Resist composition, resist pattern forming method, polymer compound, and fluorine additive component

Abstract

The present invention provides a resist composition, resist pattern forming method, polymer compound, and fluorine additive component which are capable of reducing environmental load and achieving both suppression of bridge defects and suppression of WMD required in TC-Less process. The present invention relates to a resist composition which generates an acid upon exposure, with the solubility of the resist composition in a developing solution changed by an action of the acid. The resist composition comprises (A) a base material component, with the solubility thereof in a developing solution changed by an action of an acid, (B) an acid generator component that generates an acid upon exposure, and (F) a fluorine additive component, wherein the fluorine additive component (F) contains a polymer compound (F1) having a constituent unit (f1) and a constituent unit (fa2); the constituent unit (f1) is represented by general formula (f1-1) described in the description; the constituent unit (fa2) contains a lactone-containing cyclic group, a -SO2-containing cyclic group, or a carbonate-containing cyclic group; and the resist composition contains neither a compound having a perfluoroalkyl skeleton nor a compound having a difluoromethyl group.

Description

Resist composition, resist pattern formation method, polymer compound, and fluorine additive component 【0001】 The present invention relates to a resist composition, a resist pattern formation method, a polymer compound, and a fluorine additive component. 【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. To obtain good lithographic properties, it is necessary to appropriately adjust the solubility and water repellency during development. Furthermore, due to the growing environmental awareness in recent years, the manufacture and use of compounds that fall under PFAS (Per- and Polyfluoroalkyl Substances) may be restricted. For this reason, the development of organofluorine compounds that contain both perfluoroalkyl groups and perfluoroalkylene groups, as well as difluoromethyl groups, is desired. 【0009】 However, when resist patterns were formed using compounds containing both a perfluoroalkyl skeleton and a difluoromethyl group as fluorine additive components, 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). Furthermore, insufficient base degradability resulted in insufficient hydrophilization during the development process, leading to the precipitation of resin and other components, and the occurrence of bridge defects adhering to the highly hydrophobic resist pattern surface could not be suppressed. 【0010】 The present invention has been made in view of the above circumstances, and aims to provide a resist composition, a resist pattern formation method, a polymer compound, and a fluorine additive component that can form a resist pattern that reduces environmental impact and achieves both the suppression of WMD and the suppression of bridge defects necessary in the TC-Less process. 【0011】 As a result of diligent research to solve the above problems, the present inventors have found that a resist composition, a resist pattern formation method, a polymer compound, and a fluorine additive component can be obtained with the following configuration, which can form a resist pattern that reduces environmental impact and achieves both the suppression of WMD and the suppression of bridge defects necessary in the TC-Less process, 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 constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - A polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or a difluoromethyl group. 【0013】 【0014】 [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. nf ２ It is either 1 or 2. Lf １ 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 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 polymer compound according to the third embodiment of the present invention comprises a constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - A polymer compound having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0017】 【0018】 [In general formula (f1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. nf ２ is 1 or 2. Lf １ is a divalent linking group. Rf １ is a chain hydrocarbon group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, a nitro group, or a cyano group. Ar is an aryl group. nf １ is an integer of 1 or more.] 【0019】 Further, the fluorine additive component according to the fourth embodiment of the present invention includes a structural unit (f1) represented by the above general formula (f1-1) and a structural unit (fa2) containing a lactone-containing cyclic group, a -SO ２ -containing cyclic group or a carbonate-containing cyclic group, and does not contain any compound having a perfluoroalkyl skeleton and a compound having a difluoromethyl group. 【0020】 The present invention can provide a resist composition, a resist pattern forming method, a polymer compound, and a fluorine additive component that can reduce environmental impact and achieve both suppression of WMD required in the TC-Less process and suppression of bridge defects. 【0021】 FIG. 1 is a diagram for explaining the advancing angle (θ １ ), the receding angle (θ ２ ), and the falling angle (θ ３ ). 【0022】 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below. 【0023】In this disclosure, "aliphatic" is defined as a concept relative to aromatic, meaning groups, compounds, etc., that do not possess aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. "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 such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. "Fluorinated alkyl group" or "fluorinated alkylene group" means a group in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms. "Constituent unit" means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer). When it is stated that "may have substituents," this refers to the case where a hydrogen atom (-H) is substituted with a monovalent group, and the case where a methylene group (-CH) is substituted with a monomer. ２ This includes both cases where the negative (-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation irradiation. 