Resist composition and resist pattern formation method

Abstract

The present invention relates to a resist composition containing: a base component (A) that exhibits changed solubility in a developing solution under the action of an acid; an acid generator component (B) that generates an acid upon exposure; and a fluorine additive component (F), wherein the fluorine additive component (F) contains a polymer compound (F1) having a constituent unit (f1) represented by general formula (f1-1) in the description, and neither a compound having a perfluoroalkyl skeleton nor a compound having a difluoromethyl group is contained in the resist composition.

Description

Resist composition and method for forming a resist pattern 【0001】 The present invention relates to a resist composition and a resist pattern forming method. 【0002】 In lithography technology, for example, a resist film made of a resist material is formed on a substrate, the resist film is selectively exposed to light, and a developing process is performed to form a resist pattern of a predetermined shape on the resist film. A resist material in which the exposed area of ​​the resist film changes its properties to dissolve in the developing solution is called a positive type, and a resist material in which the exposed area changes its properties to not dissolve in the developing solution is called a negative type. 【0003】 In recent years, advances in lithography technology have led to rapid miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display elements. Generally, miniaturization is achieved by shortening the wavelength (increasing the energy) of the exposure light source. Specifically, while ultraviolet light, such as the g-line and i-line, was conventionally used, mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers has now begun. Furthermore, even shorter wavelengths (higher energy) than these excimer lasers, such as EUV (extreme ultraviolet), EB (electron beam), and X-rays, are also being investigated. In this context, resist materials require lithographic characteristics such as sensitivity to these exposure light sources or energy sources, and resolution capable of reproducing patterns of fine dimensions. 【0004】One technique for further improving resolution is lithography, also known as liquid immersion lithography (hereinafter sometimes referred to as liquid immersion exposure), which involves placing a liquid with a higher refractive index than air (immersion medium) between the objective lens of the exposure machine and the sample during exposure (immersion exposure). It is said that with liquid immersion exposure, even when using a light source with the same exposure wavelength, the same high resolution as when using a shorter wavelength light source or a high NA lens can be achieved without any reduction in depth of field. Furthermore, liquid immersion exposure can be performed using existing exposure equipment. Therefore, liquid immersion exposure is expected to enable the formation of resist patterns that are low-cost, high-resolution, and have excellent depth of field, and is attracting considerable attention as it will have a significant impact on the semiconductor industry, both in terms of cost and lithographic characteristics such as resolution, in the manufacturing of semiconductor devices, which require large capital investments. Immersion lithography is effective for forming all kinds of pattern shapes and can also be combined with super-resolution techniques such as phase-shift and deformation illumination, which are currently under investigation. Currently, immersion lithography techniques using ArF excimer lasers as the light source are being actively researched. Also, water is currently being considered as the main immersion medium. 【0005】 Furthermore, in processes using TC-less resist films, which are advantageous for cost reduction in immersion lithography, the resist film surface is susceptible to the effects of its properties (hydrophilicity, hydrophobicity, etc.). For example, by increasing the hydrophobicity of the resist film surface, material elution is reduced, thereby improving lithography characteristics. 【0006】 In such resist compositions, it has been proposed to add compounds containing fluorine atoms (for example, Patent Documents 1-4). 【0007】 Japanese Patent Publication No. 5386236 Japanese Patent Publication No. 2010-275498 Japanese Patent Publication No. 5569402 Japanese Patent Publication No. 5713011 【0008】As lithography technology continues to advance and resist patterns become increasingly miniaturized, resist compositions are required to have good lithographic properties. Due to growing environmental awareness in recent years, the manufacture and use of compounds that fall under the category of PFAS (Per- and Polyfluoroalkyl Substances) may be restricted. Therefore, there is a need for the development of organofluorine compounds that do not contain perfluoroalkyl skeletons such as perfluoroalkyl groups and perfluoroalkylene groups, nor difluoromethyl groups. 【0009】 However, when a resist pattern was formed using a compound that does not contain either a perfluoroalkyl skeleton or a difluoromethyl group as a fluorine additive component, it was difficult to achieve sufficient water repellency and base degradability, and water droplets tended to remain on the wafer surface after immersion lithography. Therefore, conventional resist compositions were unable to suppress the occurrence of watermark defects (WMDs). 【0010】 The present invention has been made in view of the above circumstances, and aims to provide a resist composition and a resist pattern formation method that can form a resist pattern that can achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact. 【0011】 As a result of diligent research to solve the above problems, the present inventors have found that a resist composition and a resist pattern formation method can be obtained that can form a resist pattern that can achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact, with the following configuration, and have completed the present invention. 【0012】In other words, the present invention is as follows. The resist composition according to the first embodiment 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, comprising a base component (A) whose solubility in a developer changes due to the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and a fluorine additive component (F), wherein the fluorine additive component (F) comprises a polymer compound (F1) having a constituent unit (f1) represented by the following general formula (f1-1), and the resist composition does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0013】 【0014】 [In general formula (f1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. Lf is a divalent linking group. Ar is an aryl group. nf １ [ is an integer greater than or equal to 1.] 【0015】 A resist pattern formation method according to a second embodiment of the present invention is a resist pattern formation method comprising the steps of forming a resist film on a support using a resist composition according to an embodiment of the present invention, exposing the resist film, and developing the resist film to form a resist pattern. 【0016】 The present invention provides a resist composition and a resist pattern formation method that can achieve both the suppression of WMD required in the TC-Less process and the reduction of environmental impact. 【0017】 Figure 1 shows the advance angle (θ １ ), sweepback angle (θ ２ ) and fall angle (θ ３ This is a diagram explaining ). 【0018】 The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below. 【0019】In the present disclosure, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group, compound, etc. that does not have aromaticity. The "alkyl group" shall include linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. The "alkylene group" shall include linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms. The "constituent unit" means a monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer). When it is described as "may have a substituent", it includes both the case where a hydrogen atom (-H) is substituted with a monovalent group and the case where a methylene group (-CH ２ -) is substituted with a divalent group. "Exposure" is a concept that includes the entire irradiation of radiation. 【0020】 The "constituent unit derived from an acrylate ester" means a constituent unit formed by cleavage of the ethylenic double bond of an acrylate ester. The "acrylate ester" is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ２ =CH-COOH) is substituted with an organic group. In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R α０ ) that substitutes the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the like. Further, the acrylate ester is an itaconic acid diester in which the substituent (R α０ ) is substituted with a substituent containing an ester bond, or the substituent (R α０This also includes α-hydroxyacrylic esters in which the α-hydroxyalkyl group is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group thereof. Unless otherwise specified, the α-carbon atom of the acrylic ester refers to the carbon atom to which the carbonyl group of the acrylic ester is bonded. Hereinafter, an acrylic ester in which the hydrogen atom bonded to the α-carbon atom is substituted with a substituent may be called an α-substituted acrylic ester. Furthermore, acrylic esters and α-substituted acrylic esters may be collectively referred to as "(α-substituted) acrylic esters". 【0021】 In this disclosure, numerical ranges expressed using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits. Furthermore, in this disclosure, the amount of each component in a composition means the total amount of multiple substances corresponding to each component present in the composition, unless otherwise specified. Also, chemical structural formulas in this disclosure may be written as simplified structural formulas with hydrogen atoms omitted. In this disclosure, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and enantioisomers or diastereoisomers may exist. In such cases, one chemical formula represents all of these isomers. These isomers may be used individually or as a mixture. In this disclosure, "mass%" and "weight%" are synonymous, "parts by mass" and "parts by weight" are synonymous, and "mass ratio" and "weight ratio" are synonymous. 【0022】[Resist Composition] The resist composition according to an embodiment of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid, comprising a base component (A) whose solubility in a developer solution changes due to the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and a fluorine additive component (F), wherein the fluorine additive component (F) comprises a polymer compound (F1) having a constituent unit (f1) represented by the following general formula (f1-1), and the resist composition does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. Here, a perfluoroalkyl skeleton refers to a skeleton containing a perfluoroalkyl group or a perfluoroalkylene group. 【0023】 When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, acid is generated in the exposed areas of the resist film. The solubility of component (A) in the developer changes due to the action of this acid, while the solubility of component (A) in the developer does not change in the unexposed areas of the resist film. As a result, a difference in solubility in the developer occurs between the exposed and unexposed areas of the resist film. Therefore, when the resist film is developed, if the resist composition is positive type, the exposed areas of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is negative type, the unexposed areas of the resist film are dissolved and removed to form a negative type resist pattern. 【0024】In this disclosure, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. 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 an alkaline development process that uses an alkaline developer for the development process during resist pattern formation, or for a solvent development process that uses a developer containing an organic solvent (organic developer) for the development process. In other words, the resist composition of this embodiment may be a "positive resist composition for an alkaline development process" that forms a positive resist pattern in an alkaline development process, or a "negative resist composition for a solvent development process" that forms a negative resist pattern in a solvent development process. 【0025】 The resist composition of this embodiment contains a base component (A) that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and a fluorine additive component (F), wherein the fluorine additive component (F) includes a polymer compound (F1) having a constituent unit (f1) represented by the general formula (f1-1). 【0026】 Component (A) may generate acid upon exposure, in which case component (A) becomes a "substrate component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid." When component (A) is a substrate component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1), described later, is a polymer compound that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid. As such a polymer compound, a copolymer having a constituent unit that generates acid upon exposure can be used. Examples of constituent units that generate acid upon exposure include those that are known. 【0027】In conventional resist compositions, fluorine-containing compounds commonly used as fluorine additives cause problems such as segregation on the surface of the resist pattern, resulting in a deterioration of the rectangular shape of the pattern. Furthermore, from an environmental perspective, there is a desire to reduce the use of organofluorine compounds that fall under the category of PFAS (Periodic Fluorine-Free Aspirates), but removing fluorine from fluorine-containing compounds results in extremely low water repellency. 【0028】 The resist composition according to the embodiment of the present invention contains a polymer compound (F1) having a structural unit (f1) represented by general formula (f1-1) as a fluorine additive component (F), and does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group in the resist composition. Therefore, it is possible to achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact. 【0029】 ≪Component (A)≫ In the resist composition of this embodiment, component (A) is a base material component whose solubility in the developer solution changes due to the action of an acid, and it is preferable that component (A) includes a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in the developer solution changes due to the action of an acid. Component (A) may have increased solubility in the developer solution due to the action of an acid, or it may have decreased solubility in the developer solution due to the action of an acid. By using component (A1), the polarity of base material component (A) changes before and after exposure, so that good development contrast can be obtained not only in the alkaline development process but also in the solvent development process. At least component (A1) is used as component (A), and other polymer compounds and / or low molecular weight compounds may be used in combination with component (A1). 【0030】When an alkaline development process is applied, the substrate component (A) containing component (A1) is poorly soluble in the alkaline developer before exposure. When acid is generated from component (B) upon exposure, the polarity of the substrate component (A) increases due to the action of the acid, and its solubility in the alkaline developer increases. Therefore, when a resist film obtained by coating the resist composition onto a support is selectively exposed during the formation of a resist pattern, the exposed parts of the resist film change from poorly soluble to soluble in the alkaline developer, while the unexposed parts of the resist film remain poorly soluble in the alkali. Thus, a positive-type resist pattern is formed by alkaline development. 【0031】 On the other hand, when a solvent development process is applied, the substrate component (A) containing component (A1) is highly soluble in organic developer before exposure. When acid is generated from component (B) due to exposure, the polarity of the substrate component (A) increases due to the action of the acid, and its solubility in organic developer decreases. Therefore, when selectively exposing the resist film obtained by coating the resist composition onto a support during the formation of a resist pattern, the exposed parts of the resist film change from soluble to poorly soluble in organic developer, while the unexposed parts of the resist film remain soluble. Thus, by developing with an organic developer, a contrast can be created between the exposed and unexposed parts, and a negative-type resist pattern is formed. 