Resist composition and method for forming resist pattern

Abstract

Provided is a resist composition which generates an acid upon exposure to light, and the solubility of which in a developer solution is changed by the action of the acid. The resist composition contains: a resin component (A1), the solubility of which in a developer solution is changed by the action of an acid; a compound (D01) which is represented by formula (d01); and a compound (D02) which is represented by formula (d02-1) or (d02-2). The resin component (A1) has a constituent unit (a10) which is represented by formula (a10-1). In the formulae, Rx01 to Rx03 are each a chain hydrocarbon group; Ry01 to Ry03 are each a hydrocarbon group; ny0 is an integer of 0 to 3; Rz01 and Rz02 are each a hydrocarbon group or a hydrogen atom; Rz03 is a hydrocarbon group; nz0 is an integer of 0 to 5; R is a hydrogen atom, or an alkyl group or the like; Yax1 is a single bond or a divalent linking group; Wax1 is an aromatic hydrocarbon group; and nax1 is an integer of 1 or more.

Description

Resist composition and method for forming a resist pattern

[0001] This application claims priority to Japanese Patent Application No. 2024-051159, filed on March 27, 2024, the contents of which are incorporated herein by reference.

[0002] In recent years, advances in lithography technology have led to rapid progress in miniaturization of patterns in the manufacture of semiconductor devices and liquid crystal display devices. A common method for miniaturization is to shorten the wavelength (increase the energy) of the exposure light source. Specifically, while ultraviolet rays such as g-line and i-line have traditionally been used, mass production of semiconductor devices is now being carried out using KrF excimer lasers or ArF excimer lasers. EUV (extreme ultraviolet), EB (electron beam), and X-rays, which have shorter wavelengths (higher energies) than these excimer lasers, are also being investigated.

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

[0004] In the formation of a resist pattern, the behavior of the acid generated from an acid generator component upon exposure is considered to be a factor that significantly affects lithography properties. In response to this, chemically amplified resist compositions have been proposed that contain, in addition to an acid generator component, an acid diffusion controller that controls the diffusion of the acid generated from the acid generator component upon exposure. For example, Patent Document 1 discloses a chemically amplified positive resist composition that contains an amine compound as an acid diffusion controller.

[0005] JP 2004-347852 A

[0006] Currently, with the increasing integration density of LSIs and faster communication speeds, there is a demand for increased memory capacity, and further miniaturization of patterns is progressing rapidly. In response to this, development is underway on three-dimensional structure devices that aim to increase memory capacity by stacking cells in addition to miniaturization. In the manufacture of three-dimensional structure devices, a thicker resist film than conventional is deposited on the surface of the workpiece, and a resist pattern is formed, followed by etching, etc. In the NAND memory market, where three-dimensional structures are mainstream, there is a demand for even thicker resist films.

[0007] In thick resist films, the thicker the film, the more difficult it is for the exposure light to reach the bottom. Therefore, thick resist films are prone to developing a footing (scum) near the substrate at the interface between the exposed and unexposed areas. Furthermore, in thick resist films, the exposure sensitivity decreases closer to the substrate, so when the resist pattern is resolved to the target dimensions, it is prone to becoming tapered.

[0008] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a resist composition that is capable of suppressing the generation of scum and forming a resist pattern with a good shape, and a method of forming a resist pattern using the resist composition.

[0009] In order to solve the above-mentioned problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, the resist composition containing a resin component (A1) whose solubility in a developer changes due to the action of the acid, a compound (D01) represented by the following general formula (d01), and at least one compound (D02) represented by the following general formula (d02-1) or (d02-2), wherein the resin component (A1) has a structural unit (a10) represented by the following general formula (a10-1):

[0010] [In the formula, Rx ０１ ~Rx ０３ Ry each independently represents a chain hydrocarbon group which may have a substituent. ０１ ~Ry ０３each independently represents a hydrocarbon group which may have a substituent; ny0 represents an integer of 0 to 3; Rz ０１ and Rz ０２ Rz each independently represents a hydrocarbon group which may have a substituent, or a hydrogen atom. ０３ represents a hydrocarbon group which may have a substituent; and nz0 represents an integer of 0 to 5.

[0011] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ｘ１ represents a single bond or a divalent linking group. ｘ１ represents an aromatic hydrocarbon group which may have a substituent. ａｘ１ represents an integer of 1 or more.

[0012] A second aspect of the present invention is a method of forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition related to the first aspect, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.

[0013] According to the present invention, it is possible to provide a resist composition that is capable of suppressing the generation of scum and forming a resist pattern with a good shape, and a method of forming a resist pattern that uses the resist composition.

[0014] In this specification and claims, "aliphatic" is a relative concept to aromatic, and is defined as meaning a group, compound, etc. that does not have aromaticity. "Alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The same applies to alkyl groups in alkoxy groups. "Alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups, unless otherwise specified. "Halogen atom" includes fluorine, chlorine, bromine, and iodine atoms. "Structural unit" means a monomer unit that constitutes a polymer compound (resin, polymer, copolymer). When it is written that "may have a substituent," it means a case where a hydrogen atom (-H) is replaced with a monovalent group, or a case where a methylene group (-CH２ The term "exposure" encompasses both cases where the radical (-) is substituted with a divalent group.

[0015] An "acid-decomposable group" is a group having acid decomposability in which at least a part of the bond in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of acid-decomposable groups whose polarity increases by the action of an acid include groups that decompose by the action of an acid to generate a polar group. Examples of polar groups include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO ３ More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, groups in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).

[0016] The term "acid-dissociable group" refers to either (i) a group having acid dissociability in which 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 a portion of the bond is cleaved by the action of an acid, followed by a decarboxylation reaction, in which 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 must be a group with lower polarity than the polar group generated by dissociation of the acid-dissociable group. Thus, when the acid-dissociable group is dissociated by the action of an acid, a polar group with higher polarity than the acid-dissociable group is generated, thereby increasing the polarity. As a result, the polarity of the entire component (A1) increases. The increase in polarity relatively changes the solubility in the developer, increasing the solubility when the developer is an alkaline developer and decreasing the solubility when the developer is an organic developer.

[0017] A "base component" is an organic compound having film-forming ability. Organic compounds used as base components are broadly divided into non-polymers and polymers. As non-polymers, compounds having a molecular weight of 500 or more and less than 4000 are typically used. Hereinafter, the term "low molecular weight compound" refers to a non-polymer having a molecular weight of 500 or more and less than 4000. As polymers, compounds having a molecular weight of 1000 or more are typically used. Hereinafter, the terms "resin," "high molecular weight compound," or "polymer" refer to a polymer having a molecular weight of 1000 or more. The molecular weight of a polymer is determined by the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography).

[0018] The term "derived structural unit" refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R αｘ ) is an atom or group other than a hydrogen atom. αｘ ) is substituted with a substituent containing an ester bond, or αｘ This also includes α-hydroxyacrylic esters in which the α-position carbon atom of an acrylic ester is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group. Unless otherwise specified, the α-position carbon atom of an acrylic ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, acrylic esters in which the hydrogen atom bonded to the α-position carbon atom has been replaced with a substituent may be referred to as α-substituted acrylic esters.

[0019] The term "derivative" is used to refer to a compound in which the hydrogen atom at the α-position of the target compound has been substituted with another substituent such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include a compound in which the hydrogen atom of the hydroxyl group of a target compound in which the hydrogen atom at the α-position may be substituted with a substituent has been substituted with an organic group; a compound in which the hydrogen atom at the α-position of the target compound may be substituted with a substituent to which a substituent other than a hydroxyl group is bonded; and the like. Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. Examples of substituents that can be used to replace the hydrogen atom at the α-position of hydroxystyrene include R αｘ The same can be mentioned.

[0020] In this specification and claims, some structures represented by chemical formulas may have asymmetric carbon atoms, and may exist as enantiomers or diastereoisomers. In such cases, a single chemical formula represents all of the isomers. These isomers may be used alone or as a mixture.

[0021] (Resist Composition) The resist composition of this embodiment generates acid upon exposure, and its solubility in a developer changes due to the action of the acid. This resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer changes due to the action of an acid, a compound (D01), and a compound (D02). The component (A) contains a resin component (A1) whose solubility in a developer changes due to the action of an acid. The component (A1) has a structural unit (a10) represented by general formula (a10-1) described below. The compound (D01) is a compound represented by general formula (d01). The compound (D02) is a compound represented by general formula (d02-1) or (d02-2).

[0022] In the resist composition of this embodiment, the component (A) may generate an acid upon exposure, or an additive component formulated separately from the component (A) may generate an acid upon exposure. Specifically, the resist composition of this embodiment may further contain (1) an acid generator component (B) (hereinafter referred to as "component (B)") that generates an acid upon exposure; (2) the component (A) may be a component that generates an acid upon exposure; or (3) the component (A) may be a component that generates an acid upon exposure and further contain component (B). That is, in the cases of (2) and (3) above, the component (A) is a "base component that generates an acid upon exposure and whose solubility in a developer is changed by the action of the acid." When the component (A) is a base component that generates an acid upon exposure and whose solubility in a developer is changed by the action of the acid, the component (A1) is preferably a resin that generates an acid upon exposure and whose solubility in a developer is changed 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. The structural unit that generates acid upon exposure may be the structural unit (a5) described below.

[0023]

[0043] When a resist film is formed using the resist composition of this embodiment and the resist film is subjected to selective exposure, for example, an acid is generated from the component (B) in the exposed areas of the resist film, and the solubility of the component (A) in a developer changes due to the action of the acid, whereas the solubility of the component (A) in a developer does not change in the unexposed areas of the resist film, resulting in a difference in solubility in a developer between the exposed and unexposed areas. Therefore, when the resist film is developed, if the resist composition is positive, the exposed areas of the resist film are dissolved and removed, forming a positive resist pattern, whereas if the resist composition is negative, the unexposed areas of the resist film are dissolved and removed, forming a negative resist pattern.

[0024] The resist composition of this embodiment may be a positive resist composition or a negative resist composition. Furthermore, the resist composition of this embodiment may be for use in an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or for use in a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.

[0025] <Base Component (A)> In the resist composition of this embodiment, the component (A) preferably contains a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in a developer changes under the action of acid. By using the component (A1), the polarity of the base component changes before and after exposure, making it possible to obtain good development contrast not only in an alkaline development process but also in a solvent development process. As the component (A), other polymeric compounds and / or low molecular weight compounds may be used in combination with the component (A1).

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

[0027] Regarding the Component (A1): The component (A1) is a resin component whose solubility in a developer changes under the action of acid, and includes a structural unit (a10) represented by the general formula (a10-1) described below. The component (A1) preferably includes a structural unit (a1) containing an acid-decomposable group whose polarity increases under the action of acid. In addition to the structural unit (a10) and the structural unit (a1), the component (A1) may also include other structural units as necessary.

[0028] <<Structural Unit (a1)>> The structural unit (a1) is a structural unit that contains an acid-decomposable group whose polarity increases when acted upon by an acid. The component (A1) preferably includes the structural unit (a1).

[0029] Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups for base resins of chemically amplified resist compositions. Specific examples of acid-dissociable groups that have been proposed as acid-dissociable groups for base resins of chemically amplified resist compositions include the "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," "tertiary alkyloxycarbonyl acid-dissociable groups," and "secondary alkyl alkyl ester-type acid-dissociable groups," which are explained below.

[0030] Acetal-Type Acid-Dissociable Group: Among the polar groups, examples of the acid-dissociable group that protects a carboxy group or a hydroxyl group include acid-dissociable groups represented by the following general formula (a1-r-1) (hereinafter, sometimes referred to as "acetal-type acid-dissociable group"):

[0031] [In the formula, Ra' １ , Ra' ２ is a hydrogen atom or an alkyl group. ３ is a hydrocarbon group, and Ra' ３ is Ra' １ , Ra' ２ may be bonded to any one of the following to form a ring.]

[0032] In formula (a1-r-1), Ra' １ and Ra' ２ Among Ra', at least one is preferably a hydrogen atom, and more preferably both are hydrogen atoms. １ or Ra' ２ When is an alkyl group, examples of the alkyl group include the same alkyl groups as those exemplified as the substituent that may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylic acid ester above, and alkyl groups having 1 to 5 carbon atoms are preferred. Specific examples include linear or branched alkyl groups. More specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0033] In formula (a1-r-1), Ra' ３Examples of the hydrocarbon group include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of 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.

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

[0035] Ra' ３ 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 an aliphatic hydrocarbon group that is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferred. As the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As an aliphatic hydrocarbon group that is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferred, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ ]decane, tetracyclododecane, and the like.

[0036] Ra' ３When the cyclic hydrocarbon group described above 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 aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Ra' ３ Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., 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 alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0037] Ra' ３ The cyclic hydrocarbon group in may have a substituent. Examples of the substituent include -R Ｐ１ , -R Ｐ２ -O-R Ｐ１ , -R Ｐ２ -CO-R Ｐ１ , -R Ｐ２ -CO-OR Ｐ１ , -R Ｐ２ -O-CO-R Ｐ１ , -R Ｐ２ -OH, -R Ｐ２ -CN or -RＰ２ -COOH (hereinafter, these substituents are collectively referred to as "Ra ｘ５ ") etc. Here, R Ｐ１ is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Ｐ２ is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Ｐ１ and R Ｐ２ Some or all of the hydrogen atoms in the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of one type of the above-mentioned substituents, or may have one or more of each of two or more types of the above-mentioned substituents. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0]octanyl group, and the like. ２，６ ]decanyl group, tricyclo[3.3.1.1 ３，７ ] decanyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, or phenanthrene.