【0024】 "Constituent units derived from acrylic acid esters" refers to constituent units formed when the ethylenic double bond of an acrylic acid ester is cleaved. "Acrylic acid esters" are derived from acrylic acid (CH4). ２ This is a compound in which the hydrogen atom at the carboxyl group terminus of (=CH-COOH) is replaced by an organic group. In acrylic acid esters, the hydrogen atom bonded to the carbon atom at the α position may be replaced by a substituent. Substituents that replace the hydrogen atom bonded to the carbon atom at the α position (R α０ ) is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms, or an alkyl halogenated group having 1 to 5 carbon atoms. Also, acrylic acid esters have substituents (R α０ Itaconic acid diesters in which the substituent (R) is substituted with substituents containing an ester bond, or substituents (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". 【0025】 "Constituent units derived from hydroxystyrene" refers to constituent units formed by the cleavage of the ethylenic double bond of hydroxystyrene. "Constituent units derived from hydroxystyrene derivatives" refers to constituent units formed by the cleavage of the ethylenic double bond of hydroxystyrene derivatives. "Hydroxystyrene derivatives" is a concept that includes hydroxystyrene in which the α-position hydrogen atom is substituted with other substituents such as alkyl groups and alkyl halides, as well as their derivatives. Examples of such derivatives include hydroxystyrene in which the hydrogen atom of the hydroxyl group of hydroxystyrene, which may have the α-position hydrogen atom substituted with a substituent, is substituted with an organic group; and hydroxystyrene in which a substituent other than a hydroxyl group is bonded to the benzene ring of hydroxystyrene, which may have the α-position hydrogen atom substituted with a substituent. Unless otherwise specified, the α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded. Substituents that substitute the α-position hydrogen atom of hydroxystyrene are the same as those listed as α-position substituents in the α-substituted acrylic acid esters mentioned above. 【0026】"Constituent units derived from vinylbenzoic acid or vinylbenzoic acid derivatives" refers to constituent units formed by the cleavage of the ethylenic double bond of vinylbenzoic acid or vinylbenzoic acid derivatives. "Vinylbenzoic acid derivatives" is a concept that includes vinylbenzoic acid in which the α-position hydrogen atom is substituted with other substituents such as alkyl groups and alkyl halides, as well as their derivatives. Examples of such derivatives include vinylbenzoic acid in which the hydrogen atom of the carboxyl group, which may have the α-position hydrogen atom substituted with a substituent, is substituted with an organic group; and vinylbenzoic acid in which substituents other than hydroxyl groups and carboxyl groups are bonded to the benzene ring, which may have the α-position hydrogen atom substituted with a substituent. Note that α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded, unless otherwise specified. 【0027】 The alkyl group as the α-substituent is preferably a linear or branched alkyl group, specifically an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.). Furthermore, the halogenated alkyl group as the α-substituent is specifically a group in which some or all of the hydrogen atoms of the alkyl group as the α-substituent are replaced with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Furthermore, the hydroxyalkyl group as the α-substituent is specifically a group in which some or all of the hydrogen atoms of the alkyl group as the α-substituent are replaced with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, with 1 being the most preferred. 【0028】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. 【0029】 [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 constituent unit (f1) represented by the general formula (f1-1) described later, a lactone-containing cyclic group, and -SO ２ - A resist composition comprising a polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0030】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. 【0031】 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. 【0032】 The resist composition of this embodiment 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; a constituent unit (f1) represented by the above general formula (f1-1); and a lactone-containing cyclic group, -SO ２- Contains a fluorine-containing additive component (F) which includes a polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group. 【0033】 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. 【0034】 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). However, removing fluorine from fluorine-containing compounds results in extremely low water repellency and surface segregation properties. 【0035】 The fluorine additive component (F) according to the embodiment of the present invention comprises a constituent unit (f1) represented by the general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - It contains a polymer compound having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and the fluorine additive component (F) does not contain any compounds having a perfluoroalkyl skeleton or a compound having a difluoromethyl group, thus reducing the environmental burden and achieving both the suppression of WMD and the suppression of bridge defects necessary in the TC-Less process. 【0036】≪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). 【0037】 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. 【0038】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. 