【0032】 Component (A) is preferably a polymer compound (A1) having a constituent unit (a1) that contains an acid-degradable group whose polarity increases with the action of an acid (hereinafter also referred to as "component (A1)"). In addition to the constituent unit (a1), component (A1) may contain a lactone-containing cyclic group, -SO ２ - It is preferable to use a polymer compound having a constituent unit (a2) that contains a cyclic group or a carbonate-containing cyclic group. 【0033】 In the resist composition according to an embodiment of the present invention, component (A) may be used alone or in combination of two or more types. 【0034】The (A) component is a polymer compound that does not contain any compound having a perfluoroalkyl skeleton or a compound having a difluoromethyl group and does not fall under PFAS. That is, the (A1) component is a compound that does not fall under PFAS, and when the (A) component contains other components other than the (A1) component, the other components are also compounds that do not fall under PFAS. 【0035】 <Constituent unit (a1)> The constituent unit (a1) is a constituent unit containing an acid-decomposable group whose polarity increases by the action of an acid. The "acid-decomposable group" is a group having acid-decomposability such that at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of the acid-decomposable group whose polarity increases by the action of an acid include groups that decompose by the action of an acid to generate a polar group. Examples of the polar group include a carboxy group, a hydroxy group, an amino group, a sulfo group (-SO ３ H), etc. Among these, a polar group containing -OH in the structure (hereinafter sometimes referred to as "OH-containing polar group") is preferable, a carboxy group or a hydroxy group is more preferable, and a carboxy group is particularly preferable. More specifically, as the acid-decomposable group, a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group) can be mentioned. Here, the "acid-dissociable group" means (i) a group having acid-dissociability such that the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) after a part of the bonds are cleaved by the action of an acid, and then a decarboxylation reaction occurs, the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thereby, when the acid-dissociable group is dissociated by the action of an acid, a polar group having a higher polarity than the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the entire (A1) component increases. By increasing the polarity, relatively, the solubility in the developer changes. When the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases. 【0036】The structural unit (a1) preferably contains an acid-decomposable group having an alicyclic hydrocarbon group, and more preferably contains an acid-decomposable group having a monocyclic alicyclic hydrocarbon group. When the acid-decomposable group (acid dissociable group) in the structural unit (a1) has an alicyclic hydrocarbon group, the bulkiness is appropriate, so that the diffusion control of the acid and the solubility in the developer can be appropriately adjusted, and the roughness when forming a resist pattern can be reduced. Examples of the acid dissociable group in the structural unit (a1) include those proposed as the acid dissociable group of the base resin for chemically amplified resists. Specific examples of those proposed as the acid dissociable group of the base resin for chemically amplified resist compositions include "acetal-type acid dissociable groups", "tertiary alkyl ester-type acid dissociable groups", and "tertiary alkyloxycarbonyl acid dissociable groups". 【0037】 Acetal-type acid dissociable groups: As the acid dissociable group that protects a carboxy group or a hydroxy group among the polar groups, for example, an acid dissociable group represented by the following formula (a1-r-1) (hereinafter sometimes referred to as "acetal-type acid dissociable group") can be mentioned. 【0038】 【0039】 [In the formula, Ra' １ , Ra' ２ is a hydrogen atom or an alkyl group. Ra' ３ is a hydrocarbon group, and Ra' ３ may combine with either Ra' １ , Ra' ２ to form a ring.] 【0040】 In formula (a1-r-1), it is preferable that at least one of Ra' １ and Ra' ２ is a hydrogen atom, and more preferably both are hydrogen atoms. Ra' １ or Ra' ２If the alkyl group is an alkyl group, the alkyl group can be the same as those listed in the description of the α-substituted acrylic acid ester above as substituents that may be bonded to the α-carbon atom, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, linear or branched alkyl groups are preferred. More specifically, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc., with methyl group or ethyl group being more preferred, and methyl group being particularly preferred. 【0041】 In formula (a1-r-1), Ra' ３ Examples of hydrocarbon groups include linear or branched alkyl groups, or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups. Among these, the linear alkyl group is preferably methyl, ethyl, or n-butyl, with methyl or ethyl being more preferred. 【0042】 The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred. 【0043】 Ra' ３When the group 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 a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. 【0044】 Ra' ３ When a cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms 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. 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. ３Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. 【0045】 Ra' ３ The cyclic hydrocarbon group in may have substituents. Examples of substituents 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 -R Ｐ２ -COOH (These substituents are collectively referred to as "Ra ０５ It is also called "." ) are some examples. Here, R Ｐ１ This is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R Ｐ２ This is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. The cyclic hydrocarbon group may have one or more of the above substituents individually, or may have one or more of each of the above substituents. 【0046】Examples of monovalent linear saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 ２，６ ] Decanyl group, tricyclo[3.3.1.1 ３，７ ] Decanyl group, tetracyclo[6.2.1.1 ３，６ . 0 ２，７ Examples include polycyclic aliphatic saturated hydrocarbon groups such as dodecanyl groups and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene. 【0047】 Ra' ３ But, Ra' １ , Ra' ２ When the cyclic group is bonded to any of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group. 【0048】 Tertiary alkyl ester type acid-dissociating groups: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-2). Of the acid-dissociating groups represented by the following formula (a1-r-2), those composed of alkyl groups may hereafter be referred to as "tertiary alkyl ester type acid-dissociating groups" for convenience. 【0049】 【0050】 [In the formula, Ra' ４ ~Ra' ６ Each of these represents a hydrocarbon group, Ra' ５ , Ra' ６They may be joined to each other to form a ring. 【0051】 Ra' ４ The hydrocarbon group represented by Ra' includes linear or branched alkyl groups, linear or cyclic alkenyl groups, or cyclic hydrocarbon groups. ４ In the above, linear or branched alkyl groups, cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) are defined as Ra' ３ Examples include linear or branched alkyl groups and cyclic hydrocarbon groups similar to those in Ra'. ４ The linear or cyclic alkenyl group in Ra' is preferably an alkenyl group having 2 to 10 carbon atoms. ５ , Ra' ６ The hydrocarbon group is the aforementioned Ra' ３ Examples include those similar to the hydrocarbon group shown. 【0052】 Ra' ５ and Ra' ６ When these groups bond to each other to form a ring, the acid-dissociable group represented by the above formula (a1-r-2) is preferably the group represented by the following formula (a1-r2-1), the group represented by the following formula (a1-r2-2), and the group represented by the following formula (a1-r2-3). On the other hand, Ra' ４ ~Ra' ６ When these are independent hydrocarbon groups that are not bonded to each other, the group represented by the following formula (a1-r2-4) is a suitable example of the acid-dissociable group represented by the above formula (a1-r-2). 【0053】 【0054】 [In formula (a1-r2-1), Ra ０３１ This represents an alkyl group, Yab ０ Xab represents a carbon atom. ０ Yab ０This represents a group that forms an alicyclic hydrocarbon group together with Ya, and some or all of the hydrogen atoms in this alicyclic hydrocarbon group may be substituted. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra １０１ ~Ra １０３ Each of these is independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in these linear saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. Ra １０１ ~Ra １０３ Two or more of these may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra １０４ is an aromatic hydrocarbon group which may have substituents. In formula (a1-r2-4), Ra' １２ and Ra' １３ Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' １４ This is a hydrocarbon group that may have substituents. * indicates a bond. 【0055】 In the above formula (a1-r2-1), Ra ０３１ The alkyl group is preferably a linear alkyl group having 1 to 12 carbon atoms, and may be partially substituted with halogen atoms or heteroatom-containing groups. 【0056】 Ra ０３１ In this context, the linear alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. ０３１ In this, the branched alkyl group is the Ra' ４ Similar examples include the above. 【0057】 Ra ０３１In this context, the alkyl group may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms constituting the alkyl group (such as a methylene group) may be substituted with a heteroatom-containing group. Examples of heteroatoms here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, -S-, and -S(=O). ２ -, -S (=O) ２ Examples include -O-, etc. 【0058】 In formula (a1-r2-1), Xab ０ Yab ０ The alicyclic hydrocarbon group formed together is Ra' in the above formula (a1-r-1). ３ A group obtained by further removing one or more hydrogen atoms from the aliphatic hydrocarbon group (alicyclic hydrocarbon group) listed as a monocyclic or polycyclic group is preferred. Among these, a monocyclic alicyclic hydrocarbon group is more preferred, and a group obtained by removing two or more hydrogen atoms from a monocycloalkane is even more preferred. The monocycloalkane is preferably one having 3 to 8 carbon atoms, and specific examples include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. 【0059】 In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in the above formula (a1-r-2). ４ Examples include a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) from which one or more hydrogen atoms have been further removed. The cyclic hydrocarbon group formed by Xa together with Ya may have substituents. An example of such substituent is the above Ra'. ４ Examples include substituents similar to those that may be present on the cyclic hydrocarbon group in formula (a1-r2-2). １０１ ~Ra １０３Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like. Ra １０１ ~Ra １０３ Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms 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 cyclononyl group, a cyclodecyl group, a cyclododecyl group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 ２，６ decanyl group, tricyclo[3.3.1.1 ３，７ decanyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ dodecanyl group, adamantyl group and other polycyclic aliphatic saturated hydrocarbon groups. Ra １０１ ~Ra １０３ Among them, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among them, a hydrogen atom, a methyl group, and an ethyl group are more preferable, and a hydrogen atom is particularly preferable. 【0060】 As for the above Ra １０１ ~Ra １０３ Examples of the substituent of the linear saturated hydrocarbon group or aliphatic cyclic saturated hydrocarbon group represented by include the same groups as those of the above-mentioned Ra ０５ for example. 【0061】 Ra １０１ ~Ra １０３ Examples of the group containing a carbon-carbon double bond formed by two or more of bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, and the like. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferable as the group containing a carbon-carbon double bond. 【0062】In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-2). ４ The groups listed as aliphatic hydrocarbon groups that are monocyclic or polycyclic are preferred. In formula (a1-r2-3), Ra １０４ Aromatic hydrocarbon groups in this context include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among these, Ra １０４ The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms from which one or more hydrogen atoms have been removed; more preferably a group from which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene; even more preferably a group from which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene; particularly preferably a group from which one or more hydrogen atoms have been removed from benzene or naphthalene; and most preferably a group from which one or more hydrogen atoms have been removed from benzene. 【0063】 Ra in equation (a1-r2-3) １０４ Examples of substituents that may be present include methyl groups, ethyl groups, propyl groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and alkyloxycarbonyl groups. 【0064】 In formula (a1-r2-4), Ra' １２ and Ra' １３ Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. １２ and Ra' １３ In this, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above Ra １０１ ~Ra １０３ Examples include monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' １２ and Ra' １３ Among these, alkyl groups having 1 to 5 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. １２ and Ra' １３When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Ra ０５ Similar bases can be cited. 【0065】 In formula (a1-r2-4), Ra' １４ Ra' is a hydrocarbon group which may have substituents. １４ Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups. 【0066】 Ra' １４ The linear alkyl group in this formula preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, the linear alkyl group can be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. Among these, the linear alkyl group is preferably a methyl group, an ethyl group, or an n-butyl group, and more preferably a methyl group or an ethyl group. 【0067】 Ra' １４ The branched alkyl group in is preferably 3 to 10 carbon atoms, more preferably 3 to 5. １４ The branched alkyl group in this compound specifically includes isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, and so on, with isopropyl group being preferred. 【0068】 Ra' １４ When the hydrocarbon group is cyclic, it may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic or monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0２，６ Examples include decane, tetracyclododecane, etc. 【0069】 Ra' １４ Examples of the aromatic hydrocarbon group in Ra' are the same as those of the aromatic hydrocarbon group in Ra. １０４ Among them, Ra' is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene, and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene. Ra' １４ Examples of the substituent that Ra' may have are the same as those of the substituent that Ra may have. １４ Examples of the substituent that Ra' may have are the same as those of the substituent that Ra may have. １０４ Examples of the substituent that Ra' may have are the same as those of the substituent that Ra may have. 【0070】 Ra' in the formula (a1 - r2 - 4) １４ When Ra' is a naphthyl group, the position bonding to the tertiary carbon atom in the formula (a1 - r2 - 4) may be either the 1-position or the 2-position of the naphthyl group. Ra' in the formula (a1 - r2 - 4) １４ When Ra' is an anthryl group, the position bonding to the tertiary carbon atom in the formula (a1 - r2 - 4) may be any of the 1-position, 2-position or 9-position of the anthryl group. 【0071】 Specific examples of the group represented by the formula (a1 - r2 - 1) are listed below. 【0072】 【0073】 【0074】 【0075】 Specific examples of the group represented by the formula (a1 - r2 - 2) are listed below. 【0076】 【0077】 【0078】 【0079】 Specific examples of the group represented by the above formula (a1-r2-3) are given below. 【0080】 【0081】 Specific examples of the group represented by the above formula (a1-r2-4) are given below. 【0082】 【0083】 ・Tertiary alkyloxycarbonylic acid dissociable group: Among the polar groups, an example of an acid-dissociable group that protects a hydroxyl group is the acid-dissociable group represented by the following formula (a1-r-3) (hereinafter referred to as the "tertiary alkyloxycarbonylic acid dissociable group" for convenience). 【0084】 【0085】 [In the formula, Ra' ７ ~Ra' ９ Each of these represents an alkyl group. 【0086】 In formula (a1-r-3), Ra' ７ ~Ra' ９ Each alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4. 【0087】 As for the acid-dissociable group, among the groups represented by the general formulas (a1-r2-1) to (a1-r2-4) above, the group represented by the general formula (a1-r2-1) or (a1-r2-4) above is preferred. 【0088】 As a constituent unit (a1), a specific example of a constituent unit can be given, which is represented by the following general formula (a1-1). 