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

[0039] Tertiary alkyl ester acid-dissociable group: Among the above polar groups, examples of the acid-dissociable group protecting the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-2): Of the acid-dissociable groups represented by the following formula (a1-r-2), those constituted by an alkyl group will hereinafter be referred to as "tertiary alkyl ester acid-dissociable groups" for convenience.

[0040] [In the formula, Ra' ４ ~Ra' ６ are each a hydrocarbon group, and Ra' ５ , Ra' ６ may be bonded to each other to form a ring.

[0041] Ra' ４ Examples of the hydrocarbon group of Ra' include a linear or branched alkyl group, a linear or cyclic alkenyl group, and a cyclic hydrocarbon group. ４ The linear or branched alkyl group and the cyclic hydrocarbon group (a monocyclic aliphatic hydrocarbon group, a polycyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group) in ３ The same as Ra' can be mentioned. ４ The chain or cyclic alkenyl group in Ra' is preferably an alkenyl group having 2 to 10 carbon atoms. ５ , Ra' ６ The hydrocarbon group of Ra' ３ The same can be mentioned.

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

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

[0044] 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.

[0045] Ra' １０The linear alkyl group in Ra' has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. １０ In the formula (I), the branched alkyl group is the above-mentioned Ra' ３ The same can be mentioned.

[0046] Ra' １０ In the above, the alkyl group may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Furthermore, 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 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-, and -S(=O) ２ -, -S(=O) ２ -O- and the like.

[0047] In formula (a1-r2-1), Ra' １１ (Ra' １０ The aliphatic cyclic group formed together with the carbon atom to which Ra' is bonded in formula (a1-r-1) is ３ Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl and cyclohexyl groups are more preferred.

[0048] In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya includes Ra' in the formula (a1-r-1). ３ Examples of the cyclic hydrocarbon group include a group in which one or more hydrogen atoms have been further removed from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in the formula (I). The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of the substituent include the above-mentioned Ra' ３ In formula (a1-r2-2), the substituents that the cyclic hydrocarbon group in formula (a1-r2-2) may have are the same as those in formula (a1-r2-2). １０１ ~Ra１０３ In the formula, examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. １０１ ~Ra １０３ In the above formula, examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group; ２，６ ]decanyl group, tricyclo[3.3.1.1 ３，７ ] decanyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ ] and polycyclic aliphatic saturated hydrocarbon groups such as a dodecanyl group and an adamantyl group. １０１ ~Ra １０３ Among these, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among these, a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.

[0049] The above Ra １０１ ~Ra １０３ Examples of the substituents that the chain saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the formula (I) include the above-mentioned Ra ｘ５ The same groups as those shown below can be mentioned.

[0050] Ra １０１ ~Ra １０３ Examples of the group containing a carbon-carbon double bond formed by two or more of the above being bonded to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.

[0051] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). ３ In formula (a1-r2-3), the groups exemplified as the aliphatic hydrocarbon group are preferably monocyclic or polycyclic groups. １０４ Examples of the aromatic hydrocarbon group in the formula (I) include a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. １０４ is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.

[0052] Ra in formula (a1-r2-3) １０４ Examples of the substituent that may be possessed by the group include a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group), an alkyloxycarbonyl group, and the like.

[0053] In formula (a1-r2-4), Ra' １２ and Ra' １３ are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. １２ and Ra' １３ In the formula (I), the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms includes the above-mentioned Ra １０１ ~Ra １０３ The monovalent saturated chain hydrocarbon group having 1 to 10 carbon atoms in the formula (1) may be substituted in part or in whole. １２ and Ra' １３ Among these, Ra' is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. １２ and Ra'１３ When the chain saturated hydrocarbon group represented by the formula (I) is substituted, examples of the substituent include the above-mentioned Ra ｘ５ The same groups as those shown below can be mentioned.

[0054] In formula (a1-r2-4), Ra' １４ is a hydrocarbon group which may have a substituent. １４ The hydrocarbon group in the formula (I) includes a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0055] Ra' １４ The linear alkyl group in the formula (I) preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of 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.

[0056] Ra' １４ The branched alkyl group in the formula (I) preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

[0057] 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 an aliphatic hydrocarbon group that is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferred. As the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As an aliphatic hydrocarbon group that is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferred, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ ]decane, tetracyclododecane, and the like.

[0058] Ra' １４ As the aromatic hydrocarbon group in １０４ Among them, the aromatic hydrocarbon groups Ra' are the same as those in １４ is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene. １４ Examples of the substituent that may be possessed by Ra include １０４ Examples of the substituents include the same as those that may be possessed by the group.

[0059] Ra' in formula (a1-r2-4) １４ When Ra' in formula (a1-r2-4) is a naphthyl group, the position at which it is bonded to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group. １４ When is an anthryl group, the position at which it is bonded to the tertiary carbon atom in the formula (a1-r2-4) may be any one of the 1st, 2nd, and 9th positions of the anthryl group.

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

[0061]

[0062]

[0063]

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

[0065]

[0066]

[0067]

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

[0069]

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

[0071]

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

[0073] [In the formula, Ra' ７ ~Ra' ９ are each an alkyl group.

[0074] In formula (a1-r-3), Ra' ７ ~Ra' ９ are each preferably an alkyl group having 1 to 5 carbon atoms, 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.

[0075] Secondary Alkyl Ester-Type Acid-Dissociable Group: Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-4).

[0076] [In the formula, Ra' １０ is a hydrocarbon group. １１ａ and Ra' １１ｂ are each independently 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.

[0077] In the formula, Ra' １０ and Ra' １２ The hydrocarbon group in Ra' is ３ In the formula, Ra' １１ａ and Ra' １１ｂ The alkyl group in Ra' is １ In the formula, Ra' is the same as the alkyl group in １０ and Ra' １２ and the hydrocarbon group in Ra' １１ａ and Ra' １１ｂ The alkyl group in may have a substituent. Examples of the substituent include the above-mentioned Ra ｘ５ etc.

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

[0079] Ra' １０ and Ra' １１ａ or Ra' １１ｂ and are bonded to each other to form a ring, among the above, a monocycloalkene, a ring in which a portion of the carbon atoms of a monocycloalkene is substituted with a heteroatom (such as an oxygen atom or a sulfur atom), or a monocycloalkadiene is preferred, a cycloalkene having 3 to 6 carbon atoms is preferred, and cyclopentene or cyclohexene is preferred.

[0080] Ra' １０ and Ra' １１ａ or Ra' １１ｂ The ring formed by bonding these may be a fused ring. Specific examples of such a fused ring include indan.

[0081] Ra' １０ and Ra' １１ａ or Ra' １１ｂThe ring formed by bonding together may have a substituent. Examples of the substituent include the above-mentioned Ra ｘ５ etc.

[0082] Ra' １１ａ or Ra' １１ｂ and Ra' １２ and may be bonded to each other to form a ring, and the ring may include Ra' １０ and Ra' １１ａ or Ra' １１ｂ and the ring formed by bonding with each other are exemplified.

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

[0084]

[0085] Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, a structural unit derived from hydroxystyrene or a hydroxystyrene derivative in which at least some of the hydrogen atoms in the hydroxyl groups are protected with a substituent containing the above-mentioned acid-decomposable group, and a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative in which at least some of the hydrogen atoms in -C(═O)-OH are protected with a substituent containing the above-mentioned acid-decomposable group.

[0086] Of the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. Preferred specific examples of such structural unit (a1) include structural units represented by the following general formulas (a1-1), (a1-2), and (a1-3):

[0087] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. １ is a divalent hydrocarbon group which may have an ether bond. ａ１ is an integer from 0 to 2. １is an acid-dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4). １ is n ａ２ + is a monovalent hydrocarbon group. ａ２ is an integer from 1 to 3. ２ represents an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3). ００１ represents a single bond or a divalent linking group. ０１ is a single bond or a divalent linking group. ０１ is an acid-dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4). ０１ is an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group; q is an integer of 0 to 3; and n is an integer of 0 or greater, provided that n≦q×2+4.

[0088] In the formulas (a1-1) to (a1-3), the alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. A fluorine atom is particularly preferred as the halogen atom. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

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

[0090] Va １The aliphatic hydrocarbon group as the divalent hydrocarbon group in may be saturated or unsaturated, and is usually preferably saturated. More specific examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.

[0091] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and 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 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0092] Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

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

[0094] In the formula (a1-1), Ra １ is preferably an acid-dissociable group represented by the above general formula (a1-r-2) or (a1-r-4), and among these, a group represented by the general formula (a1-r2-1) or an acid-dissociable group represented by the general formula (a1-r-4) is more preferred.

[0095] In the formula (a1-2), Wa １ n in ａ２The +1-valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups combining linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure. ａ２ The +1 valence is preferably 2 to 4, more preferably 2 or 3. ２ is preferably an acid-dissociable group represented by the above general formula (a1-r-1).

[0096] In the formula (a1-3), Ya ００１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. 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 alkylene 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. Among these, Ya ００１ The alkyl group is preferably a combination of an ester bond [—C(═O)—O—, —O—C(═O)—] and a linear alkylene group, or a single bond, and more preferably a single bond.

[0097] In the formula (a1-3), Ya ０１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. ０１Among the above, it is preferable that Ya is 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. ０１ The alkyl group is preferably a combination of an ester bond [—C(═O)—O—, —O—C(═O)—] and a linear alkylene group, or a single bond, and more preferably a single bond.

[0098] In the formula (a1-3), Rax ０１ is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4), and among these, an acid dissociable group represented by the general formula (a1-r-2) is more preferred, and a group represented by the general formula (a1-r2-1) is even more preferred.

[0099] In the formula (a1-3), Rz ０１ The alkyl group, halogenated alkyl group, and alkoxy group in Rz preferably have 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. ０１ The halogen atom in Rz is preferably an iodine atom. ０１ The halogen atom of the halogenated alkyl group in Rz is preferably a fluorine atom, an iodine atom, or a bromine atom, and more preferably a fluorine atom. ０１ As the alkyl group, an alkoxy group or a hydroxy group is preferred, and a hydroxy group is more preferred.

[0100] In the formula (a1-3), q is an integer of 0 to 3. When q is 0, the structure is a benzene structure, when q is 1, the structure is a naphthalene structure, when q is 2, the structure is an anthracene structure, and when q is 3, the structure is a tetracene structure. In the formula (a1-3), n is an integer of 0 or more, preferably 0 to 5, more preferably 0 to 3, and even more preferably 1 or 2. When n is an integer of 2 or more, Rz is 2 or more. ０１may be the same or different. In the formula (a1-3), n≦q×2+4. For example, when q is 1 and the naphthalene structure is formed, all six hydrogen atoms of the naphthalene may be substituted with hydroxy groups. In addition, in the naphthalene, Ya ００１ , -Ya ０１ -C(=O)-O-Ra ０１ The substitution positions of the group and the hydroxy group are not particularly limited.

[0101] Specific examples of the structural unit (a1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] In each of 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.

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The structural unit (a1) contained in the component (A1) may be of one type, or may be of two or more types. As the structural unit (a1), a structural unit represented by the above formula (a1-1) or a structural unit represented by the above formula (a1-3) is more preferred, as these tend to further improve the properties (sensitivity, shape, etc.) in lithography using electron beams or EUV. Among these, an acid-dissociable group (Ra １ , Rax ０１ ) are preferably acid-dissociable groups represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), respectively, and among these, it is particularly preferable to select those which are cyclic groups.

[0118] Alternatively, the structural unit (a1) may include a structural unit represented by the following general formula (a1-1-1):

[0119] [In the formula, Ra １ " is an acid-dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4). * represents a bond.]

[0120] In the formula (a1-1-1), R, Va １ and n ａ１ represents R, Va in the formula (a1-1). １ and n ａ１ is the same as:

[0121] The acid-dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4) is as described above. Among these, it is preferable to select an acid-dissociable group that is a cyclic group, as this is suitable for use with EB or EUV and can enhance reactivity.

[0122] The proportion of the structural unit (a1) in the component (A1) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, even more preferably 15 to 50 mol %, and particularly preferably 20 to 40 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a1) is at least the lower limit of the above-mentioned preferred range, lithography properties such as sensitivity, resolution, and CDU improvement are improved. On the other hand, by ensuring that the proportion is at most the upper limit of the above-mentioned preferred range, a balance with other structural units can be achieved, resulting in various favorable lithography properties.

[0123] <Structural Unit (a10)> The structural unit (a10) is a structural unit represented by the following general formula (a10-1): The component (A1) contains the structural unit (a10).

[0124] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ｘ１ is a single bond or a divalent linking group. ｘ１ is an aromatic hydrocarbon group which may have a substituent. ａｘ１ is an integer of 1 or greater.

[0125] In the formula (a10-1), R is the same as R in the general formula (a1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.

[0126] In the formula (a10-1), Ya ｘ１ is a single bond or a divalent linking group. ｘ１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0127] 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.

[0128] Aliphatic hydrocarbon group: An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups that contain a ring in their structure.