【0039】 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. 【0040】 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. 【0041】 The compound contained in component (A) preferably does not contain any compounds having a perfluoroalkyl skeleton or a difluoromethyl group, and is preferably a polymer compound that does not fall under the category of PFAS. In other words, the compound contained in component (A1) preferably is a compound that does not fall under the category of PFAS. If component (A) contains other components other than component (A1), it is preferable that the other components are also compounds that do not fall under the category of PFAS. 【0042】<Constituent Unit (a1)> Constituent unit (a1) is a constituent unit that includes an acid-degradable group whose polarity increases upon the action of an acid. An "acid-degradable group" is a group that has acid-degradability, in which at least some of the bonds in the structure of the acid-degradable group can be cleaved upon the action of an acid. Examples of acid-degradable groups whose polarity increases upon the action of an acid include groups that decompose upon the action of an acid to produce polar groups. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfo groups (-SO ３ Examples include H), etc. Among these, polar groups containing -OH in their structure (hereinafter sometimes referred to as "OH-containing polar groups") are preferred, carboxyl groups or hydroxyl groups are more preferred, and carboxyl groups are particularly preferred. More specifically as acid-degradable groups, examples include groups in which the polar group is protected by an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group). Here, "acid-dissociable group" refers to both (i) a group having acid-dissociability in which the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) a group in which, after some of the bonds are cleaved by the action of an acid, a decarboxylation reaction occurs, and the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-degradable group must be less polar than the polar group generated by its dissociation. This ensures that when the acid-dissociable group dissociates due to the action of acid, a polar group with higher polarity is generated, increasing the polarity. As a result, the overall polarity of component (A1) increases. This increase in polarity relatively alters the solubility in the developer; solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer. 【0043】The constituent unit (a1) preferably contains an acid-degradable group having an alicyclic hydrocarbon group, and more preferably contains an acid-degradable group having a monocyclic alicyclic hydrocarbon group. When the acid-degradable group (acid-dissociable group) in constituent unit (a1) has an alicyclic hydrocarbon group, its bulkiness is appropriate, allowing for appropriate control of acid diffusion and solubility in the developer, thereby reducing roughness when forming the resist pattern. Examples of acid-dissociable groups in constituent unit (a1) include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resists. Specifically, examples of acid-dissociable groups proposed for base resins used in chemically amplified resist compositions include "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "tertiary alkyloxycarbonyl acid-dissociable groups." 【0044】 Acetal-type acid-dissociating group: Among the polar groups, an example of an acid-dissociating group that protects a carboxyl group or a hydroxyl group is the acid-dissociating group represented by the following formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociating group"). 【0045】 【0046】 [In the formula, Ra' １ , Ra' ２ Ra' is a hydrogen atom or an alkyl group. ３ is a hydrocarbon group, Ra' ３ Ra' １ , Ra' ２ It may combine with any of the following to form a ring. 【0047】 In formula (a1-r-1), Ra' １ and Ra' ２ Preferably, at least one of them is a hydrogen atom, and more preferably, both are hydrogen atoms. 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. 【0048】 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. 【0049】 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. 【0050】 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. 【0051】 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. 【0052】 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. 【0053】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. 【0054】 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. 【0055】 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. 【0056】 【0057】 [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. 【0058】 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. 【0059】 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). 【0060】 【0061】 [In formula (a1-r2-1), Ra ０３１ This represents an alkyl group, Yab ０ Xab represents a carbon atom. ０ Yab ０represents a group that forms an alicyclic hydrocarbon group together with, and some or all of the hydrogen atoms of 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 of this cyclic hydrocarbon group may be substituted. Ra １０１ ~Ra １０３ are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Ra １０１ ~Ra １０３ Two or more of them may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra １０４ is an aromatic hydrocarbon group that may have a substituent. In formula (a1-r2-4), Ra' １２ and Ra' １３ are each independently a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra' １４ is a hydrocarbon group that may have a substituent. * represents a bond. ] 【0062】 In the above formula (a1-r2-1), Ra ０３１ is preferably a linear alkyl group, and a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group, is preferred. 【0063】 Ra<( ０３１ As the linear alkyl group in, it has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. As the branched alkyl group in Ra ０３１ the same ones as those of the above Ra' ４ can be mentioned. 