【0089】 (Constituent unit (a1) represented by general formula (a1-1)) In the resist composition according to the embodiment of the present invention, the base component (A) preferably contains a polymer compound (A1) having a constituent unit (a1) represented by the following general formula (a1-1). 【0090】 【0091】 [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. Va １ n is a divalent hydrocarbon group which may have an ether bond. ａ１ is an integer between 0 and 2. １ This represents an acid-dissociating group. 【0092】 In formula (a1-1), the C1-C5 alkyl group of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The C1-C5 halogenated alkyl group is a group in which some or all of the hydrogen atoms of the C1-C5 alkyl group are substituted with halogen atoms. Examples of halogen atoms include chlorine, bromine, and iodine atoms. R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group due to their industrial availability. 【0093】 In the above formula (a1-1), Va １ The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. １ The aliphatic hydrocarbon group as the divalent hydrocarbon group in this product may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of such aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure. 【0094】 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. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, 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 Examples include -]. 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. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, 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 - Alkyl methylene 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 - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred. 【0095】 Examples of aliphatic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ Examples include decane and tetracyclododecane. 【0096】 Va １In this context, the aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings in an 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 an aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, the aromatic hydrocarbon group may be a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); or a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. In formula (a1-1), Ra １ represents an acid-dissociable group. Examples of acid-dissociable groups include those listed above, preferably an acid-dissociable group represented by the above formulas (a1-r2-1) to (a1-r2-4), and more preferably an acid-dissociable group represented by the above formulas (a1-r2-1) or (a1-r2-4). 【0097】 In the above formula (a1-1), n ａ１ n is an integer between 0 and 2. ａ１ The value is preferably 0 or 1, and more preferably 0. 【0098】 The above formula (a1-1) is preferably the following formula (a1-2). 【0099】 【0100】(In general formula (a1-2), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogenate having 1 to 5 carbon atoms. Va ３ represents a divalent hydrocarbon group which may have an ether bond. na ３ This represents an integer between 0 and 2. ０３１ This represents an alkyl group, Yab ０ Xab represents a carbon atom. ０ Yab ０ (This represents a group that forms an alicyclic hydrocarbon group together with the other group, and some or all of the hydrogen atoms in this alicyclic hydrocarbon group may be substituted.) 【0101】 In general formula (a1-2), R, Va ３ R, Va in equation (a1-1) １ These are similar in each case. 【0102】 In general formula (a1-2), na ３ is an integer between 0 and 2, preferably 0 or 1, and more preferably 0. 【0103】 In general formula (a1-2), Ra ０３１ Xab ０ Yab ０ Ra in equation (a1-r2-1) ０３１ Xab ０ Yab ０ These are similar in each case. 【0104】 In general formula (a1-2), Ra ０３１ Among the above, it is preferable that the alkyl group is a chain-like alkyl group, and more preferably a monovalent chain-like alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, or iso-propyl group. 【0105】 The following are specific examples of the constituent unit (a1). In the following formula, R α This represents a hydrogen atom or a methyl group. 【0106】 【0107】 【0108】 【0109】 【0110】 【0111】 【0112】 【0113】 【0114】 【0115】 【0116】 The constituent unit (a1) that component (A1) may have may be one type or two or more types. The proportion of constituent unit (a1) in component (A1) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, based on the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of constituent unit (a1) to be above the lower limit of the above preferred range, lithography characteristics such as increased sensitivity, resolution, and improved roughness are improved. Furthermore, by setting the proportion of constituent unit (a1) to be below the upper limit, a balance with other constituent units can be achieved, resulting in good lithography characteristics in various aspects. In addition, in the resist composition according to the embodiment of the present invention, the constituent unit (a1) may not contain an acetal-type acid-dissociable group. 【0117】 <Constituent Unit (a2)> Component (A1) further comprises a lactone-containing cyclic group, -SO ２ -It may also have a constituent unit (a2) containing a lactone-containing cyclic group or a carbonate-containing cyclic group (excluding those corresponding to constituent unit (a1)). -SO ２- The cyclic group containing or carbonate-containing cyclic group is effective in improving the adhesion of the resist film to the substrate when component (A1) is used to form the resist film. Furthermore, having the constituent unit (a2) improves lithography characteristics, etc., by having effects such as appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development. 【0118】 A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -O-C(=O)- within its cyclic skeleton. Counting the lactone ring as the first ring, a group consisting only of a lactone ring is called a monocyclic group, while a group with other cyclic structures is called a polycyclic group regardless of its structure. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Any lactone-containing cyclic group can be used in the constituent unit (a2) without any particular limitations. Specifically, examples of such lactone-containing cyclic groups include those represented by the following general formulas (a2-r-1) to (a2-r-7). 【0119】 【0120】 [In general formulas (a2-r-1) to (a2-r-7), Ra' ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - A cyclic group containing an oxygen atom (-O-) or a sulfur atom (-S-) is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond. 【0121】 In the general formulas (a2-r-1) to (a2-r-7), Ra' ２１The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, the alkyl group can be a methyl group, ethyl group, propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl group, iso-pentyl group, neopentyl group, hexyl group, etc. Among these, the alkyl group is preferably a methyl group or an ethyl group, and the alkyl group is particularly preferred. Ra' ２１ The alkoxy group in is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' ２１ Examples of alkyl groups in this context include groups formed by linking an alkyl group with an oxygen atom (-O-). ２１ Examples of halogen atoms in this context include chlorine, bromine, and iodine atoms. ２１ The halogenated alkyl group in is the Ra' ２１ Examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms, excluding groups having a perfluoroalkyl skeleton and difluoromethyl groups. 【0122】 Ra' ２１ In -COOR'' and -OC(=O)R'', R'' is either a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group. The alkyl group in R'' may be linear, branched, or cyclic, and the number of carbon atoms is preferably 1 to 15. 【0123】When R'' is a linear or branched alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When R'' is a cyclic alkyl group, it is preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes; groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ Examples include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as decane and tetracyclododecane. 【0124】 Examples of lactone-containing cyclic groups in R'' include those similar to the groups represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above. Examples of carbonate-containing cyclic groups in R'' include those similar to the carbonate-containing cyclic groups described later, specifically the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) mentioned above. -SO in R'' ２ - The cyclic group containing it is -SO, which will be described later. ２ - These are similar to the contained cyclic groups, and specifically include the groups represented by the general formulas (a5-r-1) to (a5-r-4), respectively. 【0125】 Ra' ２１ The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, specifically the Ra' ２１ Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group. 【0126】In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A'' is preferably a linear or branched alkylene group, such as a methylene group, ethylene group, n-propylene group, isopropylene group, etc. When the alkylene group contains an oxygen atom or a sulfur atom, a specific example is a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, such as -O-CH ２ -ien-CH ２ -O-CH ２ -, -S-CH ２ -ien-CH ２ -S-CH ２ Examples include the following. A'' is preferably an alkylene group or -O- having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group. 【0127】 The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-7). 【0128】 【0129】 【0130】 "-SO ２ - A "cyclic group containing -SO" refers to a group whose ring skeleton contains -SO ２ This indicates a cyclic group containing a ring with -, specifically -SO ２ - is a cyclic group in which the sulfur atom (S) forms part of the cyclic skeleton. ２ The ring containing the - group is counted as the first ring. If only this ring exists, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. -SO ２ - The contained cyclic group may be a monocyclic group or a polycyclic group. - SO ２ - The contained cyclic group, in particular, has -O-SO in its cyclic skeleton. ２ A cyclic group containing -, i.e., -O-SO ２ Preferably, the -O-S- in the - group is a cyclic group containing a sultone ring that forms part of the cyclic skeleton. -SO ２- More specifically, the cyclic groups included are those represented by the following general formulas (a5-r-1) to (a5-r-4). 【0131】 【0132】 [In general formulas (a5-r-1) to (a5-r-4), Ra' ５１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer from 0 to 2. 【0133】 In the above general formulas (a5-r-1) to (a5-r-2), A'' is the same as A'' in the above general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Ra' ５１ In this context, the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group are, respectively, Ra' in the general formulas (a2-r-1) to (a2-r-7). ２１ The same examples as those mentioned in the explanation are given below. Specific examples of the groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group. 【0134】 【0135】 【0136】 【0137】A "carbonate-containing cyclic group" refers to a cyclic group that contains a ring (carbonate ring) containing -O-C(=O)-O- within its cyclic framework. The carbonate ring is counted as the first ring. If it consists only of a carbonate ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A carbonate-containing cyclic group may be a monocyclic group or a polycyclic group. Any carbonate-containing cyclic group can be used without any particular limitations. Specifically, examples include the groups represented by the following general formulas (ax3-r-1) to (ax3-r-3). 【0138】 【0139】 [In the formula, Ra' ｘ３１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; p' is an integer from 0 to 3; and q' is 0 or 1. * indicates a bond. 【0140】 In the above general formulas (ax3-r-2) to (ax3-r-3), A'' is the same as A'' in the above general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Ra' Ｘ３１ In this context, the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group are, respectively, Ra' in the general formulas (a2-r-1) to (a2-r-7). ２１ The same examples as those mentioned in the explanation are given below. Specific examples of the groups represented by the general formulas (ax³-r-1) to (ax³-r-3) are given below. 【0141】 【0142】Among the constituent units (a2), those derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent are preferred. Such constituent units (a2) are preferably those represented by the following general formula (a2-1). 【0143】 【0144】 [In general formula (a2-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. Ya ２１ It is a single bond or a divalent linking group. La ２１ The elements are -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La ２１ If -O-, Ya ２１ It does not become -CO-. Ra ２１ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It contains a cyclic group. 【0145】 In formula (a2-1), R is the same as R in formula (a1-1). R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability. 【0146】 In the above formula (a2-1), Ya ２１ The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. 【0147】 • Divalent hydrocarbon group which may have substituents: Ya ２１ If is a divalent hydrocarbon group which may have substituents, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. 【0148】 Ya ２１In this context, an aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure. 【0149】 ...Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, 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 Examples include -]. 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. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, 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 - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred. 【0150】 The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include carbonyl groups. 【0151】...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), which may contain substituents containing heteroatoms in their 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 middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. As a monocycloalkane, those having 3 to 6 carbon atoms are preferred, and specifically examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ Examples include decane and tetracyclododecane. 【0152】The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. Preferably, the alkyl group is a C1-C5 alkyl group, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Preferably, the alkoxy group is a C1-C5 alkoxy group, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group, and even more preferably a methoxy group or ethoxy group. Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl halides as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. The cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with substituents containing heteroatoms. Substituents containing the heteroatom include -O-, -C(=O)-O-, -S-, and -S(=O). ２ -, -S (=O) ２ -O- is preferred. 【0153】 Ya ２１The aromatic hydrocarbon group in this context is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in 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 aromatic hydrocarbon groups include: a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. 【0154】The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the alkoxy group, halogen atom, and alkyl halide substituent are those exemplified as substituents that substitute for hydrogen atoms in the cyclic aliphatic hydrocarbon group. 【0155】 • Divalent linking group containing a heteroatom: Ya ２１ When the linking group is a divalent linking group containing a heteroatom, preferred linking groups 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 substituents such as alkyl groups or acyl groups), -S-, -S(=O) ２ -, -S (=O) ２ -O-, 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 - is represented by the base [wherein Y ２１ and Y ２２ Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 1 to 3. 【0156】When the divalent linking group containing the heteroatom is -C(=O)-NH-, -NH-, -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. 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. 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 Each of these is independently a divalent hydrocarbon group which may have substituents. The divalent hydrocarbon group is the aforementioned Ya ２１ Examples include those similar to the divalent linking groups (divalent hydrocarbon groups that may have substituents) mentioned in the description of divalent linking groups in Y. ２１ Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. 【0157】 Y ２２ Preferably, the group is a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y ２１ -C (=O) -O] ｍ” -Y ２２ In the base represented by -, m'' is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. That is, formula -[Y ２１ -C (=O) -O] ｍ”-Y ２２ As a base represented by -, see formula -Y ２１ -C(=O)-O-Y ２２ Groups represented by - are particularly preferred. Among them, the group represented by formula - (CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. 【0158】 Among the above, Ya ２１ Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof. 【0159】 In the formula (a2-1), Ra ２１ This is a lactone-containing cyclic group, -SO ２ - It is a cyclic group containing a carbonate or a cyclic group containing a carbonate. Ra ２１ Lactone-containing cyclic groups in -SO ２ - Suitable examples of the carbonate-containing cyclic groups include the groups represented by the general formulas (a2-r-1) to (a2-r-7), the groups represented by the general formulas (a5-r-1) to (a5-r-4), and the groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively. 