[0129] ...Straight-chain or branched-chain aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched chain aliphatic hydrocarbon group, a branched chain alkylene group is preferred, and 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 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0130] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0131] ...Aliphatic hydrocarbon groups containing a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon groups include 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. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0132] 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, and a carbonyl group. 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. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and even more preferably a methoxy group or an ethoxy group. The halogen atom as the substituent is preferably a fluorine atom. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. The cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with a substituent containing a heteroatom. The substituent containing a hetero atom includes —O—, —C(═O)—O—, —S—, and —S(═O) ２ -, -S(=O) ２ —O— is preferred.

[0133] 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 aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0134] In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an 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. 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 substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0135] Divalent linking group containing a hetero atom: Examples of the divalent linking group containing a hetero atom 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-, and -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 -OC(=O)-Y ２２ - or -Y ２１ -S(=O) ２ -O-Y ２２ -, wherein Y ２１ and Y ２２are 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. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H 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, and particularly preferably 1 to 5 carbon atoms. In the 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 -OC(=O)-Y ２２ - or -Y ２１ -S(=O) ２ -O-Y ２２ -Middle, 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 as those described above. ２１ As Y, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred. 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. 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 group represented by the formula -[Y ２１ -C(=O)-O] ｍ”-Y ２２ The group represented by - includes the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ Among them, groups represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ 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, even 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, even more preferably 1 or 2, and most preferably 1.

[0136] Ya ｘ１ is preferably 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, and more preferably a single bond or an ester bond [-C(=O)-O-, -O-C(=O)-].

[0137] In the formula (a10-1), Wa ｘ１ is an aromatic hydrocarbon group which may have a substituent. ｘ１ The aromatic hydrocarbon group in the formula (n) is an aromatic ring which may have a substituent. ａｘ１ Examples of the aromatic ring include a group in which 4n+1) hydrogen atoms have been removed. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. Wa ｘ１The aromatic hydrocarbon group in (n) is selected from aromatic compounds containing an aromatic ring which may have two or more substituents (for example, biphenyl, fluorene, etc.). ａｘ１ Also included are groups in which one or more hydrogen atoms have been removed. ｘ１ Examples of the aryl group include benzene, naphthalene, anthracene, and biphenyl (n ａｘ１ A group in which (n +1) hydrogen atoms have been removed is preferred, and a group in which (n +1) hydrogen atoms have been removed from benzene or naphthalene is preferred. ａｘ１ A group in which (n +1) hydrogen atoms have been removed from benzene is more preferred, ａｘ１ A group in which 1) hydrogen atoms have been removed is more preferred.

[0138] Wa ｘ１ The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include Ya ｘ１ Examples of the substituent include the same as those exemplified as the substituent of the cyclic aliphatic hydrocarbon group in Wa. 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, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. ｘ１ The aromatic hydrocarbon group in the formula (I) preferably does not have a substituent.

[0139] 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.

[0140] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below. α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0141]

[0142]

[0143]

[0144] The structural unit (a10) contained in the component (A1) may be of one type, or may contain two or more types. The component (A1) may or may not contain the structural unit (a10), but preferably contains the structural unit (a10). When the component (A1) contains the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol%, relative to the total (100 mol%) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a10) is at or above the lower limit, sensitivity is likely to be further improved. Furthermore, when a resist pattern is formed, scum generation is more likely to be suppressed, and the pattern shape is less likely to become tapered. On the other hand, by ensuring that the proportion of the structural unit (a10) is at or below the upper limit, it is easier to achieve a balance with the other structural units.

[0145] <<Other Structural Units>> The component (A1) may include, as necessary, other structural units in addition to the aforementioned structural unit (a10), or in addition to the structural unit (a1) and the structural unit (a10). Examples of other structural units include a structural unit (a2) containing a lactone-containing cyclic group, a structural unit (a5) that generates acid upon exposure, a structural unit (a6) that has acid diffusion controllability, a structural unit (a3) ​​containing a polar group-containing aliphatic hydrocarbon group, a structural unit (a4) containing an acid-non-dissociable aliphatic cyclic group, and a structural unit (st) derived from styrene or a styrene derivative.

[0146] Structural unit (a2): The component (A1) may or may not have a structural unit (a2) (excluding those corresponding to the structural unit (a1)) that contains a lactone-containing cyclic group. When the component (A1) is used to form a resist film, the lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate. Furthermore, the presence of the structural unit (a2) provides effects such as appropriate adjustment of the acid diffusion length, improved adhesion of the resist film to the substrate, and appropriate adjustment of solubility during development, resulting in improved lithography properties.

[0147] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) that contains -O-C(=O)- within its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is also another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. There are no particular restrictions on the lactone-containing cyclic group in the structural unit (a2), and any group can be used. Specific examples include groups represented by the following general formulae (a2-r-1) to (a2-r-7).

[0148] [In the formula, Ra' ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (—O—) or a sulfur atom (—S—), an oxygen atom, or a sulfur atom; n′ is an integer of 0 to 2, and m′ is 0 or 1. * represents a bond (the same applies hereinafter).

[0149] In the general formulas (a2-r-1) to (a2-r-7), Ra' ２１ The alkyl group in Ra' is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred. Ra' ２１ The alkoxy group in the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, ２１ Examples of the alkyl groups include those mentioned as examples of the alkyl group in the above formula and an oxygen atom (—O—). ２１The halogen atom in Ra' is preferably a fluorine atom. ２１ As the halogenated alkyl group in the formula Ra′, ２１ Examples of the halogenated alkyl group include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0150] Ra' ２１ In -COOR" and -OC(=O)R" in the formula (I), R" is either 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 has 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group. When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably has 4 to 12 carbon atoms, and most preferably has 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; ２，６ ] decane, tetracyclododecane, and other polycycloalkanes in which one or more hydrogen atoms have been removed. Examples of the lactone-containing cyclic group in R" include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7). Ra' ２１ The hydroxyalkyl group in the formula (Ra') preferably has 1 to 6 carbon atoms. ２１ and a group in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0151] Ra' ２１ Among the above, each of the groups is preferably independently a hydrogen atom or a cyano group.

[0152] In the general formulae (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms for A" is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between carbon atoms of the alkylene group, such as -O-CH ２ -, -CH ２ -O-CH ２ -, -S-CH ２ -, -CH ２ -S-CH ２ A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

[0153] Specific examples of the groups represented by general formulae (a2-r-1) to (a2-r-7) are listed below.

[0154]

[0155]

[0156] Of the structural units (a2), structural units derived from acrylate esters in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent are preferred. Such structural units (a2) are preferably structural units represented by the following general formula (a2-1):

[0157] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ２１ is a single bond or a divalent linking group. ２１ represents -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group.２１ When is -O-, Ya ２１ does not become -CO-. ２１ is a lactone-containing cyclic group.

[0158] In the formula (a2-1), R is the same as defined above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.

[0159] In the formula (a2-1), Ya ２１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. ２１ As the divalent linking group in the general formula (a10-1), ｘ１ Examples of the divalent linking group include the same as the divalent linking group in the above formula.

[0160] 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.

[0161] In the formula (a2-1), Ya ２１ is a single bond, and La ２１ is preferably —COO— or —OCO—.

[0162] In the formula (a2-1), Ra ２１ is a lactone-containing cyclic group. ２１ Suitable examples of the lactone-containing cyclic group in the formula (a2-r-1) include the groups represented by the general formulae (a2-r-1) to (a2-r-7) described above.

[0163] The structural unit (a2) contained in the component (A1) may be of one type, or may contain two or more types. The component (A1) may or may not contain the structural unit (a2). When the component (A1) contains the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, relative to the total (100 mol %) of all structural units constituting the component (A1). When the proportion of the structural unit (a2) is at least the preferred lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the aforementioned effects. When the proportion is at or below the upper limit, a balance with the other structural units can be achieved, resulting in various favorable lithography properties.

[0164] Structural Unit (a5): The component (A1) may or may not include a structural unit (a5) that generates acid upon exposure. Known structural units can be used as the structural unit (a5). By including the structural unit (a5), the acid generated upon exposure tends to be more uniformly distributed within the resist film. Examples of the structural unit (a5) include structural units containing a structure as described below for the component (B). Examples include structural units containing a structure represented by any of the below-described general formulas (b-1) to (b-3). Suitable examples of the structural unit (a5) include structural units represented by the following general formula (a5-1):

[0165] [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. ５０ is a divalent linking group or a single bond. ５０ represents a divalent hydrocarbon group which may have a substituent. ａ５ is an integer from 0 to 2. ５１ is a divalent linking group. ５ is a divalent linking group which may have a heteroatom, or a single bond. 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.

[0166] {Anion moiety} 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. ｍ The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen atom in the halogenated alkyl group, a fluorine atom is particularly preferred. R ｍ As the alkyl group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0167] In the formula (a5-1), La ５０ is a divalent linking group or a single bond. ５０ The divalent linking group in the formula (I) is not particularly limited, but a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom are preferred. ｘ１ The divalent linking group is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified in the above. 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. ５is more preferably an ester bond [—C(═O)—O—, —O—C(═O)—] or a single bond, and further preferably an ester bond [—C(═O)—O—, —O—C(═O)—].

[0168] In the formula (a5-1), Ra ５０ is a divalent hydrocarbon group which may have a substituent. ５０ The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0169] .Ra ５０ The aliphatic hydrocarbon group in the above formula (1) means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.

[0170] ...Straight-chain or branched-chain aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and 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 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0171] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0172] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon groups include 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. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0173] 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, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. 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 preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. The cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with a substituent containing a heteroatom. The substituent containing a hetero atom includes —O—, —C(═O)—O—, —S—, and —S(═O) ２ -, -S(=O) ２ —O— is preferred.

[0174] .Ra ５０The aromatic hydrocarbon group in the above formula (1) 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 aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0175] In the aromatic hydrocarbon group, a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an 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. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent that substitutes a hydrogen atom contained in the cyclic aliphatic hydrocarbon group.

[0176] In the formula (a5-1), n ａ５ is an integer of 0 to 2. Among the above, Ra ５０ is preferably an aliphatic hydrocarbon group containing a ring in its structure, more preferably a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure, and even more preferably an alicyclic hydrocarbon group which is a polycyclic group or a monocyclic group and may have a substituent. ５０ is preferably an aromatic hydrocarbon group.

[0177] n ａ５ If is 2, then two Ra ５０ may all be alicyclic hydrocarbon groups which may have a substituent, may all be aromatic hydrocarbon groups, or may be a combination of alicyclic hydrocarbon groups which may have a substituent and aromatic hydrocarbon groups.

[0178] In the formula (a5-1), La ５１ is a divalent linking group. ５１Examples of the divalent linking group in the formula (I) include non-hydrocarbon 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-); and combinations of such non-hydrocarbon oxygen atom-containing linking groups with alkylene groups. These combinations may also be further combined with a sulfonyl group (-SO ２ Examples of such a divalent linking group include the linking groups represented by the following general formulae (L-al-1) to (L-al-8). In the following general formulae (L-al-1) to (L-al-8), Ra in the above formula (a5-1) may be ５０ and V' in the following general formulae (L-al-1) to (L-al-8) １０１ is.

[0179] [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.

[0180] V' １０２ The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0181] V' １０１ and V' １０２ The alkylene group in V' may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. １０１ and V' １０２ Specific examples of the alkylene group in ２ -]; -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; ethylene groups [-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 -, etc.; a 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 an alkyltrimethylene group such as -; a 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 -, etc.; an alkyltetramethylene group such as a pentamethylene group [—CH ２ CH ２ CH ２ CH ２ CH ２ -]. Also, V' １０１ or V' １０２ In the formula (a1-r-1), some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by Ra' in the formula (a1-r-1).３ A divalent group obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group) of the above formula (I) is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0182] La ５１ As the linking group, a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, the linking groups represented by the above formulae (L-al-1) to (L-al-5) and (L-al-8) are more preferable, and the linking group represented by (L-al-3) or (L-al-8) is even more preferable.

[0183] In the formula (a5-1), Ya ５ represents a divalent linking group which may have a heteroatom, or a single bond. ５ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. ５ The divalent hydrocarbon group which may have a substituent and the divalent linking group which contains a hetero atom in ｘ１ The divalent linking group is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified in the above. ５ is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0184] In the formula (a5-1), Ra ５１ and Ra ５２ are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. ５１ and Ra ５２ In the formula (a5-1), the fluorinated alkyl group is preferably a linear or branched fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a trifluoromethyl group. ３ － Ra bonded to the carbon atom adjacent to ５１ and Ra ５２From the viewpoint of acid strength, it is preferable that at least one of the groups is a fluorine atom.

[0185] In the formula (a5-1), n5 represents an integer of 1 to 4, and is preferably 1, 2, or 3.

[0186] {Cation moiety} In the formula (a5-1), M' ｍ＋ represents an m-valent onium cation. ｍ＋ is preferably a sulfonium cation or an iodonium cation, and m is an integer of 1 or more.

[0187] Preferred cationic moieties ((M' ｍ＋ ) １／ｍ ) includes organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0188] [In the formula, R ２０１ ~R ２０７ R each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. ２０１ ~R ２０３ , R ２０６ ~R ２０７ may be bonded to each other to form a ring together with the sulfur atom in the formula. ２０８ ~R ２０９ R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０ represents 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 an —SO ２ -containing cyclic group. ２０１ represents —C(═O)— or —C(═O)—O—.]