【0064】 Ra ０３１The alkyl group in [description] may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms (such as methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group. Here, examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O) ２ -, -S(=O) ２ -O- and the like can be mentioned. 【0065】 In formula (a1-r2-1), Xab ０ and Yab ０ together form an alicyclic hydrocarbon group which is preferably a group obtained by further removing one or more hydrogen atoms from the group mentioned as the monocyclic group or polycyclic group of Ra' ３ in the above formula (a1-r-1), which is an aliphatic hydrocarbon group (alicyclic hydrocarbon group). Among them, the alicyclic hydrocarbon group is more preferably a monocyclic alicyclic hydrocarbon group, and more preferably a group obtained by removing two or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. 【0066】 In formula (a1-r2-2), examples of the cyclic hydrocarbon group formed by Xa and Ya together include a group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) of Ra' ４ in the above formula (a1-r-2). The cyclic hydrocarbon group formed by Xa and Ya together may have a substituent. Examples of this substituent include the same ones as those that the cyclic hydrocarbon group of Ra' ４ in the above may have. In formula (a1-r2-2), Ra １０１ ~Ra １０３Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. １０１ ~Ra １０３ 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, cyclononyl, and cyclododecyl groups; bicyclo[2.2.2]octanyl, 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. １０１ ~Ra １０３ Of these, from the viewpoint of ease of synthesis, hydrogen atoms and monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred, and among these, hydrogen atoms, methyl groups, and ethyl groups are more preferred, with hydrogen atoms being particularly preferred. 【0067】 The above Ra １０１ ~Ra １０３ Examples of substituents on a chain-like saturated hydrocarbon group or an aliphatic cyclic saturated hydrocarbon group represented by the above Ra ０５ Similar bases can be cited. 【0068】 Ra １０１ ~Ra １０３ Groups containing a carbon-carbon double bond formed by two or more of these groups bonding to each other to form a cyclic structure include, for example, cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylideneethenyl group, and cyclohexyllideneethenyl group. Among these, from the viewpoint of ease of synthesis, cyclopentenyl group, cyclohexenyl group, and cyclopentylideneethenyl group are preferred as the carbon-carbon double bond group. 【0069】In the formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is a group obtained by further removing one or more hydrogen atoms from the groups exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of Ra' in the above formula (a1-r-2). ４ It is preferably a group obtained by further removing one or more hydrogen atoms from the groups exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of ４ . In the formula (a1-r2-3), Ra １０４ Examples of the aromatic hydrocarbon group in Ra １０４ include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra １０４ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably a group obtained by removing one or more hydrogen atoms from benzene, and most preferably a group obtained by removing one or more hydrogen atoms from benzene. 【0070】 Examples of the substituent that Ra １０４ in the formula (a1-r2-3) may have include, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkyloxycarbonyl group, and the like. 【0071】 In the formula (a1-r2-4), Ra' １２ and Ra' １３ are each independently a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms in Ra' １２ and Ra' １３ are the same as those of the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms in Ra １０１ to Ra １０３ above. Some or all of the hydrogen atoms of this chain-like saturated hydrocarbon group may be substituted. Ra' １２ and Ra' １３ are more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The above Ra' １２ and Ra'１３ When the chain-like saturated hydrocarbon group represented by is substituted, examples of the substituent include Ra as described above ０５ and the same groups as those described above can be mentioned. 【0072】 In formula (a1-r2-4), Ra' １４ is a hydrocarbon group which may have a substituent. The hydrocarbon group in Ra' １４ includes a linear or branched alkyl group, or a cyclic hydrocarbon group. 【0073】 Ra' １４ The linear alkyl group in 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 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. 【0074】 Ra' １４ The branched alkyl group in preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples of the branched alkyl group in Ra' １４ include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group, etc., and is preferably an iso-propyl group. 【0075】 Ra' １４When 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[5.2.1.0 ２，６ Examples include decane and tetracyclododecane. 【0076】 Ra' １４ As for aromatic hydrocarbon groups in this context, Ra １０４ Examples include those similar to aromatic hydrocarbon groups in [the text]. Among them, Ra' １４ The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed, more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed, even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed, particularly preferably a group from naphthalene or anthracene with one or more hydrogen atoms removed, and most preferably a group from naphthalene with one or more hydrogen atoms removed. １４ A substituent that may be present is Ra １０４ Examples of substituents that may be present include those similar to those that the molecule may have. 【0077】 Ra' in equation (a1-r2-4) １４ When is a naphthyl group, the position where it bonds to the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. １４ If is an anthyl group, the position of the bond with the tertiary carbon atom in formula (a1-r2-4) may be position 1, 2, or 9 of the anthyl group. 【0078】Specific examples of the group represented by the above formula (a1-r2-1) are given below. 【0079】 【0080】 【0081】 【0082】 Specific examples of the group represented by the above formula (a1-r2-2) are given below. 