, a 1:1 LS pattern with a line width of 50 nm was formed. In the above method for forming a resist pattern, the exposure dose at which an LS pattern with a target size is formed was determined as the optimum exposure dose Eop (μC / cm 2 ) and the result is shown in Table 2 as "Eop (μC / cm 2 )".

[0446] [Evaluation of LWR (Line Width Roughness)] For the LS pattern formed in the above <Formation of resist pattern>, 3σ, which is a measure indicating LWR, was determined. "3σ" represents three times the standard deviation (σ) (unit: nm) obtained from measuring the line positions at 400 locations in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800 V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 2 as "LWR (nm)". The smaller the value of 3σ, the smaller the roughness of the line sidewall, meaning that an LS pattern with a more uniform width was obtained.

[0447] [Evaluation of film loss suppression] In the <formation of resist pattern>, the film thickness of the resist film after PAB in the large-area unexposed portion outside the pattern and the film thickness of the resist film after water rinsing were measured, and the film thickness change rate of the resist film after water rinsing with respect to the film thickness of the resist film after PAB was determined. This is shown in Table 2 as "remaining film rate (%)". The larger the value of the remaining film rate, the more the unexposed portion of the resist film remains undissolved in the developer after development, meaning that the development loss (film loss) is suppressed.

[0448]

Table 2

[0449] From the results shown in Table 2, it was confirmed that the resist compositions of Examples 1 to 13 to which the present invention was applied had higher and better effects of improving sensitivity, reducing roughness, and suppressing film loss in resist pattern formation compared to the resist compositions of Comparative Examples 1 to 4.

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, comprising: a base material component (A) whose solubility in a developer changes due to the action of an acid; and an acid generator component (B) that generates an acid upon exposure, wherein the acid generator component (B) contains a compound (B0) represented by the following general formula (b0). 【Chemical 1】 [In the formula, Ar １ and Ar ２ are each an aromatic ring. R ｂ１ and R ｂ２ are each a substituent other than an iodine atom. R ｆ is a trifluoromethyl group or a fluorine atom. R ｂ３ is a substituent other than a trifluoromethyl group and a fluorine atom. L １ and L ２ are each a divalent linking group. nb1 and nb2 are each an integer of 1 or more as long as the valence allows. nb3 is an integer of 1 to 4. 3 ≤ nb1 + nb2. nr1 and nr2 are each an integer of 0 or more as long as the valence allows. nr3 is an integer of 0 to 3. When nb3 is an integer of 2 or more, a plurality of R ｆ may be the same or different. When nr1 is an integer of 2 or more, a plurality of R ｂ１ may be the same or different. When nr2 is an integer of 2 or more, a plurality of R ｂ２ may be the same or different. When nr3 is an integer of 2 or more, a plurality of R ｂ３ may be the same or different. M ｍ＋ represents an m-valent organic cation. m is an integer of 1 or more. ]

2. The resist composition according to Claim 1, wherein nb1 < nb2 in the general formula (b0).

3. The resist composition according to Claim 2, wherein nb1 is an integer of 2 or more in the general formula (b0).

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

5. A compound represented by the following general formula (b0). 【Chemical 2】 [wherein, Ar １ and Ar ２ are each an aromatic ring. R ｂ１ and R ｂ２ are each a substituent other than an iodine atom. R ｆ is a trifluoromethyl group or a fluorine atom. R ｂ３ is a substituent other than a trifluoromethyl group and a fluorine atom. L １ and L ２ are each a divalent linking group. nb1 and nb2 are each an integer of 1 or more as long as the valence allows. nb3 is an integer of 1 to 4. 3 ≤ nb1 + nb2. nr1 and nr2 are each an integer of 0 or more as long as the valence allows. nr3 is an integer of 0 to 3. When nb3 is an integer of 2 or more, a plurality of R ｆ may be the same or different. When nr1 is an integer of 2 or more, a plurality of R ｂ１ may be the same or different. When nr2 is an integer of 2 or more, a plurality of R ｂ２ may be the same or different. When nr3 is an integer of 2 or more, a plurality of R ｂ３ may be the same or different. M ｍ＋ represents an m-valent organic cation. m is an integer of 1 or more. ]

6. The compound according to Claim 5, wherein nb1 < nb2 in the general formula (b0).

7. The compound according to Claim 6, wherein nb1 is an integer of 2 or more in the general formula (b0).

8. An acid generator containing the compound according to any one of Claims 5 to 7.

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