[0189] In the above general formulas (ca-1) to (ca-3), R ２０１ ~R ２０７ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２０１ ~R ２０７The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulae (ca-r-1) to (ca-r-7):

[0190] [In the formula, R' ２０１ are each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0191] 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. An aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0192] R' ２０１ The aromatic hydrocarbon group in R' is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. ２０１ Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R' include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. ２０１Specific examples of the aromatic hydrocarbon group in the formula (I) include groups in which one hydrogen atom has been removed from the aromatic ring (aryl groups: for example, phenyl group, naphthyl group, etc.), and groups in which one hydrogen atom of the aromatic ring has been 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 alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0193] R' ２０１ Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed within a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ] Polycycloalkanes having a polycyclic skeleton of a bridged ring system, such as decane and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid skeleton, are more preferred.

[0194] Among them, R' ２０１The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0195] 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 preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ 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 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 alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0196] Also, R' ２０１ The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specifically, lactone-containing cyclic groups represented by the above general formulae (a2-r-1) to (a2-r-7), —SO ２ -containing cyclic groups, and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0197]

[0198] R' ２０１Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. The halogen atom as a substituent is preferably a fluorine atom. Examples of the halogenated alkyl group as a substituent include alkyl groups 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, in which some or all of the hydrogen atoms have been substituted with the halogen atoms. The carbonyl group as a substituent is a methylene group (-CH ２ -) is a group that substitutes

[0199] A chain alkyl group which may have a substituent: R' ２０１ The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 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. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0200] A chain alkenyl group which may have a substituent: R' ２０１The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of branched alkenyl groups include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, with a vinyl group and a propenyl group being more preferred, and a vinyl group being particularly preferred.

[0201] R' ２０１ Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above-mentioned R' ２０１ Examples of the cyclic groups include the cyclic groups shown in the formula:

[0202] R' ２０１ In addition to the above-mentioned optionally substituted cyclic groups, optionally substituted chain alkyl groups, and optionally substituted chain alkenyl groups, examples of the optionally substituted cyclic groups or optionally substituted chain alkyl groups include those similar to the acid-dissociable group represented by formula (a1-r-2) above.

[0203] Among them, R' ２０１ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7) above; -SO represented by each of the general formulae (b5-r-1) to (b5-r-4) described below; ２ -containing cyclic groups are preferred.

[0204] In the above general formulas (ca-1) to (ca-3), R ２０１ ~R ２０３ , R ２０６ ~R ２０７When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not substituted with heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or with carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -COO-, -CONH- or -N(R Ｎ )-(the R Ｎ is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0205] R ２０８ ~R ２０９ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0206] R ２１０ represents 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 an —SO ２ -containing cyclic group. ２１０ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２１０ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２１０ In the -SO ２ The -containing cyclic group is not particularly limited and any group can be used. Specific examples include groups represented by the following general formulae (b5-r-1) to (b5-r-4), and "-SO ２-containing polycyclic group" is preferred, and a group represented by general formula (b5-r-1) is more preferred.

[0207] [In the formula, Rb' ５１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or —SO ２ -containing cyclic group; B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; n' is an integer of 0 to 2; * represents a bond.

[0208] In the general formulae (b5-r-1) and (b5-r-2), B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. B" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0209] In the general formulae (b5-r-1) to (b5-r-4), Rb' ５１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group, and among these, are preferably each independently a hydrogen atom or a cyano group.

[0210] Specific examples of the groups represented by general formulae (b5-r-1) to (b5-r-4) are listed below, where "Ac" represents an acetyl group.

[0211]

[0212]

[0213]

[0214] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas.

[0215]

[0216]

[0217] [In the formula, g1, g2, and g3 represent the number of repeating units, where g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 1 to 20.]

[0218]

[0219]

[0220] [In the formula, R” ２０１ is a hydrogen atom or a substituent, and the substituent is the same as R ２０１ ~R ２０７ , and R ２１０ The substituents are the same as those exemplified as the substituents that may be possessed by

[0221]

[0222] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0223] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0224]

[0225] The cation moiety ((M' ｍ＋ ) １／ｍAs the cation represented by the formula (ca-1), a sulfonium cation is preferable, the cations represented by the formulas (ca-1) to (ca-3) are more preferable, the cation represented by the formula (ca-1) is even more preferable, and the cations represented by the formulas (ca-1-1) to (ca-1-84) are particularly preferable. In particular, from the viewpoint of increasing sensitivity, the preferred cation represented by the formula (ca-1) is preferably one having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent, and for example, a cation selected from the group consisting of the cations represented by the formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferable.

[0226] Specific preferred 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＋ represents m and M' in the general formula (a5-1). ｍ＋ is the same as:

[0227]

[0228]

[0229]

[0230] The structural unit (a5) contained in the component (A1) may be of one type, or may be of two or more types. When the component (A1) contains the structural unit (a5), the proportion of the structural unit (a5) in the component (A1) is preferably 5 to 25 mol %, more preferably 10 to 20 mol %, and even more preferably 15 to 20 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). When the proportion of the structural unit (a5) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve even higher sensitivity and improved resolution. On the other hand, when the proportion is at most the upper limit of the above-mentioned preferred range, it becomes easier to achieve a balance with other structural units.

[0231] Structural unit (a6): The structural unit (a6) is a structural unit that has acid diffusion controllability. The component (A1) may or may not have the structural unit (a6). Known structural units can be used as the structural unit (a6). Examples of the structural unit (a6) include structural units containing the structures described for the components (D1) and (D2) described below. Examples include structural units containing a structure represented by any of the general formulas (d1-1) to (d1-3) described below.

[0232] The structural unit (a6) contained in the component (A1) may be of one type, or may be of two or more types. When the component (A1) contains the structural unit (a6), the proportion of the structural unit (a6) in the component (A1) is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and even more preferably 3 to 10 mol %, relative to the total (100 mol %) of all structural units constituting the component (A1). When the proportion of the structural unit (a6) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve even higher sensitivity. On the other hand, when the proportion is at most the upper limit of the above-mentioned preferred range, it becomes easier to achieve a balance with the other structural units.

[0233] Structural Unit (a3): The structural unit (a3) ​​is a structural unit that contains a polar group-containing aliphatic hydrocarbon group (however, this structural unit excludes those that fall under the category of the structural unit (a1) and the structural unit (a2)). The component (A1) may or may not contain the structural unit (a3). Known structural units can be used as the structural unit (a3). The structural unit (a3) ​​is effective in increasing the hydrophilicity of the component (A1). This makes it possible to adjust the resolution and acid diffusion length, among other things.

[0234] Examples of polar groups include hydroxyl groups, cyano groups, carboxy groups, and hydroxyalkyl groups in which some of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms, with hydroxyl groups being particularly preferred. Examples of aliphatic hydrocarbon groups include linear or branched hydrocarbon groups (preferably alkylene groups) having 1 to 10 carbon atoms, and cyclic aliphatic hydrocarbon groups (cyclic groups). The cyclic group may be either a monocyclic group or a polycyclic group, and can be appropriately selected from the many groups proposed for use in resins for KrF excimer laser resist compositions, for example.

[0235] When the cyclic group is a monocyclic group, it more preferably has 3 to 10 carbon atoms. Among these, structural units derived from acrylate esters containing an aliphatic monocyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which some of the alkyl group's hydrogen atoms are substituted with fluorine atoms are more preferred. Examples of such monocyclic groups include groups in which two or more hydrogen atoms have been removed from a monocycloalkane. Specific examples include groups in which two or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane, or cyclooctane. Of these monocyclic groups, groups in which two or more hydrogen atoms have been removed from cyclopentane and groups in which two or more hydrogen atoms have been removed from cyclohexane are industrially preferred.

[0236] When the cyclic group is a polycyclic group, the polycyclic group more preferably has 7 to 30 carbon atoms. Among them, structural units derived from acrylate esters containing an aliphatic polycyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms are more preferred. Examples of such polycyclic groups include groups in which two or more hydrogen atoms have been removed from bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc. Specific examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and other polycycloalkanes by removing two or more hydrogen atoms. Among these polycyclic groups, groups by removing two or more hydrogen atoms from adamantane, groups by removing two or more hydrogen atoms from norbornane, and groups by removing two or more hydrogen atoms from tetracyclododecane are industrially preferred.

[0237] The structural unit (a3) ​​is not particularly limited, and any structural unit can be used as long as it contains a polar group-containing aliphatic hydrocarbon group. The structural unit (a3) ​​is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and which contains a polar group-containing aliphatic hydrocarbon group. When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a3) ​​is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid. Furthermore, when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, preferred structural units for the structural unit (a3) ​​include structural units represented by the following formulas (a3-1), (a3-2), and (a3-3); when the hydrocarbon group is a monocyclic group, preferred structural units include structural units represented by formula (a3-4).

[0238] [In the formula, R is the same as defined above, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, l is an integer of 0 to 5, and s is an integer of 1 to 3.]

[0239] In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, the hydroxyl group is preferably bonded to the 3rd position of the adamantyl group. j is preferably 1, and the hydroxyl group is particularly preferably bonded to the 3rd position of the adamantyl group.

[0240] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the norbornyl group.

[0241] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. In these, a 2-norbornyl group or a 3-norbornyl group is preferably bonded to the terminal of the carboxyl group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5- or 6-position of the norbornyl group.

[0242] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluorinated alkyl alcohol is preferably bonded to the 3- or 5-position of the cyclohexyl group.

[0243] The structural unit (a3) ​​contained in the component (A1) may be one type, or two or more types. When the component (A1) contains the structural unit (a3), the proportion of the structural unit (a3) ​​is preferably 1 to 30 mol %, more preferably 2 to 25 mol %, and even more preferably 5 to 20 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a3) ​​is at least the preferred lower limit, the effects achieved by including the structural unit (a3) ​​can be fully obtained due to the effects described above. By ensuring that the proportion is at most the preferred upper limit, a balance with the other structural units can be achieved, resulting in various favorable lithography properties.

[0244] Regarding the structural unit (a4): The structural unit (a4) is a structural unit that contains an acid-non-dissociable aliphatic cyclic group. The component (A1) may or may not contain the structural unit (a4). The structural unit (a4) is effective in improving the dry etching resistance of the resist pattern that is formed. The structural unit (a4) is also effective in increasing the hydrophobicity of the component (A1). This makes it possible to adjust the resolution, resist pattern shape, and the like. The "acid-non-dissociable cyclic group" in the structural unit (a4) is a cyclic group that, when acid is generated in the resist composition upon exposure (for example, when acid is generated from the structural unit (a5) or the component (B)), remains intact in the structural unit without dissociating even when acted upon by the acid.

[0245] Preferred examples of the structural unit (a4) include structural units derived from acrylate esters containing an acid-non-dissociable aliphatic cyclic group. The cyclic group can be any of the numerous groups conventionally known for use in resin components of resist compositions for ArF excimer lasers, KrF excimer lasers (preferably KrF excimer lasers), and the like. In terms of industrial availability, the cyclic group is preferably at least one selected from the group consisting of a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent. Specific examples of the structural unit (a4) include structural units represented by the following general formulas (a4-1) to (a4-7):

[0246] [In the formula, R α is the same as above.]

[0247] The structural unit (a4) contained in the component (A1) may be of one type, or may be of two or more types. When the component (A1) contains the structural unit (a4), the proportion of the structural unit (a4) relative to the total (100 mol%) of all structural units constituting the component (A1) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 20 to 40 mol%. By ensuring that the proportion of the structural unit (a4) is at least the preferred lower limit, the effects of including the structural unit (a4) can be fully obtained, while by ensuring that the proportion is at most the preferred upper limit, it is easier to achieve a balance with the other structural units.

[0248] Structural Unit (st): The structural unit (st) is a structural unit derived from styrene or a styrene derivative. The component (A1) may or may not have the structural unit (st).

[0249] A "structural unit derived from styrene" refers to a structural unit formed by cleavage of the ethylenic double bond of styrene. A "structural unit derived from a styrene derivative" refers to a structural unit formed by cleavage of the ethylenic double bond of a styrene derivative. A "styrene derivative" refers to a compound in which at least some of the hydrogen atoms of styrene are substituted with a substituent. Examples of styrene derivatives include those in which the hydrogen atom at the α-position of styrene is substituted with a substituent, those in which one or more hydrogen atoms on the benzene ring of styrene are substituted with a substituent, and those in which the hydrogen atom at the α-position of styrene and one or more hydrogen atoms on the benzene ring are substituted with a substituent.

[0250] Examples of the substituent substituting the hydrogen atom at the α-position of styrene include an alkyl group having 1 to 5 carbon atoms and a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. A fluorine atom is particularly preferred as the halogen atom. The substituent substituting the hydrogen atom at the α-position of styrene is preferably an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group from the viewpoint of industrial availability.

[0251] Examples of substituents substituting hydrogen atoms on the benzene ring of styrene include alkyl groups, alkoxy groups, halogen atoms, and halogenated alkyl groups. 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. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and even more preferably a methoxy group or an ethoxy group. The halogen atom as the substituent is preferably a fluorine atom. Examples of halogenated alkyl groups as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. The substituent substituting hydrogen atoms on the benzene ring of styrene is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0252] The structural unit (st) is preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, more preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with a methyl group, and even more preferably a structural unit derived from styrene.

[0253] The structural unit (st) contained in the component (A1) may be of one type, or may consist of two or more types. When the component (A1) contains the structural unit (st), the proportion of the structural unit (st) relative to the total (100 mol%) of all structural units constituting the component (A1) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 20 to 40 mol%.

[0254] The resist composition may contain one type of component (A1), or two or more types of components may be used in combination.