【0083】 【0084】 【0085】 【0086】 Specific examples of the group represented by the above formula (a1-r2-3) are given below. 【0087】 【0088】 Specific examples of the group represented by the above formula (a1-r2-4) are given below. 【0089】 【0090】 ・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). 【0091】 【0092】 [In the formula, Ra' ７ ~Ra' ９ Each of these represents an alkyl group. 【0093】 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. 【0094】As the acid dissociable group, among the groups represented by the above general formulas (a1-r2-1) to (a1-r2-4), the group represented by the above general formula (a1-r2-1) or (a1-r2-4) is preferable. 【0095】 As the structural unit (a1), specifically, the structural unit represented by the following general formula (a1-1) can be mentioned. 【0096】 (Structural unit (a1) represented by general formula (a1-1)) In the resist composition according to an embodiment of the present invention, the base material component (A) preferably contains a polymer compound (A1) having a structural unit (a1) represented by the following general formula (a1-1). 【0097】 【0098】 [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va １ is a divalent hydrocarbon group which may have an ether bond. n ａ１ is an integer of 0 to 2. Ra １ represents an acid dissociable group. ] 【0099】 In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, etc. As R, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable. 【0100】 In the above formula (a1-1), Va １ The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Va １The 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. 【0101】 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-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. 【0102】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. 【0103】 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, examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. 【0104】 In the above 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). 【0105】 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. 【0106】 The above formula (a1-1) is preferably the following formula (a1-2). 【0107】 【0108】 (In general formula (a1-2), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogenated group 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.) 【0109】 In general formula (a1-2), R, Va ３ R, Va in equation (a1-1) １ These are similar in each case. 【0110】 In general formula (a1-2), na ３ is an integer between 0 and 2, preferably 0 or 1, and more preferably 0. 【0111】 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. 【0112】 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. 【0113】 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. 【0114】 【0115】 【0116】 【0117】 【0118】 【0119】 【0120】 【0121】 【0122】 【0123】 【0124】 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. 【0125】 <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. 【0126】 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). 【0127】 【0128】 [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. 【0129】 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. Ra' ２１ Specifically, the alkoxy group in is 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 fluorine, 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. 【0130】 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. 【0131】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 that may or may not be substituted with a fluorinated alkyl group that does not have a fluorine atom or a perfluoroalkyl skeleton and a difluoromethyl group; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and 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. 【0132】 Examples of lactone-containing cyclic groups in R'' include those similar to the groups represented by formulas (a²-r-1) to (a²-r-7) 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 formulas (ax³-r-1) to (ax³-r-3) above. Examples of -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 formulas (a5-r-1) to (a5-r-4), respectively. 【0133】 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. 【0134】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. 【0135】 The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-7). 【0136】 【0137】 【0138】 "-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 formulas (a5-r-1) to (a5-r-4). 【0139】 【0140】 [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. 【0141】 In the above 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 the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group, the Ra' in the above formulas (a2-r-1) to (a2-r-7) are respectively. ２１ The same examples as those mentioned in the explanation are given below. Specific examples of the groups represented by formulas (a5-r-1) to (a5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group. 【0142】 【0143】 【0144】 【0145】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). 【0146】 【0147】 [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. 【0148】 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. 【0149】 【0150】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). 【0151】 【0152】 [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. 【0153】 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. 【0154】 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. 【0155】 • 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. 【0156】 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. 【0157】 ...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. 【0158】 The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include fluorinated alkyl groups that do not have a fluorine atom, a perfluoroalkyl skeleton having 1 to 5 carbon atoms substituted with a fluorine atom, or a difluoromethyl group, and carbonyl groups. 【0159】...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. 【0160】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 has 1 to 5 carbon atoms, and more preferably, it is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Preferably, the alkoxy group has 1 to 5 carbon atoms, and more preferably, it is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group, with methoxy and ethoxy groups being even more preferred. 