【0160】 In the formula (a2-1), Ra ２１ Among the above, lactone-containing cyclic groups or -SO ２ - A cyclic group containing a lactone is preferred, and a cyclic group containing a lactone may also be preferred, and groups represented by the general formulas (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1) are more preferred, and groups represented by the general formulas (a2-r-1) or (a2-r-2) are even more preferred. Ra ２１Specifically, the groups represented by the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), and (r-lc-6-1) are preferred, and the groups represented by the chemical formulas (r-lc-1-1), (r-lc-2-1), or (r-lc-2-12) are even more preferred. 【0161】 The constituent unit (a2) of component (A1) may be one type or two or more types. When component (A1) has constituent unit (a2), the proportion of constituent unit (a2) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is above the preferred lower limit, the effects of including constituent unit (a2) are sufficiently obtained due to the effects described above, and if it is below the upper limit, a balance with other constituent units can be maintained, resulting in good lithography characteristics in various aspects. 【0162】 <Other constituent units> Component (A1) may have other constituent units other than the constituent units (a1) and (a2) described above. Examples of other constituent units include a constituent unit (a3) ​​containing a polar group-containing aliphatic hydrocarbon group; a constituent unit (a4) containing an acid-nondissociable aliphatic cyclic group; and a constituent unit (st) derived from styrene or a styrene derivative. Many of the constituent units (a3) ​​containing a polar group-containing aliphatic hydrocarbon group, a constituent unit (a4) containing an acid-nondissociable aliphatic cyclic group, and a constituent unit (st) derived from styrene or a styrene derivative are conventionally known to be used as resin components in resist compositions. 【0163】Such component (A1) can be produced by dissolving monomers that induce each constituent unit in a polymerization solvent and adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to perform polymerization. Alternatively, such component (A1) can be produced by dissolving monomers that induce constituent unit (a1) and monomers that induce constituent unit (a2) in a polymerization solvent and adding a radical polymerization initiator as described above to perform polymerization. 【0164】 In the resist composition according to the embodiment of the present invention, the weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is preferably 4,000 or more, more preferably 5,000 or more, even more preferably 6,000 or more, and even more preferably 6,500 or more. The Mw of component (A1) is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 12,000 or less. In the resist composition according to the embodiment of the present invention, the Mw of component (A1) is preferably 4,000 to 30,000, more preferably 5,000 to 20,000, and even more preferably 6,000 to 12,000. (A1) If the Mw of component is below the preferred upper limit of this range, it has sufficient solubility in resist solvents for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance, LWR (linewise roughness), and LER. 【0165】 The dispersion of component (A1) (Mw / Mn) is not particularly limited, but is preferably 1.0 or higher, preferably 4.0 or lower, more preferably 3.0 or lower, and particularly preferably 2.0 or lower. The dispersion of component (A1) (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight. 【0166】Regarding the substrate components other than component (A1), the resist composition according to the embodiment of the present invention may also use a substrate component (hereinafter referred to as "component (A2)") that does not fall under component (A1) and whose solubility in the developer changes due to the action of an acid, as component (A). Component (A2) is not particularly limited as long as it does not have a perfluoroalkyl skeleton and does not have a difluoromethyl group, and may be arbitrarily selected from a large number of substrate components conventionally known for chemically amplified resist compositions. Component (A2) may be a single polymer compound or a low molecular weight compound, or two or more may be used in combination. 【0167】 The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, it becomes easier to form a resist pattern that is excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement. The proportion of component (A1) in component (A) is not particularly limited, but for example it can be 100% by mass or less. 【0168】 In the resist composition according to the embodiment of the present invention, the content of component (A) can be adjusted according to the resist film thickness to be formed, and is not particularly limited, but is preferably 2% by mass or more, and more preferably 3% by mass or more, based on the total mass (100% by mass) of the resist composition. The upper limit of the content of component (A) is not particularly limited as long as it is at a concentration that can form a resist film, but for example, is preferably 10% by mass or less, and more preferably 5% by mass or less. 【0169】≪Acid Generating Agent Component (B)≫ In addition to the above-mentioned component (A) and component (F) described below, the resist composition according to the embodiment of the present invention further contains an acid generating agent component (B) (hereinafter referred to as "component (B)") that generates acid upon exposure. Component (B) is not particularly limited as long as it does not have a perfluoroalkyl skeleton and does not have a difluoromethyl group, and any acid generating agent previously proposed for chemically amplified resist compositions can be used. Examples of such acid generating agents include onium salt-based acid generating agents such as iodonium salts and sulfonium salts, oximesulfonate-based acid generating agents; diazomethane-based acid generating agents such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generating agents, iminosulfonate-based acid generating agents, disulfone-based acid generating agents, and many others. Component (B) preferably contains an onium salt-based acid generator. Examples of onium salt-based acid generators include the compound represented by the following general formula (b-01) (hereinafter also referred to as "component (b-01)"), the compound represented by the general formula (b-02) (hereinafter also referred to as "component (b-02)"), the compound represented by the general formula (b-03) (hereinafter also referred to as "component (b-03)"), and the compound represented by the general formula (b-04) (hereinafter also referred to as "component (b-04)"), with component (b-04) being preferred. 【0170】 【0171】 [In the formula, R １０１ and R １０４ ~R １０８ Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. １０４ and R １０５ These may be bonded to each other to form a ring structure. １０２ This is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. １０１ This is a divalent linking group or single bond containing an oxygen atom. １０１ ~V １０３ Each of these is independently either a single bond or an alkylene group. However, Y １０１and V １０１ They cannot be single bonds at the same time. １０１ ~L １０２ Each of these is independently either a single bond or an oxygen atom. １０３ ~L １０５ These are, independently, single bonds, -CO-, or -SO-. ２ - is true. m is an integer greater than or equal to 1, and M' ｍ＋ This is an onium cation with a positive (m) charge. 【0172】 【0173】 [In the formula, Rb ２ Rb is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. ２ In this diagram, it is assumed that no fluorine atoms are bonded to carbon atoms adjacent to the sulfur atom. m is an integer greater than or equal to 1, and M' ｍ＋ This is an onium cation with a positive (m) charge. 【0174】 {Anion part} • In the anion formula (b-01) of component (b-01), R １０１ This is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 【0175】 A cyclic group which may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated. 【0176】 R １０１ The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. １０１Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. １０１ Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, benzyl groups, phenethyl groups, 1-naphthylmethyl groups, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. 【0177】 R １０１ The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a monocycloalkane. The preferred monocycloalkane has 3 to 6 carbon atoms, and specifically includes cyclopentane and cyclohexane. A preferred polycyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a polycycloalkane, and the preferred polycycloalkane has 7 to 30 carbon atoms. Among these, the polycycloalkanes include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 ２，６Polycycloalkanes having a cross-linked ring system polycyclic skeleton, such as decane and tetracyclododecane; polycycloalkanes having a fused ring system polycyclic skeleton, such as a cyclic group having a steroid skeleton, are more preferred. 【0178】 Among them, R １０１ The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group. 【0179】 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. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH₂]. ２ -], ethylene group [- (CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -]. The branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, 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 - Alkyl methylene 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 - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred. 【0180】 Also, R １０１ The cyclic hydrocarbon group in may contain heteroatoms, such as heterocycles. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), and -SO groups represented by the general formulas (a5-r-1) to (a5-r-4). ２ - Examples include cyclic groups and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * represents Y in general formula (b-01). １０１ This represents a coupling that connects to something. 【0181】 【0182】 R １０１Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. C1-C5 alkyl groups are preferred as substituents. C1-C5 alkoxy groups are preferred as substituents, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being more preferred, and methoxy and ethoxy groups being most preferred. Bromine and iodine atoms are preferred as substituents. C1-C5 alkyl halides are examples of alkyl groups, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. Carbonyl groups are examples of methylene groups (-CH4) that constitute the cyclic hydrocarbon group. ２ It is a substituting group for -). 【0183】 R １０１ The cyclic hydrocarbon group in may be a fused ring group containing a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridging ring system with one or more aromatic rings fused to it. Specific examples of the bridging ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to a bicycloalkane, and more preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to bicyclo[2.2.2]octane. １０１ Specific examples of fused ring groups in this context include those represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in formula (b-01). １０１ This represents a coupling that connects to something. 【0184】 【0185】 R １０１Examples of substituents that the fused ring group in R may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, etc. The alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents of the fused ring group are as described above. １０１ Examples of substituents for cyclic groups in the above are similar to those listed above. Aromatic hydrocarbon groups as substituents for the fused cyclic group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: e.g., phenyl group, naphthyl group, etc.), groups in which one hydrogen atom of the aromatic ring is replaced by an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Alicyclic hydrocarbon groups as substituents for the fused cyclic group include groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ ] Groups obtained by removing one hydrogen atom from polycycloalkanes such as decane and tetracyclododecane; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively; -SO groups represented by the general formulas (a5-r-1) to (a5-r-4), respectively. ２ - Containing cyclic groups; examples include heterocyclic groups represented by formulas (r-hr-7) to (r-hr-16), respectively. 【0186】 R １０１ The cyclic hydrocarbon group in may be a group linked by two or more linear or branched aliphatic hydrocarbon groups, which may have substituents on two or more aliphatic rings and / or aromatic rings. The linear or branched aliphatic hydrocarbon group linking the alicyclic hydrocarbon group may be a methylene group (-CH) constituting the aliphatic hydrocarbon chain. ２The -) may be substituted with a divalent group containing a heteroatom. Examples of divalent groups containing a heteroatom 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 Examples include -O-, etc. 【0187】 A chain-like alkyl group which may have substituents: R １０１ The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Branched alkyl groups preferably have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group. 【0188】 A chain-like alkenyl group which may have substituents: R １０１ The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups listed above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred. 【0189】 R １０１ Examples of substituents in the chain-like alkyl or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R１０１ Examples include cyclic groups in this context. 【0190】 Among the above, R １０１ It is preferably a chain-like alkyl group which may have substituents, or an alicyclic hydrocarbon group which may have substituents, and may be a chain-like alkyl group which may have halogen atoms, a group obtained by removing one or more hydrogen atoms from a polycycloalkane which may have substituents, or -SO represented by any of the general formulas (a5-r-1) to (a5-r-4) above. ２ -More preferably a cyclic group containing one or more hydrogen atoms obtained by removing one or more hydrogen atoms from a polycycloalkane which may have substituents, or -SO represented by any of the general formulas (a5-r-1) to (a5-r-4) above. ２ -The contained cyclic group is more preferably an adamantyl group which may have a hydroxyl group or -SO represented by the general formula (a5-r-1) above. ２ - A cyclic group is particularly preferred. 【0191】 In formula (b-01), Y １０１ Y is a single bond or a divalent linking group containing an oxygen atom. １０１ If Y is a divalent linking group containing an oxygen atom, １０１ It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of divalent linking groups containing oxygen atoms include the linking groups represented by the following general formulas (y-al-1) to (y-al-7). Note that in the following general formulas (y-al-1) to (y-al-7), R in formula (b-01) above １０１ The combination with this is V' in the following general formulas (y-al-1) to (y-al-7). １０１ That is the case. 【0192】 【0193】 [In the formula, V' １０１ V' is a single bond or an alkylene group having 1 to 5 carbon atoms. １０２ [This refers to a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.] 【0194】 V' １０２The 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. 【0195】 V ’１０１ and V' １０２ The alkylene group in this can be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. ’１０１ and V' １０２ Specifically, the alkylene group in this case is the methylene group [-CH ２ -come; -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkylmethylene groups such as; ethylene groups [-CH ２ CH ２ -come; -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ - Alkylethylene groups such as; trimethylene group (n-propylene group) [-CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as; tetramethylene groups [-CH２ CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ - Alkyltetramethylene groups such as; pentamethylene groups [-CH ２ CH ２ CH ２ CH ２ CH ２ -] are some examples. Also, V ’１０１ or V' １０２ Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is Ra' in formula (a1-r-1). ３ A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred. 【0196】 In formula (b-01), V １０１ These are single bonds and alkylene groups. Among them, V １０１ It is preferable that the alkylene group is a single bond or a linear alkylene group having 1 to 4 carbon atoms. 【0197】 In formula (b-01), R １０２ This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 【0198】 A specific example of the anion part represented by the above formula (b-01) is, for example, Y １０１ When is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) are included. 