[0255] Examples of the component (A1) include a polymeric compound having the structural unit (a1) and the structural unit (a10); a polymeric compound having the structural unit (a1), the structural unit (a10), and the structural unit (a4); a polymeric compound having the structural unit (a1), the structural unit (a10), and the structural unit (st). Preferred examples of the component (A1) include a polymeric compound consisting of the structural unit (a1) and the structural unit (a10); a polymeric compound consisting of the structural unit (a1), the structural unit (a10), and the structural unit (a4); a polymeric compound consisting of the structural unit (a1), the structural unit (a10), and the structural unit (st).

[0256] In a polymeric compound composed of the structural unit (a1) and the structural unit (a10), the proportion of the structural unit (a1) relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and even more preferably 20 to 60 mol%. The proportion of the structural unit (a10) in the polymeric compound relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 20 to 90 mol%, more preferably 30 to 85 mol%, and even more preferably 40 to 80 mol%.

[0257] In a polymeric compound comprising the structural unit (a1), the structural unit (a10), and the structural unit (a4), the proportion of the structural unit (a1) is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound. The proportion of the structural unit (a10) in the polymeric compound is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound. The proportion of the structural unit (a4) in the polymeric compound is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, even more preferably 20 to 40 mol%, and particularly preferably 25 to 40 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound.

[0258] In a polymeric compound comprising the structural unit (a1), the structural unit (a10), and the structural unit (st), the proportion of the structural unit (a1) is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound. The proportion of the structural unit (a10) in the polymeric compound is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound. The proportion of the structural unit (st) in the polymeric compound is preferably 10 to 40 mol%, more preferably 20 to 40 mol%, and particularly preferably 25 to 40 mol%, relative to the total (100 mol%) of all structural units constituting the polymeric compound.

[0259] The component (A1) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601), followed by polymerization. Examples of monomers from which each structural unit is derived include monomers from which structural unit (a10) is derived, monomers from which structural unit (a1), and monomers from which other optional structural units are derived (e.g., structural unit (a4), structural unit (st), etc.). These monomers (e.g., monomers from which structural unit (a10) is derived) may have protected hydroxyl groups, etc., as necessary. In this case, the component (A1) can be produced by carrying out the polymerization reaction as described above, followed by a deprotection reaction. During polymerization, for example, HS-CH ２ -CH ２ -CH ２ -C(CF ３ ) ２ By using a chain transfer agent such as —OH in combination, it is possible to obtain a chain with —C(CF ３ ) ２ A copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms is thus introduced, and is effective in reducing development defects and LER (line edge roughness: non-uniform irregularities on the line sidewalls).

[0260] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene standards measured by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 30,000. When the Mw of component (A1) is equal to or less than the preferred upper limit of this range, the component has sufficient solubility in a resist solvent for use as a resist, while when the Mw is equal to or greater than the preferred lower limit of this range, the component exhibits good dry etching resistance and resist pattern cross-sectional shape. The dispersity (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Here, Mn represents the number-average molecular weight.

[0261] Regarding the component (A2): The resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as "component (A2)") that does not fall under the category of the component (A1) and whose solubility in a developer changes under the action of acid. There are no particular limitations on the component (A2), and it may be arbitrarily selected from the many base components conventionally known for use in chemically amplified resist compositions. The component (A2) may be a polymeric compound or a low molecular weight compound, and may be used either alone or in combination of two or more types.

[0262] The proportion of the component (A1) within the component (A), relative to the total mass of the component (A), is preferably 25 mass% or more, more preferably 50 mass% or more, and even more preferably 75 mass% or more, and may even be 100 mass%. When this proportion is 25 mass% or more, sensitivity is likely to be improved and a resist pattern that is excellent in various lithography properties such as resolution and roughness is likely to be formed.

[0263] The amount of the component (A) in the resist composition of this embodiment may be adjusted depending on factors such as the thickness of the resist film to be formed.

[0264] <Base Component (D)> In addition to the component (A), the resist composition of this embodiment contains a base component (component (D)) that traps acid generated upon exposure (i.e., controls the diffusion of acid). The component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure. The component (D) includes a compound (D01) (hereinafter also referred to as "component (D01)") and a compound (D02) (hereinafter also referred to as "component (D02)").

[0265] <Component (D01)> The component (D01) is a compound represented by the following general formula (d01).

[0266] [In the formula, Rx ０１ ~Rx ０３ each independently represents a chain hydrocarbon group which may have a substituent.

[0267] In the formula (d01), Rx ０１ ~Rx ０３ The optionally substituted chain hydrocarbon group in Rx includes an optionally substituted chain aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. ０１ ~Rx ０３ The chain hydrocarbon group in preferably has 1 to 15 carbon atoms, more preferably has 2 to 15 carbon atoms, and even more preferably has 2 to 10 carbon atoms.

[0268] Rx ０１ ~Rx ０３is preferably a linear alkyl group which may have a substituent, or a branched alkyl group which may have a substituent. The linear alkyl group preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, even more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group. The branched alkyl group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms. Specific examples of the branched alkyl group include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.

[0269] Rx ０１ ~Rx ０３ The chain hydrocarbon group in may or may not have a substituent. The substituent may be a monovalent group that substitutes a hydrogen atom of the hydrocarbon chain, and may be a methylene group (—CH ２ The monovalent group that substitutes a hydrogen atom may be, for example, a halogen atom or a hydroxy group. The halogen atom is preferably a fluorine atom. A methylene group (-CH ２ Examples of the divalent group substituting Rx include an oxo group (=O), an ester bond [-C(=O)-O-], and an ether bond (-O-). ０１ ~Rx ０３ The substituent of the chain hydrocarbon group in the formula (I) is preferably a hydroxy group.

[0270] The component (D01) is preferably a compound represented by any one of the following general formulas (d01-1) to (d01-3).

[0271] [In the formula, n01 to n03 each independently represent an integer of 1 to 15. p01 to p03 each independently represent an integer of 1 to 5. q01 to q03 each independently represent an integer of 0 to 5.]

[0272] In the formulas (d01-1) and (d01-2), n01 to n03 are preferably integers of 1 to 14, more preferably integers of 1 to 13, even more preferably integers of 1 to 11, and particularly preferably integers of 1 to 9.

[0273] In formula (d01-3), p01 to p03 are preferably integers of 1 to 5, more preferably integers of 1 to 3, and even more preferably 1 or 2. In formula (d01-3), q01 to q03 are preferably integers of 0 to 5, more preferably integers of 0 to 3, still more preferably integers of 0 to 2, and particularly preferably 0 or 1.

[0274] Specific examples of the component (D01) are shown below, but are not limited to these.

[0275]

[0276] In addition to the above-mentioned examples, specific examples of the component (D01) include trialkylamines such as trimethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-nonylamine, and tri-n-dodecylamine; trialkylalcoholamines such as tri-n-octanolamine; 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, and triethanolamine triacetate.

[0277] The component (D01) may be used alone, or two or more types may be used in combination. In the resist composition of this embodiment, the amount of the component (D01) relative to 100 parts by mass of the component (A) is typically 0.001 to 0.500 parts by mass. The amount of the component (D01) relative to 100 parts by mass of the component (A) is preferably 0.010 to 0.500 parts by mass, more preferably 0.020 to 0.100 parts by mass, even more preferably 0.025 to 0.075 parts by mass, and particularly preferably 0.025 to 0.050 parts by mass.

[0278] <<Component (D02)>> The component (D02) is at least one compound selected from the group consisting of a compound represented by the following general formula (d02-1) (hereinafter also referred to as “component (D02-1)”) and a compound represented by the following general formula (d02-2) (hereinafter also referred to as “component (D02-2)”):

[0279] [In the formula, Ry ０１ ~Ry ０３ each independently represents a hydrocarbon group which may have a substituent; ny0 represents an integer of 0 to 3; Rz ０１ and Rz ０２ Rz each independently represents a hydrocarbon group which may have a substituent, or a hydrogen atom. ０３ represents a hydrocarbon group which may have a substituent; and nz0 represents an integer of 0 to 5.

[0280] Component (D02-1) In the formula (d02-1), Ry ０１ ~Ry ０３ The hydrocarbon group in Ry may be an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, but is preferably an aliphatic hydrocarbon group which may have a substituent. ０１ ~Ry ０３ The hydrocarbon group in the formula (I) preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0281] Ry ０１ ~Ry ０３The aliphatic hydrocarbon group in may be linear, branched, or contain a ring structure. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated.

[0282] Ry ０１ ~Ry ０３ The linear aliphatic hydrocarbon group in Ry is preferably a linear alkyl group. ０１ and Ry ０２ The linear alkyl group in Ry preferably has 1 to 10 carbon atoms, more preferably has 2 to 6 carbon atoms, and even more preferably has 2 to 4 carbon atoms. ０１ and Ry ０２ Specific examples of the linear alkyl group in the formula (d01) include Rx １ , Rx ２ and Rx ３ The straight-chain alkyl groups in Ry are the same as those in Ry. ０３ The linear alkyl group in Ry preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and even more preferably has 1 to 4 carbon atoms. ０３ Specific examples of the linear alkyl group in the formula (d01) include Rx ０１ ~Rx ０３ Examples of the straight-chain alkyl group include the same as the straight-chain alkyl group in the above.

[0283] Ry ０１ ~Ry ０３ The branched aliphatic hydrocarbon group in Ry is preferably a branched alkyl group. ０１ ~Ry ０３ The branched alkyl group in Ry preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms. ０１ ~Ry ０３ Specific examples of the linear alkyl group in the formula (d01) include Rx ０１ ~Rx ０３ Examples of the branched alkyl group include the same as those in the above.

[0284] Ry ０１ ~Ry ０３The linear or branched alkyl group in the formula (d01) may or may not have a substituent. ０１ ~Rx ０３ The substituents are the same as those in the above.

[0285] Ry ０１ ~Ry ０３ Examples of the aliphatic hydrocarbon group containing a ring structure in the formula (I) include cyclic aliphatic hydrocarbon groups (cycloalkyl groups or heterocycloalkyl groups) that may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched alkylene group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in a linear or branched alkyl group. The cyclic aliphatic hydrocarbon group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms. The ring structure may be a polycyclic group or a monocyclic group. Preferred monocyclic ring structures are monocycloalkanes. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopropane, cyclobutane, cyclopentane, and cyclohexane. Preferred polycyclic ring structures are polycycloalkanes. The polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0286] Ry ０１ ~Ry ０３ The cyclic aliphatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), an alkyl group, an ester bond [-C(=O)-O-], and an ether bond (-O-). The ester bond and the ether bond as the substituent are groups that substitute the methylene group that constitutes the cyclic aliphatic hydrocarbon group. Ry ０１ ~Ry ０３The cyclic aliphatic hydrocarbon group in the formula (I) preferably does not have an amino group as a substituent. The halogen atom as the substituent is preferably a fluorine atom or a bromine atom. The alkyl group as the substituent preferably has 1 to 6 carbon atoms. Of these, the substituent is preferably a hydroxy group or an alkyl group.

[0287] Ry ０１ ~Ry ０３ The aromatic hydrocarbon group in the formula (I) is a group containing at least one aromatic ring. The aromatic ring 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. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms (excluding nitrogen atoms). Examples of heteroatoms in aromatic heterocycles include oxygen atoms and sulfur atoms. Specific examples of aromatic heterocycles include furan rings and thiophene rings.

[0288] Ry ０１ ~Ry ０３ Examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., 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 alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and even more preferably 1.

[0289] Ry ０１ ~Ry ０３The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), an alkyl group, etc. Examples of the halogen atom and alkyl group as the substituent include the same as those exemplified as the substituents for the cyclic aliphatic hydrocarbon group. Among them, a hydroxy group or an alkyl group is preferred as the substituent.

[0290] Ry ０１ and Ry ０２ R is preferably an aliphatic hydrocarbon group, more preferably a branched alkyl group, and even more preferably a branched alkyl group having 3 to 6 carbon atoms. ０１ and Ry ０２ Preferred specific examples of Ry include an isopropyl group, an isobutyl group, and a tert-butyl group. ０１ and Ry ０２ are preferably the same group.

[0291] Ry ０３ As the alkyl group, a linear or branched alkyl group is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred.

[0292] In formula (d02-1), ny0 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0293] Specific examples of the component (D02-1) are shown below, but are not limited to these.

[0294]

[0295] Component (D02-2) In the formula (d02-2), Rz ０１ ~Rz ０３ The hydrocarbon group in Rz may be an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, but is preferably an aliphatic hydrocarbon group which may have a substituent. ０１ ~Rz ０３The hydrocarbon group in the formula (I) preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0296] Rz ０１ ~Rz ０３ The aliphatic hydrocarbon group in may be linear, branched, or contain a ring structure. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated.

[0297] Rz ０１ ~Rz ０３ The linear aliphatic hydrocarbon group in Rz is preferably a linear alkyl group. ０１ and Rz ０２ The linear alkyl group in Rz preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. ０１ and Rz ０２ Specific examples of the linear alkyl group in the formula (d01) include Rx １ , Rx ２ and Rx ３ The straight-chain alkyl groups in Rz are the same as those in Rz. ０３ The linear alkyl group in Rz preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. ０３ Specific examples of the linear alkyl group in the formula (d01) include Rx ０１ ~Rx ０３ Examples of the straight-chain alkyl group include the same as the straight-chain alkyl group in the above.