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 (provided that neither a perfluoroalkyl skeleton nor a difluoromethyl group is present). A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with substituents containing heteroatoms. Examples of such substituents containing heteroatoms include -O-, -C(=O)-O-, -S-, and -S(=O). ２ -, -S (=O) ２ -O- is preferred. 【0161】 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. 【0162】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. 【0163】 • 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. 【0164】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. 【0165】 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. 【0166】 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. 【0167】 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 carbonate-containing cyclic groups include the groups represented by formulas (a2-r-1) to (a2-r-7), the groups represented by formulas (a5-r-1) to (a5-r-4), and the groups represented by formulas (ax3-r-1) to (ax3-r-3), respectively. 【0168】 In the formula (a2-1), Ra ２１ Among the above, lactone-containing cyclic groups or -SO ２ - A cyclic group is preferred, the group represented by formula (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1) is more preferred, and the group represented by formula (a2-r-1) or (a2-r-2) is 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. 【0169】 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. 【0170】 <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. 【0171】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. 【0172】 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 5,000 or more, more preferably 5,500 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. 【0173】 In the resist composition according to the embodiment of the present invention, the Mw of component (A1) is preferably 5,500 to 30,000, more preferably 6,000 to 20,000, and even more preferably 6,500 to 12,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance, LWR (linewise roughness), and LER. 【0174】 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. 【0175】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. 【0176】 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. 【0177】 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. 【0178】≪Acid Generating Agent Component (B)≫ In addition to the above-described 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, 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 a compound consisting of an onium salt, and more preferably contains a compound (B1) represented by the following general formula (b-01) (hereinafter sometimes referred to as "component (B1)"). 【0179】 【0180】 [In general formula (b-01), Rf ０１ and Rf ０２ Each of these independently represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group, and Rf ０１ , Rf ０２ At least one of the groups contains a fluorine atom. X represents a divalent linking group. Y represents an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. m represents an integer of 1 or more, M ｍ＋ This represents an m-valent organic cation. 【0181】 [Anion Department (Y-X-C (Rf ０１ ) (Rf ０２ ) - SO ３ － )] In the general formula (b-01), Y-X-C(Rf ０１ ) (Rf ０２ ) - SO ３ －This is a counter anion. The counter anion is not particularly limited, and those proposed as the anionic portion of acid generators for chemically amplified resist compositions can be used. 【0182】 In general formula (b-01), Rf ０１ and Rf ０２ Each of these independently represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. 【0183】 Rf ０１ and Rf ０２ The fluorinated alkyl groups represented by may be linear or cyclic, and are preferably linear or branched. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. 【0184】 Rf ０１ and Rf ０２ Fluorinated alkyl groups represented by include, specifically, groups in which some or all of the hydrogen atoms constituting a linear alkyl group such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group are substituted with fluorine atoms, and groups in which some or all of the hydrogen atoms constituting a branched alkyl group such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, and a 3-methylbutyl group are substituted with fluorine atoms. ０１ and Rf ０２ The fluorinated alkyl groups represented by may each independently contain atoms other than fluorine, carbon, and hydrogen atoms, such as oxygen, sulfur, nitrogen, etc. In particular, Rf ０１ and Rf ０２ The fluorinated alkyl group represented by is preferably a group in which some or all of the hydrogen atoms constituting a linear alkyl group are substituted with fluorine atoms, and preferably a group in which all of the hydrogen atoms constituting a linear alkyl group are substituted with fluorine atoms (perfluoroalkyl group). 【0185】 In general formula (b-01), Rf ０１ and Rf ０２Preferably, each of these represents a fluorine atom. 【0186】 In general formula (b-01), X represents a divalent linking group, and is preferably a divalent linking group containing an oxygen atom. If X is a divalent linking group containing an oxygen atom, X may contain atoms other than oxygen. Examples of atoms other than oxygen include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, and so on. 【0187】 Examples of divalent linking groups containing an oxygen atom include non-hydrocarbon oxygen-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-O-C(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-O-C(=O)-O-); and combinations of these non-hydrocarbon oxygen-containing linking groups with alkylene groups. Further additions to these combinations include sulfonyl groups (-SO ２ A -) may be linked. Examples of such divalent linking groups containing an oxygen atom include the linking groups represented by the following general formulas (y-al-1) to (y-al-7). Note that in the following general formulas (y-al-1) to (y-al-7), the Y in the above general formula (b-01) is bonded to V' in the following general formulas (y-al-1) to (y-al-7). １０１ That is the case. 