【0199】 【0200】 [In the formula, R” １０１R'' is an optionally substituted aliphatic cyclic group, a monovalent heterocyclic group represented by 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), an optionally substituted linear alkyl group, or an optionally substituted aromatic cyclic group. １０２ This includes an aliphatic cyclic group which may have substituents, a fused cyclic group represented by formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively, or -SO represented by the general formulas (a5-r-1) to (a5-r-4), respectively. ２ - Contains a cyclic group. R'' １０３ V'' is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted linear alkenyl group. １０１ R is a single bond or an alkylene group having 1 to 4 carbon atoms. １０２ [wherein ' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; where 'v'' is an independent integer from 0 to 3, where 'q'' is an independent integer from 0 to 20, and where 'n'' is 0 or 1.] 【0201】 R" １０１ , R” １０２ and R” １０３ The aliphatic cyclic group which may have substituents is R in formula (b-01). １０１ It is preferable that the substituent is the group exemplified as a cyclic aliphatic hydrocarbon group in formula (b-01). １０１ Examples include substituents similar to those that may be substituted for the cyclic aliphatic hydrocarbon group in the above. 【0202】 R" １０１ and R” １０３ The aromatic cyclic group which may have substituents in formula (b-01) is R １０１ It is preferable that the substituent is the group exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group in formula (b-01). １０１ Examples include substituents similar to those that may be substituted for the aromatic hydrocarbon group in the above. 【0203】 R"１０１ The chain-like alkyl group which may have substituents in formula (b-01) is R １０１ The group exemplified as the chain-like alkyl group in R is preferred. １０３ The chain-like alkenyl group which may have substituents in formula (b-01) is R １０１ It is preferable that the group is one of the examples given as a chain-like alkenyl group in the formula. 【0204】 • In the anionic formula (b-02) of component (b-02), R １０４ , R １０５ Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-01). １０１ Similar examples can be given. However, R １０４ , R １０５ They may be bonded to each other to form a ring. １０４ , R １０５ The alkyl group is preferably a linear alkyl group which may have substituents, and more preferably a linear or branched alkyl group. The number of carbon atoms in the linear alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. １０４ , R １０５ The number of carbon atoms in the chain-like alkyl group is preferably small within the above range of carbon atoms, for reasons such as good solubility in the resist solvent. In formula (b-02), V １０２ , V １０３ Each is independently a single bond or an alkylene group, and each is V in formula (b-01). １０１ Similar examples include those mentioned above. In formula (b-02), L １０１ , L １０２ Each of these is either a single bond or an oxygen atom, independently of the others. 【0205】 • In the anionic formula (b-03) of component (b-03), R １０６ ~R １０８Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-01). １０１ Similar examples include the following. In formula (b-03), L １０３ ~L １０５ These are, independently, single bonds, -CO-, or -SO-. ２ - is the case. 【0206】 • In the anionic formula (b-04) of component (b-04), Rb ２ R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, as described later. ２０１ Similar examples include the following. However, Rb ２ In this example, assume that the carbon atom adjacent to the S atom is not bonded to a fluorine atom (i.e., not fluorine-substituted). Rb ２ Preferably, the group is a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents, and more preferably an aliphatic cyclic group which may have substituents. 【0207】 The linear alkyl group is preferably having 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ A group obtained by removing one or more hydrogen atoms from decane, tetracyclododecane, etc. (which may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor. 【0208】 Rb ２ The hydrocarbon group (cyclic group, linear alkyl group, linear alkenyl group) may have substituents, and such substituents may be Rd of formula (d1-1) described below. １ Examples include substituents similar to those that may be present on hydrocarbon groups (cyclic groups, linear alkyl groups, linear alkenyl groups) in the above. 【0209】 The following are preferred specific examples of the anion portion of component (b-04). 【0210】 【0211】 [Cation part: (M ｍ＋ ) １／ｍ ] In the general formulas (b-01) to (b-04), M ｍ＋ This represents an m-valent organic cation. ｍ＋ In this compound, onium cations are preferred as the organic cation, sulfonium cations, iodonium cations, and ammonium cations are more preferred, sulfonium cations and iodonium cations are even more preferred, and sulfonium cations are particularly preferred. m is an integer of 1 or more. 【0212】 Preferred cation portion ((M ｍ＋ ) １／ｍ Examples of organic cations include those represented by any of the following general formulas (ca-1) to (ca-3), with the organic cation represented by general formula (ca-1) being preferred. 【0213】 【0214】 [In general formulas (ca-1) to (ca-3), R ２０１ ~R ２０７ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group, and R ２０１ ~R ２０３ , R ２０６ ~R ２０７ These atoms may bond to each other to form a ring with the sulfur atom in the formula. ２０８ ~R ２０９ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group, L ２０１ represents -C(=O)- or -C(=O)-O-. 【0215】 R ２０１ ~R ２０７Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２０１ ~R ２０７ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ The alkenyl group in is preferably one with 2 to 10 carbon atoms. ２０１ ~R ２０７ Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, arylthio groups, and groups represented by any of the following formulas (ca-r-1) to (ca-r-7). Examples of aryl groups in the arylthio group as a substituent include aryl groups having 6 to 20 carbon atoms, with phenyl groups, naphthyl groups, and biphenyl groups being preferred. Examples of arylthio groups include phenylthio groups, naphthylthio groups, and biphenylthio groups. 【0216】 【0217】 [In the formula, R' ２０１ Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. 【0218】 R' ２０１ The cyclic group which may have substituents represented by is preferably a cyclic hydrocarbon group, and this cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of aromatic hydrocarbon groups include aromatic hydrocarbon rings or aryl groups obtained by removing one hydrogen atom from aromatic compounds containing two or more aromatic rings, with phenyl groups and naphthyl groups being preferred. Examples of aliphatic hydrocarbon groups include groups obtained by removing one hydrogen atom from monocycloalkanes or polycycloalkanes, with adamantyl groups and norbornyl groups being preferred. 【0219】 R' ２０１The linear alkyl group, which may have substituents represented by , may be linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specific examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, and docosyl groups. 【0220】 R' ２０１ The linear alkenyl group, which may have substituents represented by , may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylpropenyl groups and 2-methylpropenyl groups. Among the above, propenyl groups are particularly preferred as linear alkenyl groups. 【0221】 R' ２０１ Examples of optionally substituted cyclic groups or optionally substituted linear alkyl groups represented by include those similar to the acid-dissociable groups described above. 【0222】 R' ２０１Substituents in the cyclic group, linear alkyl group, or linear alkenyl group represented by include, for example, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. Preferably, alkyl groups have 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferably, alkoxy groups have 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being more preferred, with methoxy and ethoxy groups being the most preferred. Examples of halogen atoms as substituents include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl halides as substituents include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. 【0223】 R ２０１ ~R ２０３ , R ２０６ ~R ２０７ When these atoms bond to each other and form a ring with the sulfur atom in the formula, they can be heteroatoms such as sulfur, oxygen, and nitrogen atoms, or 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. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, thiazole ring, benzothiophene ring, thianthlene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthlene ring, phenoxatiyne ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring, thioxanium ring, and the like. 【0224】 R２０８ ~R ２０９ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or an alkyl group having 1 to 3 carbon atoms being preferred. ２０８ ~R ２０９ However, if each element independently becomes an alkyl group, they may bond to each other to form a ring. 【0225】 R ２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an -SO group having a substituent. ２ - Contains a cyclic group. R ２１０ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２１０ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in is preferably one with 2 to 10 carbon atoms. ２１０ In which, the substituent may be -SO ２ - In the contained cyclic group, "-SO ２ - A "cyclic group containing -SO" refers to a group whose ring skeleton contains -SO ２ This indicates a cyclic group containing a ring with -, specifically -SO ２ - is a cyclic group in which the sulfur atom (S) forms part of the cyclic skeleton. ２ The ring containing the - group is counted as the first ring. If only this ring exists, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. -SO ２ - The contained cyclic group may be a monocyclic group or a polycyclic group. - SO ２ - The contained cyclic group, in particular, has -O-SO in its cyclic skeleton. ２ A cyclic group containing -, i.e., -O-SO ２ It is preferable that the -O-S- in the - group contains a cyclic group that includes a sultone ring, which forms part of the cyclic skeleton. ２１０ In which, the substituent may be -SO ２- The cyclic group contained is preferably the group represented by the above formula (a5-r-1). ２１０ The substituents that may be present are the above-mentioned R ２０１ ~R ２０７ Examples of substituents that may be present include: 【0226】 The cation represented by formula (ca-1) is preferably the cation represented by the following formula (b-2). 【0227】 【0228】 [In formula (b-2), Rb ２０１ ~Rb ２０２ Each of these represents an aryl group which may have substituents, and Rb ２０３ Rb represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ２０１ ~Rb ２０３ These atoms may bond to each other to form a ring with the sulfur atom in formula (b-2). 【0229】 Rb ２０１ ~Rb ２０２ The aryl group which may have substituents represented by the above R ２０１ ~R ２０７ This is synonymous with an aryl group which may have substituents as Rb, and the preferred example is similar. ２０３ The optionally substituted aryl group, optionally substituted alkyl group, or optionally substituted alkenyl group represented by R is as follows: ２０１ ~R ２０７ This is synonymous with an aryl group which may have substituents, an alkyl group which may have substituents, or an alkenyl group which may have substituents, and the preferred examples are similar. 【0230】 Specific examples of preferred cations represented by formula (ca-1) include cations represented by any of the following formulas: (ca-1-1) to (ca-1-42), (ca-1-49) to (ca-1-67). 【0231】 【0232】 【0233】 【0234】 [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 1 to 20.] 【0235】 【0236】 [In the formula, R” ２０１ is a hydrogen atom or a substituent, and the substituent is R ２０１ ~R ２０７ , and R ２１０ These are the same as those listed as substituents that may be present. 【0237】 Specific examples of preferred cations represented by the above formula (ca-3) include cations represented by any of the following formulas (ca-3-1) to (ca-3-6). 【0238】 【0239】 In the resist composition according to the embodiment of the present invention, component (B1) may be used alone or in combination of two or more types. 【0240】 In the resist composition according to the embodiment of the present invention, the content of component (B1) is preferably 1 to 60 parts by mass, more preferably 2.5 to 50 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of component (A). When the proportion of component (B1) is above the preferred lower limit, lithography characteristics such as roughness reduction and increased sensitivity are further improved. On the other hand, when it is below the upper limit, it becomes easier to form a resist pattern with excellent exposure latitude. 【0241】Regarding component (B2), the resist composition according to the embodiment of the present invention may contain an acid generating agent component other than component (B1) (hereinafter referred to as "component (B2)"), to the extent that it does not impair the effects of the present invention. Component (B2) is not particularly limited as long as it does not have a perfluoroalkyl skeleton and does not have a difluoromethyl group, and any acid generating agent previously proposed for chemically amplified resist compositions can be used. Examples of such acid generating agents include onium salt-based acid generating agents such as iodonium salts and sulfonium salts, oximesulfonate-based acid generating agents; diazomethane-based acid generating agents such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generating agents, iminosulfonate-based acid generating agents, disulfone-based acid generating agents, and many others. 【0242】 In the resist composition according to the embodiment of the present invention, component (B2) may be used alone or in combination of two or more types. When the resist composition contains component (B2), the content of component (B2) in the resist composition is preferably 30 parts by mass or less, and more preferably 1 to 25 parts by mass, per 100 parts by mass of component (A). By setting the content of component (B2) in the resist composition within the above range, sufficient pattern formation is achieved. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, which is preferable as it results in good storage stability as a resist composition. 【0243】 In the resist composition according to the embodiment of the present invention, the content of the acid generator component (B) is preferably 1 to 40 parts by mass, more preferably 2.5 to 30 parts by mass, and even more preferably 5 to 25 parts by mass, per 100 parts by mass of the base component (A). By setting the content of the acid generator component (B) in the resist composition within the above range, it becomes easier to obtain a resist composition with excellent aging stability and to form a resist pattern that achieves both high exposure latitude and high sensitivity to the exposure light source. 【0244】≪Component (F): Fluorine Additive Component≫ The resist composition in this embodiment contains the fluorine additive component in this embodiment (hereinafter referred to as "component (F)"). Component (F) is used to impart water repellency to the resist film and is used as a hydrophobic resin separate from component (A) to obtain segregation ability to the upper layer of the film by fluorine atoms and water repellency. Component (F) contains a polymer compound (F1) having a constituent unit (f1) represented by the following general formula (f1-1). Component (F) does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. For this reason, the resist composition in this embodiment has excellent lithography properties and can achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact. 【0245】 <Constituent Unit (f1)> The constituent unit (f1) represented by the general formula (f1-1) has a fluorine atom in the aryl group, and therefore has excellent segregation ability to the upper layer of the resist film due to the fluorine atom. As a result, the resist film formed by the resist composition in this embodiment exhibits high water repellency and has the effect of suppressing residual water on the wafer and the elution of the resist composition during immersion lithography. 【0246】 【0247】 [In general formula (f1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. Lf is a divalent linking group. Ar is an aryl group. nf １ [ is an integer greater than or equal to 1.] 【0248】 As stated above, the general formula (f1-1) does not contain either a perfluoroalkyl skeleton or a difluoromethyl group. 【0249】In the general formula (f1-1), 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. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. A halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of halogen atoms include chlorine atoms, bromine atoms, iodine atoms, etc. As for R, a hydrogen atom or a methyl group is most preferred due to the ease of industrial availability of hydrogen atoms and alkyl groups having 1 to 5 carbon atoms. 【0250】 Lf is a divalent linking group, and Ya of the general formula (a2-1) ２１ Examples of divalent linking groups are similar to those listed in the description of divalent linking groups in [reference]. As Lf, divalent linking groups containing heteroatoms are preferred, such as -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 substituents such as alkyl groups or acyl groups), -S-, -S(=O) ２ -, -S (=O) ２ -O-, 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 -, -[C(=O)-O] ｍ” -Y ２１ -C(=O)-O-Y ２２ -, -[C(=O)-O] ｍ” -Y ２２ -C(=O)-O-, -Y ２１ -OC(=O)-Y ２２ - or - Y ２１ -S (=O) ２ -O-Y ２２ A group represented by - is even more preferable, -[C(=O)-O] ｍ” -Y２１ -C(=O)-O-Y ２２ - is particularly preferable [in the formula, Y ２１ and Y ２２ Each of these is a divalent hydrocarbon group which may have substituents, O is an oxygen atom, and m'' is an integer from 1 to 3. 