[0298] Rz ０１ ~Rz ０３ The branched aliphatic hydrocarbon group in Rz is preferably a branched alkyl group. ０１ ~Rz ０３ The branched alkyl group in Rz preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms. ０１ ~Rz ０３ Specific examples of the linear alkyl group in the formula (d01) include Rx ０１ ~Rx ０３Examples of the branched alkyl group include the same as those in the above.

[0299] Rz ０１ ~Rz ０３ The linear or branched alkyl group in the formula (d01) may or may not have a substituent. ０１ ~Rx ０３ The substituents are the same as those in the above.

[0300] Rz ０１ ~Rz ０３ Examples of the aliphatic hydrocarbon group containing a ring structure in the formula (I) include cyclic aliphatic hydrocarbon groups (cycloalkyl groups or heterocycloalkyl groups) that may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched alkylene group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in a linear or branched alkyl group. The cyclic aliphatic hydrocarbon group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms. The ring structure may be a polycyclic group or a monocyclic group. Preferred monocyclic ring structures are monocycloalkanes. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopropane, cyclobutane, cyclopentane, and cyclohexane. Preferred polycyclic ring structures are polycycloalkanes. The polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0301] Rz ０１ ~Rz ０３The cyclic aliphatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), an alkyl group, an ester bond [-C(=O)-O-], and an ether bond (-O-). The ester bond and the ether bond as the substituent are groups that substitute the methylene group that constitutes the cyclic aliphatic hydrocarbon group. ０１ ~Rz ０３ The cyclic aliphatic hydrocarbon group in the formula (I) preferably does not have an amino group as a substituent. The halogen atom as the substituent is preferably a fluorine atom or a bromine atom. The alkyl group as the substituent preferably has 1 to 6 carbon atoms. Of these, the substituent is preferably a hydroxy group or an alkyl group.

[0302] Rz ０１ ~Rz ０３ The aromatic hydrocarbon group in the formula (I) is a group containing at least one aromatic ring. The aromatic ring 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. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms (excluding nitrogen atoms). Examples of heteroatoms in aromatic heterocycles include oxygen atoms and sulfur atoms. Specific examples of aromatic heterocycles include furan rings and thiophene rings.

[0303] Rz ０１ ~Rz ０３Examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., 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 alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and even more preferably 1.

[0304] Rz ０１ ~Rz ０３ The aromatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), an alkyl group, etc. Examples of the halogen atom and alkyl group as the substituent include the same as those exemplified as the substituents for the cyclic aliphatic hydrocarbon group. Among them, a hydroxy group or an alkyl group is preferred as the substituent.

[0305] Rz ０１ and Rz ０２ Rz is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms. ０１ and Rz ０２ are preferably the same group.

[0306] Rz ０３ As the alkyl group, a linear or branched alkyl group is preferred, and a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms is more preferred.

[0307] In the formula (d02-2), nz0 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0 or 2.

[0308] The component (D02-2) is preferably a compound represented by the following general formula (d02-2-1) or (d02-2-2).

[0309] [In the formula, Rz ０１３ ~Rz ０１５ each independently represents a hydrocarbon group which may have a substituent; nz01 represents an integer of 0 to 3; Rz ０２３ ~Rz ０２５ each independently represents a hydrocarbon group which may have a substituent; and nz02 represents an integer of 0 to 5.

[0310] In the formula (d02-2-1), Rz ０１３ Examples of the hydrocarbon group which may have a substituent include Rz in formula (d02-2). ０３ Examples of the hydrocarbon group include the same hydrocarbon groups as those optionally having a substituent in the above.

[0311] In the formula (d02-2-1), Rz ０１４ and Rz ０１５ Examples of the hydrocarbon group which may have a substituent include Rz in formula (d02-2). ０１ and Rz ０２ The hydrocarbon groups may be the same as those in the group Rz, which may have a substituent. ０１４ and Rz ０１５ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, and even more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. ０１４ and Rz ０１５ is preferably a branched alkyl group having 3 to 6 carbon atoms, more preferably a branched alkyl group having 3 or 4 carbon atoms, and even more preferably an isopropyl group. ０１４ and Rz ０１５ are preferably the same group.

[0312] In the formula (d02-2-1), nz01 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0313] In the formula (d02-2-2), Rz ０２３Examples of the hydrocarbon group which may have a substituent include Rz in formula (d02-2). ０３ Examples of the hydrocarbon group include the same hydrocarbon groups as those optionally having a substituent in the above.

[0314] In the formula (d02-2-2), Rz ０２４ and Rz ０２５ Examples of the hydrocarbon group which may have a substituent include Rz in formula (d02-2). ０１ and Rz ０２ The hydrocarbon groups may be the same as those in the group Rz, which may have a substituent. ０２４ and Rz ０２５ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, and even more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. ０２４ and Rz ０２５ is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group having 2 to 6 carbon atoms, and even more preferably a linear alkyl group having 3 or 4 carbon atoms. ０２４ and Rz ０２５ are preferably the same group.

[0315] In the formula (d02-2-2), nz02 is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0316] Specific examples of the component (D02-2) are shown below, but are not limited to these.

[0317]

[0318] The component (D02) may be used alone or in combination of two or more. The component (D02) may be the component (D02-1) or the component (D02-2), or a combination of the components (D02-1) and (D02-2).

[0319] In the resist composition of this embodiment, the amount of the component (D02) relative to 100 parts by mass of the component (A) is typically 0.001 to 0.500 parts by mass. The amount of the component (D02) relative to 100 parts by mass of the component (A) is preferably 0.010 to 0.500 parts by mass, more preferably 0.020 to 0.100 parts by mass, even more preferably 0.025 to 0.075 parts by mass, and particularly preferably 0.050 to 0.075 parts by mass.

[0320] In the resist composition of this embodiment, the mass ratio of the component (D01) to the component (D02) (component (D01):component (D02)) is typically from 5:1 to 1:5, preferably from 3:1 to 1:3, and more preferably from 1:1 to 1:3. When the mass ratio is within this range, the generation of scum is suppressed when a resist pattern is formed, making it easier to form a good pattern.

[0321] In the resist composition of this embodiment, the total amount of component (D01) and component (D02) per 100 parts by mass of component (A) is typically 0.005 to 1.000 parts by mass, preferably 0.010 to 1.000 parts by mass, more preferably 0.050 to 0.500 parts by mass, even more preferably 0.070 to 0.300 parts by mass, and particularly preferably 0.100 to 0.200 parts by mass. By ensuring that the total amount of component (D01) and component (D02) falls within this range, the generation of scum is suppressed when a resist pattern is formed, making it easier to form a good pattern.

[0322] Other (D) Components In addition to the components (D01) and (D02), the component (D) may contain another acid diffusion controller. Examples of the other acid diffusion controller include a photodegradable base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure and loses its acid diffusion control properties, and a nitrogen-containing organic compound (D2) (not corresponding to the components (D1), (D01), and (D02)) (hereinafter referred to as "component (D2)"). The components (D1) and (D2) may be contained in the form of a compound, or may be incorporated into the component (A1) as the structural unit (a6), or may take both of these forms. The compounds exemplified below as the component (D1) may be used as the acid generator component (component (B)) depending on the combination with other compounds.

[0323] Regarding the component (D1): The component (D1) is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"). The components (d1-1) to (d1-3) decompose and lose their acid diffusion controllability (basicity) in the exposed areas of the resist film, and therefore do not act as quenchers, but act as quenchers in the unexposed areas of the resist film.

[0324] [In the formula, Rd １ ~Rd ４ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. ２ In the formula, no fluorine atom is bonded to the carbon atom adjacent to the S atom. １ is a single bond or a divalent linking group; m is an integer of 1 or more; M ｍ＋ are each independently an m-valent organic cation.

[0325] {Component (d1-1)} Anion portion In formula (d1-1), Rd１ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each of the R' ２０１ Among these, Rd １ is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-7), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (L-al-1) to (L-al-8). Note that Rd １ In the case where the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in the formula (d1-1) has a linking group represented by each of the general formulae (L-al-1) to (L-al-8) as a substituent, in the general formulae (L-al-1) to (L-al-8), Rd in formula (d1-1) １ The carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in the formula (L-al-1) to (L-al-8) is bonded to V' １０１ Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure). Suitable examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, tricyclo[5.2.1.0], ２，６

[0033] More preferably, it is a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as decane or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0326] When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and 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.

[0327] Specific examples of preferred anion moieties of component (d1-1) are shown below.

[0328]

[0329] ...cation moiety In formula (d1-1), M ｍ＋ is an m-valent organic cation. ｍ＋ Suitable examples of the organic cation include the same as the cations represented by the general formulae (ca-1) to (ca-3), with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the general formulae (ca-1-1) to (ca-1-84) being even more preferred. One type of component (d1-1) may be used alone, or two or more types may be used in combination.

[0330] {Component (d1-2)} Anion portion In formula (d1-2), Rd ２is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ However, Rd ２ In the formula, the carbon atom adjacent to the S atom is not bonded to a fluorine atom (is not substituted with fluorine). This makes the anion of component (d1-2) an appropriately weak acid anion, improving the quenching ability of component (D). ２ The alkyl group is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.

[0331] The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10. The aliphatic cyclic group includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0], ２，６ ] a group (which may have a substituent) in which one or more hydrogen atoms have been removed from decane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor is more preferred.

[0332] Rd ２ The hydrocarbon group may have a substituent, and the substituent may be Rd １ Examples of the substituents include the same as those that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above.

[0333] Specific examples of preferred anion moieties of component (d1-2) are shown below.

[0334]

[0335] ...cation moiety In formula (d1-2), M ｍ＋ is an m-valent organic cation, and M in the formula (d1-1) ｍ＋ The component (d1-2) may be used alone or in combination of two or more.

[0336] {Component (d1-3)} Anion portion In formula (d1-3), Rd３ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ Among these, a fluorinated alkyl group is preferred, and the Rd １ The same fluorinated alkyl groups as those mentioned above are more preferred.

[0337] In formula (d1-3), Rd ４ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent, is preferable. ４ The alkyl group in Rd is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. ４ A part of the hydrogen atoms of the alkyl group may be substituted with a hydroxyl group, a cyano group, etc. ４ The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.

[0338] Rd ４ The alkenyl group in R' ２０１ Examples include the same alkenyl groups as those in the above, and vinyl, propenyl (allyl), 1-methylpropenyl, and 2-methylpropenyl groups are preferred. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

[0339] Rd ４ The cyclic group in２０１ Examples thereof include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0], and the like. ２，６ ] An alicyclic group in which one or more hydrogen atoms have been removed from a cycloalkane such as decane or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group is preferred. ４ When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in excellent lithography properties. ４ When is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition exhibits excellent light absorption efficiency, and exhibits favorable sensitivity and lithography properties.

[0340] In formula (d1-3), Yd １ represents a single bond or a divalent linking group. １ The divalent linking group in is not particularly limited, but examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. ２１ Examples of the divalent linking group include the same divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom as those mentioned in the description of the divalent linking group in １ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.

[0341] Specific examples of preferred anion moieties of component (d1-3) are shown below.

[0342]

[0343]

[0344] In formula (d1-3), M ｍ＋ is an m-valent organic cation, and M in the formula (d1-1) ｍ＋The component (d1-3) may be used alone or in combination of two or more.

[0345] The component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them. When the resist composition contains the component (D1), the amount of the component (D1) within 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, relative to 100 parts by mass of the component (A).

[0346] The component (D1) preferably contains the component (d1-1). The content of the component (d1-1) in the entire component (D1) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. The component (D1) may consist solely of the compound component (d1-1).

[0347] Production method of component (D1): The production method of the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods. Furthermore, the production method of component (d1-3) is not particularly limited, and they can be produced, for example, by the same method as described in US 2012-0149916. The compound of component (D1) has been shown as an example of a base component (component (D)) that traps acid generated by exposure, but the compound of component (D1) may also be used as component (B).

[0348] Regarding the component (D2): The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not fall under any of the above-mentioned components (D1), (D01), and (D02). The component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under any of the above-mentioned components (D1), (D01), and (D02), and any known component may be used. Examples of the component (D2) include aliphatic amines and aromatic amines.

[0349] The aliphatic amines include ammonia (NH ３) in which one or two hydrogen atoms have been substituted with an alkyl group or a hydroxyalkyl group (alkylamine or alkyl alcohol amine) or 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; and alkyl alcohol amines such as diethanolamine, diisopropanolamine, and di-n-octanolamine.

[0350] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. Specific examples of aliphatic polycyclic amines include those having 6 to 10 carbon atoms, such as 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0351] Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, and the like.

[0352] The component (D2) may be used singly, or in combination of two or more types. When the resist composition contains the component (D2), the amount of the component (D2) within the resist composition is typically within a range from 0.01 to 5 parts by mass per 100 parts by mass of the component (A). By ensuring that the amount is within this range, the resist pattern shape and stability over time during storage can be improved.

[0353] The resist composition of this embodiment preferably does not contain the component (D1) or the component (D2).

[0354] <Optional Components> The resist composition of this embodiment may further contain other components in addition to the above-described components (A) and (D). Examples of other components include the below-described components (B), (E), (F), and (S).

[0355] <Acid Generator Component (B)> The resist composition of this embodiment may contain an acid generator component (B) that generates acid upon exposure. The component (B) is not particularly limited, and any of the components that have been proposed as acid generators for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators. The component (B) may be contained in the form of a compound, or may be incorporated into the component (A1) as the structural unit (a5) described above, or may be in both of these forms.