【0188】 【0189】 [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.] 【0190】 V' １０２ The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms. 【0191】 V ’１０１ and V' １０２The 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 [-CH ２ 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. 【0192】 X is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, and more preferably a linking group represented by any of the above formulas (y-al-1) to (y-al-5). 【0193】 In general formula (b-01), Y represents a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. Cyclic group which may have substituents: The cyclic group which may have substituents in Y is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. 【0194】The aromatic hydrocarbon group in Y 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. Specific examples of aromatic rings in the aromatic hydrocarbon group in Y 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. Specific examples of aromatic hydrocarbon groups in Y include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, and 2-naphthylethyl groups). 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. 【0195】The cyclic aliphatic hydrocarbon group in Y is an aliphatic hydrocarbon group that contains a ring in its structure. The cyclic aliphatic hydrocarbon group in Y preferably has 3 to 50 carbon atoms, preferably 4 to 45 carbon atoms, and more preferably 5 to 40 carbon atoms. 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. As a monocyclic alicyclic hydrocarbon group, a group from which one or more hydrogen atoms have been removed from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, a group having 7 to 30 carbon atoms is preferred. Among these, the polycycloalkane is adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ Polycycloalkanes 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. 【0196】 In particular, as the cyclic aliphatic hydrocarbon group in Y, a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane is preferred, a group obtained by removing one hydrogen atom from a polycycloalkane is more preferred, an adamantyl group and a norbornyl group are even more preferred, and an adamantyl group is particularly preferred. 【0197】 The following are some preferred examples of cyclic aliphatic hydrocarbon groups in Y. * indicates a bond. 【0198】 【0199】The linear aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. 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(CH３ )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. 【0200】 Furthermore, the cyclic hydrocarbon group in Y 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), respectively. 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 a bond attached to X in the general formula (b-01). 【0201】 【0202】Examples of substituents on the cyclic group of Y include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. Preferred alkyl groups as substituents are alkyl groups having 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferred alkoxy groups as substituents are alkoxy groups having 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 having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. Carbonyl groups as substituents include methylene groups (-CH) that constitute the cyclic hydrocarbon group. ２ It is a substituting group for -). 【0203】 The cyclic hydrocarbon group in Y 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. Specific examples of the fused ring group in Y include the groups represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents a bond that connects to X in the general formula (b-01). 【0204】 【0205】Examples of substituents that the fused ring group in Y may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups. The alkyl groups, alkoxy groups, halogen atoms, and alkyl halides used as substituents for the fused ring group are the same as those listed above as substituents for the cyclic group in Y. Examples of aromatic hydrocarbon groups used as substituents for the fused ring group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), groups in which one hydrogen atom of the aromatic ring is replaced by an alkylene group (for example, aryl alkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, and 2-naphthylethyl groups), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups as substituents on the aforementioned fused ring group include monocycloalkanes such as cyclopentane and cyclohexane from which one hydrogen atom has been removed; 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 formulas (a2-r-1) to (a2-r-7); -SO groups represented by formulas (a5-r-1) to (a5-r-4) ２ - Containing cyclic groups; examples include heterocyclic groups represented by formulas (r-hr-7) to (r-hr-16), respectively. 【0206】 The cyclic hydrocarbon group in Y 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. ２ The -) 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. 【0207】 Optionally substituted linear alkyl groups: The linear alkyl group in Y 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. Specific examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, and docosyl groups. Branched alkyl groups preferably have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Examples of branched alkyl groups include, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group. 【0208】 Chain-like alkenyl groups which may have substituents: The chain-like alkenyl groups in Y may be linear or branched, and preferably have 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 above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred. 【0209】Examples of substituents on the chain-like alkyl or alkenyl group in Y include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in Y. 【0210】 Among the above, Y is preferably a chain-like alkyl group which may have substituents, or an alicyclic hydrocarbon group which may have substituents, 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 above formulas (a5-r-1) to (a5-r-4). 