【0251】 Examples of aryl groups represented by Ar include aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, and phenanthryl groups, with phenyl being preferred. Ar can also have nf as a substituent. １ It has 1 fluorine atom and may further have substituents other than fluorine atoms. Examples of substituents include groups represented by alkyl groups, halogen atoms other than fluorine atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, arylthio groups, hydroxyl groups, and nitro groups. 【0252】 nf １ It is preferably an integer greater than or equal to 1, and is a number that can substitute all the hydrogen atoms on the aryl group represented by Ar. 【0253】 In the constituent unit (f1), the above general formula (f1-1) is preferably represented by the following general formula (f1-2). 【0254】 【0255】 [In the general formula (f1-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. nf ３ Lf is either 1 or 2. ２ Rf is a divalent linking group. １ is an optionally substituted linear hydrocarbon group, an optionally substituted cyclic hydrocarbon group, a nitro group, or a cyano group. Ar is an aryl group. nf ２ [ is an integer greater than or equal to 1.] 【0256】 In general formula (f1-2), R, Ar, nf ２ R, Ar, nf in the general formula (f1-1) １ These are similar in each case. 【0257】 Rf in general formula (f1-2) １ Since the group is a chain-like hydrocarbon group that may have substituents, a cyclic hydrocarbon group that may have substituents, a nitro group, or a cyano group, the decomposition reaction caused by the abstraction of hydrogen fluoride (HF) by basic compounds is more likely to occur, and sufficient basic decomposition properties are easily obtained. As a result, it is presumed that segregation of the fluorine additive component (F) onto the resist pattern surface is eliminated, and a resist pattern with a good shape can be formed. 【0258】 Lf １ is a divalent linking group, and Ya of the general formula (a2-1) ２１ The same examples as those listed in the explanation of divalent linking groups in Lf can be cited. １ Preferably, the linking group is a divalent linking group containing a heteroatom, such as -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 substituents such as alkyl groups or acyl groups), -S-, -S(=O) ２ -, -S (=O) ２ -O-, 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 A group represented by - is even more preferable, -Y ２１ -C(=O)-O- is particularly preferred [where Y ２１ and Y ２２ Each of these is a divalent hydrocarbon group which may have substituents, O is an oxygen atom, and m'' is an integer from 1 to 3. 【0259】 Rf １Examples of the chain-like hydrocarbon group represented include linear or branched alkyl groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, the linear alkyl group is preferably a methyl group, ethyl group, or n-butyl group, and more preferably a methyl group or an ethyl group. 【0260】 The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred. 【0261】 Rf １ Examples of substituents that the chain-like hydrocarbon group may have include a halogen atom, a carbonyl group, a cyano group, an amino group, an aryl group, an arylthio group, a hydroxyl group, or a nitro group, with a nitro group or a cyano group being preferred. 【0262】 Rf １ The cyclic hydrocarbon group represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic or monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. 【0263】 Rf １When the cyclic hydrocarbon group represented by becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms 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. 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. Rf １ Specifically, examples of aromatic hydrocarbon groups represented by include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. 【0264】 Rf １ Examples of substituents that the cyclic hydrocarbon group in the compound may have include groups represented by any of the following: halogen atoms other than fluorine, carbonyl groups, cyano groups, amino groups, aryl groups, arylthio groups, hydroxyl groups, and nitro groups. 【0265】 Examples of aryl groups represented by Ar include aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, and phenanthryl groups, with phenyl being preferred. Ar can also have nf as a substituent.１ It has a fluorine atom and may further have substituents other than fluorine atoms. Examples of such substituents include groups represented by any of the following: alkyl groups, halogen atoms other than fluorine atoms, halogenated alkyl groups that do not have a perfluoroalkyl skeleton or a difluoromethyl group, carbonyl groups, cyano groups, amino groups, aryl groups, arylthio groups, hydroxyl groups, and nitro groups. 【0266】 nf １ It is preferably an integer greater than or equal to 1, and is a number that can substitute all the hydrogen atoms on the aryl group represented by Ar. 【0267】 Specific examples of constituent units (f1) are given below. In the following formula, R a This represents a hydrogen atom or a methyl group. 【0268】 【0269】 【0270】 【0271】 The constituent units (f1) of component (F1) may be one type or two or more types. The proportion of constituent units (f1) in component (F1) is preferably 40 to 90 mol%, more preferably 50 to 80 mol%, and particularly preferably 60 to 80 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (F1). If the proportion of constituent units (f1) is above the preferred lower limit, the effects of high water repellency and WMD improvement due to high segregation by including constituent units (f1) can be sufficiently obtained, and if it is below the upper limit, a balance with other constituent units can be maintained, resulting in good defect characteristics. 【0272】 The polymer compound (F1) contains, in addition to the constituent unit (f1) represented by the general formula (f1-1) above, a constituent unit (fa1) containing an acid-degradable group or a lactone-containing cyclic group, -SO ２ - Preferably, the material has a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group (excluding those that correspond to constituent unit (f1) and those that have a perfluoroalkyl skeleton). 【0273】<Constituent Unit (fa1)> Constituent unit (fa1) is a constituent unit containing an acid-degradable group, and examples include those similar to the above constituent unit (a1). 【0274】 The constituent unit (fa1) containing an acid-degradable group preferably includes the constituent unit (fa-1) represented by the following general formula (fa-1). 【0275】 【0276】 [In general formula (fa-1), R ０１ Vfa is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. ０１ n is a divalent hydrocarbon group which may have an ether bond. ｆ０１ Rfa is an integer between 0 and 2. ０１ It is an acid-dissociating group. 【0277】 R in the general formula (fa-1) ０１ , Vfa ０１ , n ｆ０１ , and Rfa ０１ These are R and Va in the general formula (a1-1) mentioned above, respectively. １ , n ａ１ , and Ra １ It is similar to that. 【0278】 R ０１ Preferably, the atoms are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and due to their industrial availability, hydrogen atoms or methyl groups are most preferred. 【0279】 Vfa ０１ Va in the general formula (a1-1) １ The same applies to the desirable ones. 【0280】 n ｆ０１ The value is preferably 0 or 1, and more preferably 0. 【0281】 Rfa ０１ Preferably, the acid-dissociable group is represented by the above formulas (a1-r2-1) to (a1-r2-4), and more preferably, it is represented by the above formulas (a1-r2-1) or (a1-r2-4). 【0282】The polymer compound (F1) may have one or more constituent units (fa1). The proportion of constituent units (fa1) in the polymer compound (F1) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound (F1). By setting the proportion of constituent units (fa1) to be above the lower limit of the above preferred range, the lithography properties are improved. Furthermore, by setting it to be below the upper limit, good water repellency is achieved. 【0283】 <Constituent Unit (fa2)> Lactone-containing cyclic group, -SO ２ - In a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, the lactone-containing cyclic group, -SO ２ -The cyclic groups containing -SO include the lactone-containing cyclic groups listed in the above constituent unit (a2), and -SO ２ - Examples include cyclic groups containing carbonates and cyclic groups containing carbonates. The constituent unit (fa2) does not contain either a perfluoroalkyl skeleton or a difluoromethyl group. 【0284】 Lactone-containing cyclic group, -SO ２ - The constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group preferably includes the constituent unit (fa-2) represented by the following general formula (fa-2). 【0285】 【0286】 [In general formula (fa-2), R ０２ Vfa is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. ０２ n is a divalent hydrocarbon group which may have an ether bond. ｆ０２ Rfa is an integer between 0 and 2. ０２ This refers to a lactone-containing cyclic group represented by any of the following formulas (a2-r-1) to (a2-r-7), and -SO represented by any of the following formulas (a5-r-1) to (a5-r-4). ２ - A carbonate-containing cyclic group, or a carbonate-containing cyclic group represented by any of the following formulas (ax3-r-1) to (ax3-r-3). 【0287】 【0288】 [In formulas (a2-r-1) to (a2-r-7), Ra' ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - A cyclic group containing an oxygen atom (-O-) or a sulfur atom (-S-) is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond. 【0289】 【0290】 [In formulas (a5-r-1) to (a5-r-4), Ra' ５１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer from 0 to 2. 【0291】 【0292】 [In the formula, Ra' ｘ３１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２- It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; p' is an integer from 0 to 3; and q' is 0 or 1. * indicates a bond. 【0293】 R in the general formula (fa-2) ０２ , Vfa ０２ , and n ｆ０２ These are R and Va in the general formula (a1-1) of the above constituent unit (a1), respectively. １ , and n ａ１ It is similar to that. 【0294】 Ra' in equations (a² - r - 1) to (a² - r - 7) ２１ A'', n', and m' are Ra' in formulas (a2-r-1) to (a2-r-7) in the above constituent unit (a2). ２１ This is similar to A'', n', and m'. 【0295】 Ra' in equations (a5-r-1) to (a5-r-4) ５１ A'' is Ra' in formulas (a5-r-1) to (a5-r-4) in the above constituent unit (a2). ２１ It is the same as A''. 【0296】 Ra' in equations (ax3-r-1) to (ax3-r-3) ｘ３１ A'' is Ra' in the formulas (ax3-r-1) to (ax3-r-3) in the above constituent unit (a2). ｘ３１ It is the same as A''. 【0297】 R ０２ Preferably, the atoms are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and due to their industrial availability, hydrogen atoms or methyl groups are most preferred. 【0298】 Vfa ０２ This is Va in the general formula (a1-1) of the above constituent unit (a1) １ The same applies to preferred materials. However, they do not contain either a perfluoroalkyl skeleton or a difluoromethyl group. 【0299】 n ｆ０２ The value is preferably 0 or 1, and more preferably 0. 【0300】 Rfa０２ Preferably, the lactone-containing cyclic group is represented by any of the formulas (a2-r-1) to (a2-r-7), and the group represented by formula (a2-r-1) or (a2-r-2) is preferred. 【0301】 Furthermore, the constituent units (fa2) of the polymer compound (F1) may be one type or two or more types. The proportion of constituent units (fa2) in the polymer compound (F1) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound (F1). By setting the proportion of constituent units (fa2) to be above the lower limit of the above preferred range, the lithography characteristics are improved. Conversely, by setting it to be below the upper limit, good water repellency is achieved. 【0302】 <Other constituent units> The polymer compound (F1) may have a constituent unit (a12) other than the above constituent units (f1), (fa1), and (fa2) (however, excluding constituent units (f1), (fa1), (fa2), those having a perfluoroalkyl skeleton, and those having a difluoromethyl group). 【0303】Compounds that derive the constituent unit (a12) include, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetra Examples include alkyl (meth)acrylates such as cyclododecyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide; and polymerizable compounds containing epoxy groups. 【0304】 In particular, the constituent unit (a12) represented by the following general formula (a12-1) is more preferred. 【0305】 【0306】 [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. Ra １２ It is an alkyl group. 【0307】In the above formula (a12-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and due to the ease of industrial availability, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is even more preferred. 【0308】 In the above formula (a12-1), Ra １２ Examples of alkyl groups include linear or branched alkyl groups and cyclic alkyl groups. Linear or branched alkyl groups with 1 to 5 carbon atoms are preferred, with methyl, ethyl, or butyl groups being more preferred. Cyclic alkyl groups include cyclopentyl, cyclohexyl, adamantyl, norbornyl, isobornyl, tricyclodecyl, and tetracyclododecyl groups, with cyclohexyl or adamantyl groups being more preferred. 【0309】 The constituent unit (a12) of component (F1) may be one type or two or more types. When component (F1) has constituent unit (a12), the proportion of constituent unit (a12) in component (F1) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, even more preferably 2 to 30 mol%, and particularly preferably 5 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (F1). By setting the proportion of constituent unit (a12) above the lower limit, the contact angle is increased due to high hydrophobicity, and the risk of WMD can be further suppressed. On the other hand, by setting the proportion of constituent unit (a12) below the upper limit, it becomes easier to balance it with other constituent units. 【0310】In the resist composition of this embodiment, component (F) includes a polymer compound (F1) having a constituent unit (f1) (component (F1)). Preferred components of (F1) include polymer compounds having at least one constituent unit (f1). Specifically, preferred components of (F1) include polymer compounds having a repeating structure of constituent unit (f1) (homopolymers consisting of constituent unit (f1)); polymer compounds having a repeating structure of constituent unit (f1) and constituent unit (fa1); polymer compounds having a repeating structure of constituent unit (f1) and constituent unit (fa2); polymer compounds having a repeating structure of constituent unit (f1), constituent unit (fa1), and constituent unit (a12); and polymer compounds having a repeating structure of constituent unit (f1), constituent unit (fa2), and constituent unit (a12). 【0311】 The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 3,000 to 40,000, and most preferably 4,000 to 30,000. If the weight-average molecular weight is below the upper limit of this range, the resist composition in this embodiment has sufficient solubility in resist solvents for use as a resist, and if the weight-average molecular weight is above the lower limit of this range, the resist composition in this embodiment has good dry etching resistance and a good resist pattern cross-sectional shape. The degree of dispersion (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. 【0312】 As component (F), in addition to the polymer compound (F1) described above, for example, any fluorine-containing polymer compound described in Japanese Patent Publication No. 2010-002870, Japanese Patent Publication No. 2010-032994, Japanese Patent Publication No. 2010-277043, Japanese Patent Publication No. 2011-13569, and Japanese Patent Publication No. 2011-128226 that does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group can be used. Furthermore, in the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. 【0313】 The content of component (F) in the resist composition is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 7 parts by mass, per 100 parts by mass of component (A). 【0314】 <Optional Components> The resist composition of this embodiment may further contain components other than the above-mentioned components (A), (B), and (F) (optional components). Examples of such optional components include the following components (D) and (S). 【0315】 Component (D) and component (S) do not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. Furthermore, it is more preferable that component (D) and component (S) do not contain any compounds having a fluorine atom. 【0316】 ≪Acid Diffusion Controlling Agent Component (D)≫ In addition to components (A), (B), and (F), the resist composition according to the embodiment of the present invention may further contain an acid diffusion controlling agent component (D). The acid diffusion controlling agent component (D) (component (D)) acts as a quencher (acid diffusion controlling agent) that traps the acid generated by exposure in the resist composition. Component (D) may be, for example, a photodegradable base (D1) that decomposes upon exposure and loses its acid diffusion controlling properties (hereinafter referred to as "component (D1)"), or a nitrogen-containing organic compound (D2) that does not fall under component (D1) (hereinafter referred to as "component (D2)"), but component (D1) is preferred. By using a resist composition containing component (D), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern. 