[0356] Examples of the onium salt acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), a compound represented by general formula (b-2) (hereinafter also referred to as "component (b-2)"), or a compound represented by general formula (b-3) (hereinafter also referred to as "component (b-3)"):

[0357] [In the formula, R １０１ and R １０４ ~R １０８ R are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. １０４ and R １０５ may be bonded to each other to form a ring structure. １０２ is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. １０１ is a divalent linking group containing an oxygen atom or a single bond. １０１ ~V １０３are each independently a single bond, an alkylene group, or a fluorinated alkylene group. １０１ and V １０１ cannot be a single bond at the same time. １０１ ~L １０２ are each independently a single bond or an oxygen atom. １０３ ~L １０５ each independently represents a single bond, —CO— or —SO ２ m is an integer of 1 or more, and M' ｍ＋ is an m-valent onium cation.

[0358] {Anion moiety} Anion in component (b-1) In formula (b-1), R １０１ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0359] 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 which does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated.

[0360] R １０１ The aromatic hydrocarbon group in R is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. １０１ Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. １０１Specific examples of the aromatic hydrocarbon group in include groups in which one hydrogen atom has been removed from the aromatic ring (aryl groups: for example, phenyl group, naphthyl group, etc.), and groups in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0361] R １０１ Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed within a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ] Polycycloalkanes having a polycyclic skeleton of a bridged ring system, such as decane and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid skeleton, are more preferred.

[0362] Among them, R １０１The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0363] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ -] and the like. The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even 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, and 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 alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0364] Also, R １０１ The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specifically, lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7), —SO 2 represented by the general formulae (b5-r-1) to (b5-r-4), ２ -containing cyclic groups, and other heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16), respectively.

[0365] R １０１Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. The halogen atom as a substituent is preferably a fluorine atom, a bromine atom, or an iodine atom. Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the halogen atoms. The carbonyl group as a substituent is a methylene group (-CH) constituting a cyclic hydrocarbon group. ２ -) is a group that substitutes

[0366] R １０１ The cyclic hydrocarbon group in may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a bridged ring polycyclic skeleton to which one or more aromatic rings are fused. Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. １０１ Specific examples of the fused cyclic group in formula (b-1) include groups represented by the following formulae (r-br-1) and (r-br-2). １０１ represents a bond bonded to

[0367]

[0368] R １０１Examples of the substituent that the fused cyclic group in the formula (I) may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, etc. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the fused cyclic group can be selected from the group consisting of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the fused cyclic group described above in R １０１ Examples of the aromatic hydrocarbon group as a substituent of the fused cyclic group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been 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). Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include a group in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane or cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ a group in which one hydrogen atom has been removed from a polycycloalkane such as decane or tetracyclododecane; a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7); a —SO 2 group represented by each of the general formulae (b5-r-1) to (b5-r-4), ２ -containing cyclic group: heterocyclic groups represented by the above formulae (r-hr-7) to (r-hr-16), respectively.

[0369] A chain alkyl group which may have a substituent: R １０１The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0370] A chain alkenyl group which may have a substituent: R １０１ The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, a linear alkenyl group is preferred, a vinyl group or a propenyl group is more preferred, and a vinyl group is particularly preferred.

[0371] R １０１ Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the R １０１ Examples of the cyclic groups include the cyclic groups shown in the formula:

[0372] In formula (b-1), Y １０１ is a single bond or a divalent linking group containing an oxygen atom. １０１ is a divalent linking group containing an oxygen atom, １０１may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of divalent linking groups containing oxygen atoms include the linking groups represented by the above general formulas (L-a1-1) to (L-a1-8). In the following general formulas (L-a1-1) to (L-a1-8), R in the above formula (b-1) １０１ and V' in the following general formulae (L-al-1) to (L-al-8) １０１ is.

[0373] In formula (b-1), V １０１ is a single bond, an alkylene group or a fluorinated alkylene group. １０１ is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0374] In formula (b-1), R １０２ is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. １０２ is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0375] Specific examples of the anion moiety represented by the formula (b-1) include, for example, Y １０１ When Y is a single bond, examples of the anion include a fluorinated alkylsulfonate anion such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion; １０１ When is a divalent linking group containing an oxygen atom, examples of the anion include those represented by any one of the following formulae (an-1) to (an-3).

[0376] [In the formula, R” １０１ R" is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-16), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a chain alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent. １０２represents an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the formula (r-br-1) or (r-br-2) above, a lactone-containing cyclic group represented by each of the general formulae (a2-r-1), (a2-r-3) to (a2-r-7) above, or —SO ２ -containing cyclic group. １０３ V" is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. １０１ is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. １０２ is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; each v" is independently an integer of 0 to 3; each q" is independently an integer of 0 to 20; and n" is 0 or 1.

[0377] R” １０１ , R” １０２ and R” １０３ The aliphatic cyclic group which may have a substituent is represented by R １０１ The substituent is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in the formula (b-1). １０１ Examples of the substituents that may be substituted on the cyclic aliphatic hydrocarbon group in the above formula (1) include the same as those that may be substituted on the cyclic aliphatic hydrocarbon group in the above formula (1).

[0378] R” １０１ and R” １０３ The aromatic cyclic group which may have a substituent in the formula (b-1) is R １０１ The substituent is preferably a group exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group in the formula (b-1). １０１ Examples of the substituents that may substitute the aromatic hydrocarbon group in the above formula (1) include the same as those in the above formula (1).

[0379] R” １０１ The chain alkyl group which may have a substituent in the formula (b-1) is R １０１ R" is preferably a group exemplified as a chain alkyl group in １０３The chain alkenyl group which may have a substituent is R １０１ Preferably, it is a group exemplified as the chain alkenyl group in the above formula.

[0380] Anion in component (b-2) In formula (b-2), R １０４ , R １０５ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each is represented by R １０１ However, R １０４ , R １０５ may be bonded to each other to form a ring. １０４ , R １０５ is preferably a chain alkyl group which may have a substituent, more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms in the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. １０４ , R １０５ The number of carbon atoms in the chain alkyl group of R is preferably as small as possible within the above range of carbon atoms, for reasons such as good solubility in resist solvents. １０４ , R １０５ In the chain alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength and the improved transparency to high-energy light of 250 nm or less and electron beams, which is preferable. The proportion of fluorine atoms in the chain alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V １０２ , V １０３ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each represents V in formula (b-1). １０１ In formula (b-2), L １０１ , L １０２are each independently a single bond or an oxygen atom.

[0381] Anion in component (b-3) In formula (b-3), R １０６ ~R １０８ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each is represented by R １０１ In formula (b-3), L １０３ ~L １０５ each independently represents a single bond, —CO— or —SO ２ - is.

[0382] Of the above, the anion moiety of component (B) is preferably the anion in component (b-1), and more preferably the anion represented by formula (an-1).

[0383] {Cation Moiety} In the formula (b-1), formula (b-2), and formula (b-3), M' ｍ＋ represents an m-valent onium cation. Among these, sulfonium cation and iodonium cation are preferred. m is an integer of 1 or more.

[0384] The cation moiety of the component (B) is preferably a sulfonium cation, more preferably a cation represented by each of the formulas (ca-1) to (ca-3), still more preferably a cation represented by the formula (ca-1), and particularly preferably a cation represented by each of the formulas (ca-1-1) to (ca-1-84).

[0385] The component (B) may be a compound that generates an organic acid represented by the following general formula (b-I) upon exposure (hereinafter also referred to as "component (BI)"), or a compound that generates a sulfonic acid represented by the following general formula (b-II) upon exposure (hereinafter also referred to as "component (B-II)").

[0386] [wherein, Xb １ represents a divalent organic group; Xb ２ is SO (NSO ２ R ｂ ) represents; Xb ３ is SO ２or SO (NSO ２ R ｂ ) represents; R ｂ represents a monovalent organic group. ｂ may be the same as or different from each other, and may be bonded to each other to form a ring structure.

[0387] [In the formula, Yb １ represents an n-valent linking group; Yb ２ represents a single bond or a divalent aliphatic group; n Yb ２ may be the same or different from each other, provided that Yb １ and Yb ２ At least one of the groups is a group containing a fluorine atom, and ny represents an integer of 2 to 4.

[0388] The component (BI) is a compound represented by the following general formula (bI-1):

[0389] [wherein, Xb １ , Xb ２ and Xb ３ is the same as in the formula (b-I), m is an integer of 1 or more, and M' ｍ＋ is an m-valent onium cation.

[0390] The component (B-II) is a compound represented by the following general formula (b-II-1):

[0391] [In the formula, Yb １ , Yb ２ and ny are the same as those in the formula (b-II). m is an integer of 1 or more, and M' ｍ＋ is an m-valent onium cation.

[0392] The resist composition of this embodiment may or may not contain the component (BI). The resist composition of this embodiment may or may not contain the component (B-II). From the standpoint of suppressing the generation of scum during resist pattern formation, it is preferable that the resist composition of this embodiment does not contain the component (BI) or the component (B-II).

[0393] In the resist composition of this embodiment, the component (B) may be used singly, or two or more types may be used in combination. When the resist composition contains the component (B), the amount of the component (B) in the resist composition, relative to 100 parts by mass of the component (A), is preferably less than 30 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass. By ensuring that the amount of the component (B) falls within the above-mentioned preferred range, a homogeneous solution is more likely to be obtained when the respective components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is favorable.

[0394] <<At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxo acids, and derivatives thereof>> The resist composition of this embodiment may contain at least one compound (E) (hereinafter referred to as "component (E)") selected from the group consisting of organic carboxylic acids, phosphorus oxo acids, and derivatives thereof as an optional component for the purposes of preventing sensitivity degradation and improving resist pattern shape and post-exposure stability. Specific examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, with salicylic acid being preferred. Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred. Specific examples of phosphonic acids include phenylphosphonic acid.

[0395] In the resist composition of this embodiment, the component (E) may be used singly, or two or more different components may be used in combination. When the resist composition contains the component (E), the amount of the component (E) per 100 parts by mass of the component (A) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. By ensuring that the amount is within this range, lithography properties are further improved.

[0396] <Fluorine Additive Component (F)> The resist composition of this embodiment may contain a fluorine additive component (hereafter referred to as "component (F)") as a hydrophobic resin. The component (F) is used to impart water repellency to the resist film, and by using it as a resin separate from component (A), it is possible to improve lithography properties. Examples of the component (F) that can be used include the fluorine-containing polymer compounds described in JP 2010-002870 A, JP 2010-032994 A, JP 2010-277043 A, JP 2011-13569 A, and JP 2011-128226 A. More specific examples of the component (F) include polymers having a structural unit (f1) represented by the following general formula (f1-1): This polymer is preferably a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) with the structural unit (a1); or a copolymer of the structural unit (f1) with a structural unit derived from acrylic acid or methacrylic acid and the structural unit (a1), and more preferably a copolymer of the structural unit (f1) with the structural unit (a1). Here, the structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl(meth)acrylate or a structural unit derived from 1-methyl-1-adamantyl(meth)acrylate, and more preferably a structural unit derived from 1-ethyl-1-cyclooctyl(meth)acrylate.

[0397] [wherein R is the same as defined above, and Rf １０２ and Rf １０３ Rf each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; １０２ and Rf １０３ may be the same or different. １ is an integer of 0 to 5, and Rf １０１ is an organic group containing a fluorine atom.

[0398] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as defined above. R is preferably a hydrogen atom or a methyl group. １０２ and Rf １０３ The halogen atom in Rf is preferably a fluorine atom. １０２ and Rf １０３ Examples of the alkyl group having 1 to 5 carbon atoms in Rf include the same alkyl groups having 1 to 5 carbon atoms as those in R, and a methyl group or an ethyl group is preferred. １０２ and Rf １０３ Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is preferred. Among these, Rf １０２ and Rf １０３ In formula (f1-1), nf is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom. １ is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

[0399] In formula (f1-1), Rf １０１ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. In addition, the hydrocarbon group containing a fluorine atom is preferably one in which 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more, and particularly preferably 60% or more, because this increases the hydrophobicity of the resist film during immersion exposure. Among these, Rf １０１ is preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group, —CH ２ -CF ３ , -CH ２ -CF２ -CF ３ , -CH(CF ３ ) ２ , -CH ２ -CH ２ -CF ３ , -CH ２ -CH ２ -CF ２ -CF ２ -CF ２ -CF ３ is particularly preferred.

[0400] The weight-average molecular weight (Mw) of component (F) (based on polystyrene standards measured by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. When the Mw is below the upper limit of this range, the component has sufficient solubility in a resist solvent for use as a resist, while when the Mw is above the lower limit of this range, the resulting resist film has good water repellency. The dispersity (Mw / Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0401] In the resist composition of this embodiment, the component (F) may be used either as a single type, or as a combination of two or more types. When the resist composition contains the component (F), the amount of the component (F) relative to 100 parts by mass of the component (A) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass.

[0402] <Organic Solvent Component (S)> The resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as "component (S)"). In the resist composition of this embodiment, the component (S) may be used alone, or as a mixed solvent of two or more different solvents. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), cyclohexanone, and butyl acetate are preferred.

[0403] Also preferred as component (S) is a mixed solvent of PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into consideration the compatibility of PGMEA with the polar solvent, etc. Examples of polar solvents include PGME, butyl acetate, EL, and cyclohexanone. Also preferred as component (S) is a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone. In this case, the mixing ratio between the former and the latter is preferably 70:30 to 95:5 by mass. Also preferred as component (S) is a mixed solvent of PGMEA, PGME, and butyl acetate.