【0317】Component (D) does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. Preferably, component (D) contains only compounds that do not fall under the category of compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. In other words, preferably, component (D) does not contain any compounds that fall under the category of PFAS. Furthermore, preferably, component (D) does not contain any fluorine atoms. 【0318】 ・Regarding component (D1) By using a resist composition containing component (D1), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern. Component (D1) may be used as an acid generator in addition to or instead of component (B) above. Component (D1) is not particularly limited as long as it does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group, and decomposes upon exposure, losing its acid diffusion controllability. Preferably, it is 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)") and a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), with component (d1-2) being more preferred. Components (d1-1) and (d1-2) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion controllability (basicity), but they act as quenchers in the unexposed areas of the resist film. 【0319】 【0320】 [In general formula (d1-1) and general formula (d1-2), Rd １ and Rd ２ Each of these is independently an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, Rd in formula (d1-2) ２ In this example, assume that no fluorine atoms are bonded to carbon atoms adjacent to the sulfur atom. m is an integer greater than or equal to 1, and M ｍ＋ These are each independently m-valent organic cations. 【0321】{(d1-1) component} - In the anionic component of formula (d1-1), Rd １ R' is a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and each of the above R' is... ２０１ Similar examples include Rd １ Preferred substituents are optionally substituted aromatic hydrocarbon groups, optionally substituted aliphatic cyclic groups, or optionally substituted linear alkyl groups. Optional substituents on these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and in this case, preferred substituents are linking groups represented by any of the above formulas (y-al-1) to (y-al-5). 【0322】 Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). Suitable examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 ２，６ It is more preferable that the group is obtained by removing one or more hydrogen atoms from a polycycloalkane such as decane or tetracyclododecane. The chain-like alkyl group is preferably one to ten carbon atoms in number, and specifically, examples include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; and branched alkyl groups such as 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group. 【0323】 The following are preferred specific examples of the anion portion of component (d1-1). 【0324】 【0325】 - In the cation component formula (d1-1), M ｍ＋ M is an organic cation with an m-valence. ｍ＋ Suitable organic cations include those similar to the cations represented by any of the general formulas (ca-1) to (ca-3), with the cation represented by the general formula (ca-1) being more preferred, and cations represented by any of the formulas (ca-1-1) to (ca-1-42) or (ca-1-49) to (ca-1-67) being even more preferred. The (d1-1) component may be used alone or in combination of two or more types. 【0326】 {(d1-2) component} - In the anionic component of formula (d1-2), Rd ２ R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. ２０１ Similar examples include the following. However, Rd ２ In this case, the carbon atom adjacent to the S atom is assumed to be unbonded to a fluorine atom (not fluorine-substituted). This results in the anions of components (d1-2) becoming appropriately weak acid anions, improving the quenching ability of component (D). Rd ２ The preferred group is a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents. The chain-like alkyl group is preferably having 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The preferred aliphatic cyclic group is adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ A group obtained by removing one or more hydrogen atoms from decane, tetracyclododecane, etc. (which may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor, etc. Rd ２ The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). １ Examples include substituents similar to those that may be present on hydrocarbon groups (aromatic hydrocarbon groups, aliphatic cyclic groups, and linear alkyl groups) in the above. 【0327】The following are preferred specific examples of the anion portion of component (d1-2). 【0328】 【0329】 - In the cation component formula (d1-2), M ｍ＋ is an m-valent organic cation, and M in formula (d1-1) above. ｍ＋ The same applies. (d1-2) Components may be used individually or in combination of two or more. 【0330】 The (D1) component may be any one of the above components (d1-1) to (d1-2), or two or more may be used in combination. When the resist composition contains the (D1) component, the content of the (D1) component in the resist composition is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2.5 to 15 parts by mass, per 100 parts by mass of the (A) component. When the content of the (D1) component is above the preferred lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, when the content of the (D1) component is below the upper limit, good sensitivity can be maintained and throughput is also excellent. 【0331】 Method for producing component (D1): The method for producing components (d1-1) and (d1-2) is not particularly limited and can be produced by known methods. For example, it can be produced in the same manner as described in U.S. Patent Application Publication No. 2012 / 0149916. 【0332】 Regarding component (D2): Component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not fall under component (D1) above, as an acid diffusion control agent component. Component (D2) is not particularly limited as long as it does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group, acts as an acid diffusion control agent, and does not fall under component (D1). Any known component may be used. Among these, aliphatic amines or aromatic amines are preferred as component (D2), with aromatic amines being more preferred. 【0333】An aliphatic amine is an amine having one or more aliphatic groups, and preferably the aliphatic group has 1 to 12 carbon atoms. Examples of aliphatic amines include ammonia (NH₃). ３ Examples include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom is substituted with an alkyl group having 12 or fewer carbon atoms or a hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred as aliphatic amines, and tri-n-pentylamine or tri-n-octylamine are particularly preferred. 【0334】 Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. Aliphatic polycyclic amines with 6 to 10 carbon atoms are preferred, and specific examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane. 【0335】 Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred. 【0336】 Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, 2,6-di-tert-butylpyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, trimenzylamine, 2,6-diisopropylaniline, and N-tert-butoxycarbonylpyrrolidine. 【0337】 The (D2) component may be used alone or in combination of two or more types. When the resist composition contains the (D2) component, the content of the (D2) component in the resist composition is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of the (A) component. By using the above range, the resist pattern shape, the stability over time, etc., are improved. 【0338】≪Organic Solvent Component (S)≫ The resist composition of this embodiment can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "component (S)"). The component (S) does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group, and can dissolve each component used to form a homogeneous solution. Any solvent known as a solvent for chemically amplified resist compositions can be appropriately selected and used. In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), γ-butyrolactone, EL (ethyl lactate), and cyclohexanone are preferred. 【0339】 Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred as component (S). The mixing ratio (mass ratio) can be appropriately determined considering the compatibility between PGMEA and the polar solvent. In addition, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred as component (S). In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited and is appropriately set according to the coating thickness at a concentration that can be applied to a substrate, etc. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass. 【0340】 The resist composition in this embodiment may further optionally contain miscible additives, such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, and the like. 【0341】The resist composition of this embodiment contains the above-described components (A), (B), and (F), and optionally the aforementioned optional components. For example, a resist composition containing component (A), component (B), component (F), and component (D) is preferred. Furthermore, a resist composition containing component (A), component (B), component (F), component (D), and component (S) is preferred. 【0342】 The resist composition of this embodiment does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. That is, the components contained in the resist composition do not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. Furthermore, it is preferable that the resist composition does not contain fluorine atoms. In addition, the resist composition may not contain any fluorine atoms other than the fluorine atoms contained in component (F). 【0343】 The resist composition of this embodiment described above is a resist composition that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid, and contains a base component (A) whose solubility in a developer solution changes due to the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and a fluorine additive component (F), wherein the fluorine additive component (F) contains a polymer compound (F1) having a constituent unit (f1) represented by the following general formula (f1-1), and the resist composition does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. Since component (F) contains an aryl group having one or more fluorine atoms in the constituent unit (f1), it is a highly hydrophobic constituent unit, and the hydrophobicity of the resist film is enhanced. Furthermore, since the resist composition of this embodiment does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group, it is possible to achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact. 【0344】The resist film formed using the resist composition of this embodiment exhibits increased hydrophobicity compared to conventional resist compositions, due to the use of component (F) described above. This results in changes to the contact angle with water, such as the static contact angle (the angle between the water droplet surface on the resist film in a horizontal state and the resist film surface), the dynamic contact angle (the contact angle when a water droplet begins to fall when the resist film is tilted; there is a contact angle at the forward endpoint in the direction of the fall (advancing angle) and a contact angle at the backward endpoint in the direction of the fall (receding angle)), and the fall angle (the tilt angle of the resist film when a water droplet begins to fall when the resist film is tilted). For example, the higher the hydrophobicity of the resist film, the larger the static and dynamic contact angles become, while the fall angle decreases. The contact angle, an indicator of hydrophobicity, shows a strong correlation with the occurrence rate of surface defects in the resist film and resist peeling due to water. 【0345】 Figure 1 shows the advance angle (θ １ ), sweepback angle (θ ２ ) and fall angle (θ ３ This is a diagram illustrating the following. Here, the advance angle is the angle θ between the surface of the droplet at the lower end 1a of the droplet 1 and the plane 2 when the plane 2 on which the droplet 1 is placed is gradually tilted, as shown in Figure 1, and the droplet 1 begins to move (fall) on the plane 2. １ Furthermore, at this time (when the droplet 1 begins to move (fall) on the plane 2), the angle θ between the droplet surface at the upper end 1b of the droplet 1 and the plane 2 ２ This is the receding angle, and the inclination angle θ of the plane 2. ３ This is the angle of fall. 【0346】In this specification, the static contact angle, dynamic contact angle, and fall angle can be measured, for example, as follows. First, a resist composition solution is spin-coated onto a silicon substrate, and then a resist film is formed by heating under predetermined conditions, for example, at a temperature of 80 to 115°C for 60 seconds. Next, the resist film can be measured using commercially available measuring devices such as DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.), AUTO SLIDING ANGLE: SA-30DM (product name, manufactured by Kyowa Interface Science Co., Ltd.), and AUTO DISPENSER: AD-31 (product name, manufactured by Kyowa Interface Science Co., Ltd.). 【0347】 In this embodiment, the resist composition is prepared by coating a 12-inch silicon wafer with the resist composition using a spinner, pre-baking it on a hot plate at 100°C for 60 seconds, and drying it. The measured value of the receding angle (receding angle 1) in the dynamic contact angle of the 80 nm thick resist film is preferably 70° or more, more preferably 72° or more, even more preferably 73° or more, and may also be 74° or more, or 75° or more. A measured receding angle of 70° or more indicates sufficient hydrophobicity of the resist film, resulting in superior lithography characteristics. Furthermore, it allows for faster scanning speeds in immersion lithography. 【0348】 Furthermore, for a film developed from the resist film described above, if the receding angle after development, measured in the same manner as the dynamic contact angle described above, is defined as receding angle 2, then the Δcontact angle calculated by the following formula 1 is preferably 3° or more, more preferably 5° or more, even more preferably 7° or more, and may be 9° or more, or 10° or more. A Δcontact angle of 7° or more is preferable because it exhibits excellent developer solubility and superior defect characteristics. Also, a Δcontact angle of 20° or less is preferable, more preferably 17° or less, even more preferably 15° or less, and may be 13° or less. A Δcontact angle of 20° or less is preferable because it exhibits excellent stability over time. 【0349】 (Formula 1): Δcontact angle = receding angle 1 - receding angle 2 【0350】The delta-contact angle is the difference between receding angle 1 and receding angle 2, and serves as an indicator of base degradation. Furthermore, the delta-contact angle can also be an indicator of defect characteristics and long-term stability. 【0351】 (Method for forming a resist pattern) A resist pattern forming method according to a second embodiment of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition of the above-described embodiment, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of such a resist pattern forming method is, for example, a resist pattern forming method carried out as follows. 【0352】 First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-apply bake (PAB)) treatment is performed for 40 to 120 seconds, preferably 50 to 90 seconds, at a temperature of, for example, 80 to 150°C, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure device such as an electron beam lithography apparatus or an EUV exposure apparatus, either through exposure via a mask (mask pattern) with a predetermined pattern formed on it, or by direct irradiation with an electron beam without a mask pattern. After that, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 50 to 90 seconds, at a temperature of, for example, 80 to 150°C. Next, the resist film is subjected to a development treatment. In the case of an alkaline development process, an alkaline developer is used, and in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used. After the development treatment, a rinsing treatment is preferably performed. For rinsing, in the case of an alkaline development process, a water rinse using pure water is preferred, and in the case of a solvent development process, a rinse solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing process, a process to remove the developer or rinse solution adhering to the pattern using a supercritical fluid may be performed. After the development or rinsing process, drying is performed. In some cases, a bake process (post-bake) may be performed after the development process. In this way, a resist pattern can be formed. 【0353】 The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, the support material can be a silicon wafer, a metal substrate such as copper, chromium, iron, or aluminum, or a glass substrate. As for the wiring pattern material, for example, copper, aluminum, nickel, or gold can be used. 【0354】 The wavelength used for exposure is not particularly limited, and can be used with radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays. The resist composition is highly useful for use with KrF excimer lasers, ArF excimer lasers, EB, or EUV. 【0355】 The method for exposing the resist film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion lithography, but liquid immersion lithography is preferred. Liquid immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is filled in advance with a solvent (liquid immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in that state. As the liquid immersion medium, a solvent having a refractive index greater than that of air and smaller than that of the resist film to be exposed is preferred. The refractive index of such a solvent is not particularly limited as long as it is within the above range. Examples of solvents having a refractive index greater than that of air and smaller than that of the resist film include water, fluorine-based inert liquids, silicone-based solvents, hydrocarbon-based solvents, etc. Water is preferably used as the liquid immersion medium. 【0356】Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. The organic solvent contained in the organic developer used in the solvent development process can be any solvent that can dissolve component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents. 【0357】 Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate. 【0358】 Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile. 【0359】 Organic developers may contain known additives as needed. Examples of such additives include surfactants. The surfactant is not particularly limited as long as it is a compound that does not fall under either a perfluoroalkyl skeleton or a difluoromethyl group; for example, ionic or nonionic fluorine-based and / or silicone-based surfactants can be used. 【0360】The development process can be carried out by known development methods, such as immersing the support in developer for a certain period of time (dip method), piling up developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), spraying developer onto the surface of the support (spray method), or continuously dispensing developer while scanning a developer dispensing nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispensing method). 【0361】 Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously dispensing the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method). 【0362】 The resist compositions of the embodiments described above, and the various materials used in the pattern forming methods of the embodiments described above (for example, resist solvents, developers, rinse solutions, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of metal atom-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device). 【0363】 In the resist pattern formation method of this embodiment described above, since the resist composition according to the embodiment of the present invention described above is used, it is possible to form a resist pattern that reduces environmental impact and has excellent lithography characteristics when forming a resist pattern. 【0364】The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 【0365】 <Examples of compound synthesis> [Synthesis Example 1: Synthesis of compound (f)-1] Compound (f)-1 was synthesized using the following synthesis method. 【0366】 【0367】 Under a nitrogen atmosphere, 4.3 g of compound (X1), 3.0 g of compound (Y1), 0.03 g of dimethylaminopyridine (DMAP), and dichloromethane (CH) were placed in a three-necked flask. ２ Cl ２ ) 15 g was added and stirred at a temperature below 10°C. Then, 2.9 g of diisopropylcarbodiimide (DIC) was added while maintaining the temperature and stirred at a temperature below 10°C for 0.5 hours, then the temperature was raised to 25°C and stirred for 12 hours. After that, the reaction mixture was filtered and the filtrate was washed three times with 100 g of 1% citric acid aqueous solution, and then washed three times with 100 g of pure water. After washing, the mixture was concentrated to dryness using a rotary pump to obtain 4.4 g of white solid (f)-1 (yield 65%). 【0368】 NMR measurements were performed on the obtained compound (f)-1, and its structure was identified based on the following analytical results. 【0369】 1 H NMR: δ 0.89 (3H, t, J = 6.8 Hz), 1.75-1.91 (5H, 1.82 (dq, J = 7.0, 6.8 Hz), 1.86 (s)), 4.80 (2H, s), 5.27 (1H, t, J = 7.0 Hz), 5.56 (1H, d, J = 3.8 Hz), 6.06 (1H, d, J = 3.8 Hz) 【0370】 [Synthesis Example 2: Synthesis of Compound (f)-2] Compound (f)-2 was synthesized using the following synthesis method. 【0371】 【0372】 Compound (f)-2 was obtained in the same manner as in Synthesis Example 1, except that compound (X1) was replaced with compound (X2) in equimolar amounts. ​【0373】 The obtained compound (f)-2 was subjected to NMR measurement, and its structure was identified based on the following analytical results. 【0374】 1 H NMR: δ 1.26-1.66 (10H, 1.33 (dtt, J = 12.1, 6.5, 2.8 Hz), 1.47 (dtt, J = 12.8, 6.5, 2.8 Hz), 1.58 (dtd, J = 13.4, 6.5, 2.8 Hz)), 1.86 (3H, s), 2.24 (1H, tdt, J = 10.3, 3.0, 2.8 Hz), 4.82 (2H, s), 5.10 (1H, d, J = 3.0 Hz), 5.56 (1H, d, J = 3.8 Hz), 6.06 (1H, d, J = 3.8 Hz). 【0375】 [Synthesis Example 3: Synthesis of Compound (f)-3] Compound (f)-3 was synthesized using the following synthesis method. 【0376】 【0377】 Compound (f)-3 was obtained in the same manner as in Synthesis Example 1, except that compound (X1) was replaced with compound (X3) in equimolar amounts. 【0378】 The obtained compound (f)-3 was subjected to NMR measurement, and its structure was identified based on the following analytical results. 【0379】 1 H NMR: δ 1.86 (3H, s), 3.60 (2H, d, J = 5.6 Hz), 4.78 (2H, s), 5.41 (1H, t, J = 5.6 Hz), 5.56 (1H, d, J = 3.8 Hz), 6.06 (1H, d, J = 3.8 Hz). 【0380】 [Synthesis of Polymer Compound (F)-1] Using the corresponding raw material monomers, the target polymer compound (F)-1 was obtained by polymerization using a conventional method. 【0381】 ​​For the obtained polymer compound (F)-1, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, was 26,000, and the molecular weight dispersion (PDI) (Mw / Mn) was 1.7. Furthermore, the carbon-13 nuclear magnetic resonance spectrum ( １３ The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by C-NMR was l / m = 75 / 25. 【0382】 [Synthesis of Polymer Compound (F)-2 to Polymer Compound (F)-6 and Polymer Compound (F2)-1] Polymer Compound (F)-2 to Polymer Compound (F)-6 and Polymer Compound (F2)-1 were obtained by polymerization using the corresponding starting monomers, in the same manner as the synthesis of [Polymer Compound (F)-1] above, by a conventional method. 【0383】 The structure, weight-average molecular weight (Mw), molecular weight dispersion (PDI), and copolymerization composition ratio (molar ratio) of each obtained polymer compound are shown below. 【0384】 【0385】 【0386】 【0387】 <Preparation of Resist Compositions> (Examples 1-11, Comparative Examples 1-2) The resist compositions for each example were prepared by mixing and dissolving the components shown in Table 1. 【0388】 【0389】 In Table 1, each abbreviation has the following meaning. The unit of composition is parts by mass. 【0390】 A-1: A polymer compound represented by the following chemical formula (A)-1. For this polymer compound (A)-1, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 7100, and the molecular weight dispersion (Mw / Mn) is 1.6. １３ The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by C-NMR was l / m = 50 / 50. 【0391】A-2: A polymer compound represented by the following chemical formula (A)-2. For this polymer compound (A)-2, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 7000, and the molecular weight dispersion (Mw / Mn) is 1.6. １３ The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by C-NMR was l / m = 50 / 50. 【0392】 A-3: A polymer compound represented by the following chemical formula (A)-3. For this polymer compound (A)-3, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 7000, and the molecular weight dispersion (Mw / Mn) is 1.6. １３ The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by C-NMR was l / m = 50 / 50. 【0393】 A-4: A polymer compound represented by the following chemical formula (A)-4. For this polymer compound (A)-4, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, is 7000, and the molecular weight dispersion (Mw / Mn) is 1.5. １３ The copolymerization ratio (the proportion (molar ratio) of each constituent unit in the structural formula) determined by C-NMR was l / m = 50 / 50. 【0394】 【0395】 B-1 to B-2: Acid generators consisting of the following compounds (B)-1 to (B)-2 respectively. (B2)-1 to (B2)-2: Acid generators consisting of the following compounds (B2)-1 to (B2)-2 respectively. 【0396】 【0397】 D-1 to D-2: Acid diffusion control agents consisting of compounds represented by the following chemical formulas (D)-1 to (D)-2. 【0398】 【0399】 F-1 to F-6, F2-1: Fluorine additive components consisting of compounds represented by (F)-1 to (F)-6 and (F2)-1 above. 【0400】S-1: Mixed solvent consisting of 2925 parts by mass of propylene glycol monomethyl ether acetate, 450 parts by mass of propylene glycol monomethyl ether, and 1125 parts by mass of cyclohexanone. 【0401】 <Formation of Resist Film> The resist compositions of Examples 1 to 11 and Comparative Examples 1 to 2 were applied to a 12-inch silicon wafer using a spinner, and a pre-bake (PAB) treatment was performed on a hot plate at 100°C for 60 seconds, followed by drying to form a resist film with a thickness of 80 nm. 【0402】 <Evaluation of Contact Angle> (Contact Angle) Water was dropped onto the surface of the resist film formed by the above <Formation of Resist Film>, and the dynamic contact angle (receding angle 1) was measured using DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.) (Contact angle measurement: 50 μL of water). (Contact Angle after Development) The resist film formed by the above <Formation of Resist Film> was subjected to alkaline development at 23°C with a 2.38 mass% TMAH aqueous solution (product name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 15 seconds, and then rinsed with pure water for 15 seconds and shaken dry. The dynamic contact angle (receding angle 2) after development was measured on the surface of the developed film in the same manner as the contact angle after coating described above. 【0403】 The Δ-contact angle was calculated using Equation 1 below and is shown in the table. (Equation 1): Δ-contact angle = receding angle 1 - receding angle 2 【0404】 <Evaluation of WMD defects> An organic anti-reflective coating composition "ARC-29A" (trade name, manufactured by Brewer Science Co., Ltd.) was applied to a 12-inch silicon wafer using a spinner, and dried by baking at 205°C for 60 seconds on a hot plate to form an organic anti-reflective coating with a thickness of 89 nm. The resist compositions of Examples 1 to 11 and Comparative Examples 1 to 2 were each applied to the organic anti-reflective coating, and a pre-bake (PAB) treatment was performed on a hot plate at 100°C for 60 seconds, followed by drying to form a resist coating with a thickness of 80 nm. 【0405】Using an immersion ArF exposure system XT1900Gi [manufactured by ASML; NA (numerical aperture) = 0.95, Dipole (in / out = 0.668 / 0.829), TE-pol, immersion medium: water], an ArF excimer laser (193 nm) was selectively irradiated through a photomask (6% halftone). Subsequently, PEB treatment was performed at 90°C for 60 seconds. Next, alkaline development was performed at 23°C for 10 seconds with a 2.38 mass% TMAH aqueous solution (product name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.), followed by a 15-second rinse with pure water and complete drying. As a result, in all examples, a 1:1 line-and-space (LS) pattern with a line width of 70 nm and a pitch of 140 nm was formed. The LS patterns obtained above were observed using a surface defect observation device KLA2905 (product name) manufactured by KLA-Tencor, and the number of WMD defects per silicon wafer was measured and evaluated according to the following evaluation criteria. The WMD particle size was limited to those with a size of 1 μm or larger. 【0406】 (Evaluation Criteria) ◎: 0 WMD defects ○: 1 to 10 WMD defects ×: More than 10 WMD defects 【0407】 <Environmental Regulations> Each example of the resist composition was evaluated according to the following evaluation criteria. OK (Good): The (F) component does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. NG (Poor): The (F) component contains either a compound having a perfluoroalkyl skeleton or a compound having a difluoromethyl group. 【0408】 As shown in Table 1, the resist film formed with the resist composition of this embodiment exhibits good environmental performance, and the difference between the contact angle with water on the surface immediately after deposition and the contact angle with water on the surface after development is larger than that of conventional materials, confirming sufficient base degradability. Furthermore, it was confirmed that the resist composition of the embodiment to which the present invention is applied can form a resist pattern that can achieve both the suppression of WMD necessary in the TC-Less process and the reduction of environmental impact. 【0409】Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-213886, filed on December 6, 2024, the contents of which are incorporated herein by reference.

Claims

A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, It contains a base component (A) whose solubility in the developer solution changes due to the action of acid, an acid generating agent component (B) that generates acid upon exposure, and a fluorine additive component (F). The fluorine additive component (F) comprises a polymer compound (F1) having a constituent unit (f1) represented by the following general formula (f1-1), The resist composition does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. Resist composition. [In the general formula (f1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. Lf is a divalent linking group. Ar is an aryl group. nf １ [ is an integer greater than or equal to 1.] The resist composition according to claim 1, wherein the polymer compound (F1) further comprises a constituent unit (fa1) containing an acid-degradable group or a constituent unit (fa2) containing a lactone-containing cyclic group. 　 The resist composition according to claim 2, wherein the constituent unit (fa1) containing the acid-degradable group comprises a constituent unit (fa-1) represented by the following general formula (fa-1). [In general formula (fa-1), R ０１ Vfa is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. ０１ n is a divalent hydrocarbon group which may have an ether bond. ｆ０１ Rfa is an integer between 0 and 2. ０１ It is an acid-dissociating group. The aforementioned lactone-containing cyclic group, -SO ２ - The resist composition according to claim 2, wherein the constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group comprises a constituent unit (fa-2) represented by the following general formula (fa-2). 〔In general formula (fa-2), R ０２ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Vfa ０２ is a divalent hydrocarbon group which may have an ether bond. n ｆ０２ is an integer of 0 to 2. Rfa ０２ represents a lactone-containing cyclic group represented by any of the following formulas (a2-r-1) to (a2-r-7), a -SO ２ -containing cyclic group represented by any of the following formulas (a5-r-1) to (a5-r-4), or a carbonate-containing cyclic group represented by any of the following formulas (ax3-r-1) to (ax3-r-3). ] [In formulas (a2-r-1) to (a2-r-7), Ra' ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR, -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - A cyclic group containing an oxygen atom (-O-) or a sulfur atom (-S-) is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond. [In formulas (a5-r-1) to (a5-r-4), Ra' ５１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer from 0 to 2. [In the formula, Ra' ｘ３１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - It is a cyclic group containing an oxygen atom or a sulfur atom; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom; p' is an integer from 0 to 3; and q' is 0 or 1. * indicates a bond. Furthermore, the resist composition according to claim 1 or 2, further comprising an acid diffusion control agent component (D) that controls the diffusion of acid generated from the acid generating agent component (B) by exposure. 　 A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition described in claim 1 or 2; exposing the resist film; and developing the resist film to form a resist pattern.

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