[0404] There are no particular limitations on the amount of component (S) used, and it is set appropriately depending on the coating film thickness and is a concentration that allows application to a substrate, etc. The solids concentration of the resist composition of this embodiment is, for example, from 1 to 50 mass%, preferably from 5 to 45 mass%, more preferably from 10 to 45 mass%, even more preferably from 20 to 45 mass%, still more preferably from 30 to 45 mass%, and particularly preferably from 30 to 40 mass%.

[0405] In the resist composition of this embodiment, after dissolving the resist material in component (S), impurities may be removed using a polyimide porous film, a polyamideimide porous film, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film. Examples of the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.

[0406] The resist composition of this embodiment as described above contains a component (D01) represented by general formula (d01) and a component (D02) represented by general formula (d02-1) or (d02-2). By containing the components (D01) and (D02), the resist composition of this embodiment exhibits the following effects: when a resist pattern is formed, the generation of scum is suppressed, and the pattern is prevented from becoming tapered, resulting in the formation of a resist pattern with a good shape. Furthermore, the resist composition also exhibits the effect of improving the CDU of the resist pattern. The reason for this effect is presumed to be as follows: When a resist film is formed using the resist composition of this embodiment, the aliphatic amine component (D01) may segregate to the upper part of the resist film, while the aromatic amine component (D02) may segregate to the lower part of the resist film. It is therefore presumed that this appropriately controls the diffusion of acid generated by exposure to both the upper and lower parts of the resist film. This is believed to suppress the generation of scum and the formation of a tapered resist pattern when the resist film is exposed and developed, and also to improve the CDU of the resist pattern.

[0407] When the resist film is thick (e.g., 5 μm or more), it is difficult for light from the exposure to reach the lower part of the resist film. Therefore, the thicker the resist film, the greater the risk of scum generation and tapered patterns. Due to the above-described effects, the resist composition of this embodiment can suppress scum generation and tapered patterns even when the resist film is thick (e.g., 5 μm or more). Therefore, the resist composition of this embodiment can be suitably used to form resist films with thicknesses of 5 μm or more. The resist composition of this embodiment can be suitably used to form resist films with thicknesses of, for example, 5 to 30 μm, 7 to 25 μm, or 10 to 20 μm.

[0408] Generally, when a basic substrate (e.g., a SiON substrate) is used, the pattern tends to have a tapered shape. The resist composition of this embodiment prevents the pattern from having a tapered shape, even when a basic substrate is used, and is able to form a resist pattern with a good shape.

[0409] (Method of Forming a Resist Pattern) The method of forming a resist pattern pertaining to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition pertaining to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern. One embodiment of the method of forming a resist pattern can be exemplified by a method of forming a resist pattern as follows.

[0410] First, the resist composition of the above-described embodiment is applied to a support using a spinner or the like, and baked (post-applied bake (PAB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C to form a resist film. Next, the resist film is selectively exposed using an exposure device such as an electron beam lithography device, an ArF exposure device, or a KrF exposure device, either through a mask (mask pattern) having a predetermined pattern formed thereon, or by direct irradiation with an electron beam without a mask pattern. The resist film is then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C. Next, the resist film is developed. In the case of an alkali development process, the development is performed using an alkaline developer, and in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0411] After the development treatment, a rinse treatment is preferably carried out. In the case of an alkaline development process, the rinse treatment is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse solution containing an organic solvent is preferably used. In the case of a solvent development process, after the development treatment or rinse treatment, a treatment may be carried out to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After the development treatment or rinse treatment, drying is carried out. Furthermore, in some cases, a bake treatment (post-bake) may be carried out after the development treatment.

[0412] The support is not particularly limited, and conventionally known supports can be used, such as substrates for electronic components and those having a predetermined wiring pattern formed thereon. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials that can be used for the wiring pattern include copper, aluminum, nickel, and gold. A basic substrate may also be used as the support. A basic substrate is a substrate whose surface is basic. Examples of basic substrates include substrates having a silicon oxynitride film (SiON substrates) and silicon nitride substrates (SiN substrates).

[0413] The thickness of the resist film formed using the resist composition related to the first aspect is preferably 5 μm or more, more preferably 7 μm or more, and even more preferably 10 μm or more. The thickness of the resist film is usually 30 μm or less. The thickness of the resist film can be 5 to 30 μm, preferably 7 to 25 μm, and more preferably 10 to 20 μm.

[0414] The wavelength used for exposure is not particularly limited, and may be an ArF excimer laser, a KrF excimer laser, or a F ２ Radiation such as excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The method of forming a resist pattern of this embodiment is particularly useful for a method in which the resist film is exposed to a KrF excimer laser in the step of exposing the resist film.

[0415] The exposure method for the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion exposure (liquid immersion lithography). Liquid immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure apparatus is filled in advance with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in this state. The liquid immersion medium is preferably a solvent having a refractive index greater than that of air and smaller than that of the resist film to be exposed, and examples thereof include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent. Water is preferably used as the liquid immersion medium.

[0416] An example of an alkaline developer used in the development treatment in the alkaline development process is a 0.1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent that can dissolve component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0417] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0418] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0419] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants.

[0420] The development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying the developer onto the surface of the support (spray method), or a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0421] The organic solvent contained in the rinse solution used in the rinsing treatment after development in the solvent development process can be appropriately selected from the organic solvents listed above as organic solvents used in the organic developer, as long as they do not easily dissolve the resist pattern. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination with two or more. They may also be used in combination with other organic solvents or water.

[0422] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method, such as a method of continuously applying the rinse solution onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse solution for a certain period of time (dipping method), or a method of spraying the rinse solution onto the surface of the support (spray method).

[0423] According to the resist pattern forming method of the present embodiment described above, the resist composition described above is used, which prevents the generation of scum, prevents the pattern from becoming tapered, and improves CDU, making it possible to form a resist pattern with a good shape.

[0424] The resist composition of the above-described embodiment and the various materials used in the pattern formation method of the above-described embodiment (e.g., resist solvent, developer, rinse, anti-reflective coating composition, top coat composition, etc.) preferably do not contain impurities such as metals, halogen-containing metal salts, acids, alkalis, or components containing sulfur or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free of impurities (below the detection limit of the measuring device).

[0425] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0426] <Preparation of Resist Compositions> (Examples 1 to 31, Comparative Examples 1 to 17) The components shown in Tables 1 to 3 were mixed and dissolved to prepare the resist compositions of each example.

[0427]

[0428]

[0429]

[0430] In Tables 1 to 3, the abbreviations have the following meanings. The values ​​in brackets [ ] indicate the blend amount (parts by mass). (A)-1: Polymer compound (A-1) shown below. The weight average molecular weight (Mw) calculated in terms of standard polystyrene as determined by GPC measurement was 10,000, and the molecular weight dispersity (Mw / Mn) was 1.90. １３The copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m / n = 40 / 35 / 25. (A)-2: Polymer compound (A-2) shown below. The weight average molecular weight (Mw) calculated in terms of standard polystyrene determined by GPC measurement was 10,000, and the molecular weight dispersity (Mw / Mn) was 1.90. １３ The copolymer composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m / n = 40 / 35 / 25. (A)-3: Polymer compound (A-3) shown below. The weight average molecular weight (Mw) calculated in terms of standard polystyrene determined by GPC measurement was 10,000, and the molecular weight dispersity (Mw / Mn) was 1.90. １３ The copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m / n = 40 / 35 / 25. (A)-4: Polymer compound (A-4) shown below. The weight average molecular weight (Mw) calculated in terms of standard polystyrene determined by GPC measurement was 10,000, and the molecular weight dispersity (Mw / Mn) was 1.75. １３ The copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m / n=40 / 40 / 20.

[0431]

[0432] (B)-1: An acid generator comprising the following compound (B-1).

[0433]

[0434] (D01)-1 to (D01)-5: Acid diffusion controllers consisting of compounds represented by the following chemical formulas (D01-1) to (D01-5).

[0435]

[0436] (D02)-1: An acid diffusion controller comprising a compound represented by the following chemical formula (D02-1-1). (D02)-2: An acid diffusion controller comprising a compound represented by the following chemical formula (D02-2-1). (D02)-3: An acid diffusion controller comprising a compound represented by the following chemical formula (D02-2-2).

[0437]

[0438] (E)-1: A compound represented by the following chemical formula (E-1).

[0439]

[0440] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / butyl acetate=50 / 50 / 25 (mass ratio).

[0441] <Formation of Resist Pattern> Step of Forming Resist Film: Each resist composition of the examples was applied using a spinner onto an 8-inch SiON substrate that had been treated with hexamethyldisilazane (HMDS) at 110°C for 60 seconds. The substrate was then pre-baked (PAB) on a hot plate at 140°C for 90 seconds and dried to form a resist film with a thickness of 14 μm or 18 μm.

[0442] Step of exposing resist film: Next, the resist film was irradiated with a KrF excimer laser (248 nm) using an exposure system NSR-203B (Nikon Corporation, NA (numerical aperture) = 0.60, σ = 0.68), followed by post-exposure bake (PEB) treatment at 120°C for 90 seconds.

[0443] Step of developing the exposed resist film: Next, alkaline development was carried out for 60 seconds at 23° C. using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) As a result, an isolated space pattern (hereinafter referred to as "IS pattern") with a space width of 5 μm or 3 μm was formed.

[0444] [Evaluation of ΔCD (top-bottom)] A resist film with a thickness of 14 μm was formed by the method described in <Formation of Resist Pattern> above, and an IS pattern with a space width of 5 μm was formed by KrF exposure and development. The dimensions (CD) of the top of the IS pattern (CD-top) and the CD of the bottom of the IS pattern (CD-bottom) were then measured using a scanning electron microscope S-9220 (manufactured by Hitachi High-Technologies Corporation). The difference between CD-top and CD-bottom was calculated, and the results are shown in Tables 4 to 6 as "ΔCD (μm)." A smaller ΔCD value indicates a more rectangular IS pattern with a better shape. The results of evaluation based on the following evaluation criteria are also shown. <Evaluation Criteria> A: ΔCD<4.5 μm B: 4.5 μm≦ΔCD<5.5 μm C: ΔCD≧5.5 μm

[0445] [Evaluation of Resist Footing Shape at Substrate Interface After Patterning] A resist film with a thickness of 14 μm was formed by the method described above in <Formation of Resist Pattern>, and an IS pattern with a space width of 3 μm was formed by KrF exposure and development. The degree of scum generation at the interface between the SiON substrate and the resist film was observed using a scanning electron microscope SU5000 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 4 to 6 as "scum (μm)." The smaller the scum value, the less footing there was and the better the shape. The results of evaluation based on the following evaluation criteria are also shown. <Evaluation Criteria> A: Scum < 0.5 μm B: 0.5 μm ≦ scum < 1.0 μm C: Scum ≧ 1.0 μm

[0446] [Evaluation of In-Plane Uniformity of Pattern Dimensions (CDU)] A resist film having a thickness of 18 μm was formed by the method described above in <Formation of Resist Pattern>, and an IS pattern with a space width of 5 μm was formed by KrF exposure and development. The CD at the bottom of the IS pattern was then measured using a scanning electron microscope S-9220 (manufactured by Hitachi High-Technologies Corporation). The value three times the measured standard deviation (σ) (3σ) was calculated. The results are shown in Tables 4 to 6 as "CDU (μm)." The smaller the 3σ value, the higher the dimensional (CD) uniformity of the space width formed in the resist film. <Evaluation Criteria> A: CDU<0.08 μm B: 0.08 μm≦CDU<1.2 μm C: CDU≧0.12 μm

[0447]

[0448]

[0449]

[0450] As shown in Tables 4 to 6, the resist compositions of Examples 1 to 31 were good in all of ΔCD, scum, and CDU. On the other hand, the resist compositions of Comparative Examples 1 to 16 were poor in any of ΔCD, scum, and CDU. The resist composition of Comparative Example 17 was unable to form a resist pattern.

[0451] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims.

Claims

1. A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, the resist composition comprising: a resin component (A1) whose solubility in a developer changes due to the action of the acid; a compound (D01) represented by the following general formula (d01); and at least one compound (D02) represented by the following general formula (d02-1) or (d02-2), wherein the resin component (A1) has a structural unit (a10) represented by the following general formula (a10-1): [In the formula, Rx ０１ ~Rx ０３ Ry each independently represents a chain hydrocarbon group which may have a substituent. ０１ ~Ry ０３ each independently represents a hydrocarbon group which may have a substituent; ny0 represents an integer of 0 to 3; Rz ０１ and Rz ０２ Rz each independently represents a hydrocarbon group which may have a substituent, or a hydrogen atom. ０３ represents a hydrocarbon group which may have a substituent; and nz0 represents an integer of 0 to 5. [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ｘ１ represents a single bond or a divalent linking group. ｘ１ represents an aromatic hydrocarbon group which may have a substituent. ａｘ１ represents an integer of 1 or more.

2. The resist composition according to claim 1, wherein the resin component (A1) further comprises a structural unit (a1) containing an acid-decomposable group whose polarity increases upon the action of an acid.

3. The resist composition according to claim 1 or 2, further comprising an acid generator component (B) that generates an acid upon exposure.

4. The resist composition according to claim 1 or 2, wherein the mass ratio of the compound (D01) to the compound (D02) is 1:1 to 1:

3.

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

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