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 above formulas (a5-r-1) to (a5-r-4). ２ -The contained cyclic group is more preferably an adamantyl group which may have a hydroxyl group or -SO represented by the formula (a5-r-1) above. ２ - A cyclic group is particularly preferred. 【0211】 X is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably a linking group represented by any of the above formulas (y-al-1) to (y-al-5), and even more preferably a linking group represented by the above formulas (y-al-1) or (y-al-3). 【0212】 Specific examples of the anion part represented by the general formula (b-01) include, for example, when X is a divalent linking group containing an oxygen atom, the anions represented by the following formulas (an-1) to (an-3) can be cited. 【0213】 【0214】 [In the formula, R” １０１ R'' is an optionally substituted aliphatic cyclic group, a monovalent heterocyclic group represented by any of the above chemical formulas (r-hr-1) to (r-hr-16), a fused cyclic group represented by the formula (r-br-1) or (r-br-2), or an optionally substituted linear alkyl group. １０２This 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 any of the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or a -SO represented by any of the general formulas (a5-r-1) to (a5-r-4). ２ - Contains a cyclic group. R'' １０３ This is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted linear alkenyl group. １０１ This is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. １０２ [wherein 'v' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; where 'v' is an independent integer from 0 to 3, where 'q' is an independent integer from 0 to 20, and where 'n' is 0 or 1.] 【0215】 R" １０１ , R” １０２ and R” １０３ The aliphatic cyclic group which may have substituents is preferably the group exemplified as the cyclic aliphatic hydrocarbon group in Y in the general formula (b-01). Examples of substituents are the same as substituents which may substitute for the cyclic aliphatic hydrocarbon group in Y in the general formula (b-01). 【0216】 R" １０３ The aromatic cyclic group in which substituents may be present is preferably one of the groups exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group in Y in the general formula (b-01). Examples of substituents include those similar to those that may substitute for the aromatic hydrocarbon group in Y in the general formula (b-01). 【0217】 R" １０１ The optionally substituted linear alkyl group in R is preferably one of the groups exemplified as the linear alkyl group in Y in the general formula (b-01). １０３The substituted linear alkenyl group in is preferably one of the groups exemplified as the linear alkenyl group in Y in the general formula (b-01). 【0218】 Among the anions in the above general formula (b-01), an anion represented by any of the above general formulas (an-1) to (an-3) is more preferred, an anion represented by either general formula (an-1) or (an-2) is even more preferred, and an anion represented by general formula (an-1) is particularly preferred. 【0219】 Specific examples of anions represented by the general formula (b-01) are shown below, but are not limited to these. 【0220】 【0221】 【0222】 [Cation part: (M ｍ＋ ) １／ｍ ] In the general formula (b-01), 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. 【0223】 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. 【0224】 【0225】 [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-. 【0226】 R ２０１ ~R ２０７ Examples 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. 【0227】 【0228】 [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. 【0229】 R' ２０１The 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. 【0230】 R' ２０１ The 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. 【0231】 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. 【0232】 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. 【0233】 R' ２０１ Substituents 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. 【0234】 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. 【0235】 R ２０８ ~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. 【0236】 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 -SO２ - 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: 【0237】 The cation represented by formula (ca-1) is preferably the cation represented by the following formula (b-2). 【0238】 【0239】 [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). 【0240】 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. 【0241】 Specific examples of preferred cations represented by formula (ca-1) include cations represented by any of the following formulas (ca-1-1) to (ca-1-67). 【0242】 【0243】 ​ 【0244】 【0245】 [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.] 【0246】 【0247】 [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. 【0248】 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). 【0249】 【0250】 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. 【0251】 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. 【0252】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. 【0253】 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. 【0254】 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. 【0255】≪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, by being used as a hydrophobic resin separate from component (A), segregation ability to the upper layer of the film by fluorine atoms and water repellency are obtained. Furthermore, by giving component (F) a base decomposition structure, better lithography characteristics and defect characteristics can be achieved simultaneously in the TC-Less process. Component (F) consists of a constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - A polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0256】 In the resist composition of this embodiment, component (F1) comprises a structural unit (f1) having a fluorine atom in an aryl group, and a lactone-containing cyclic group, -SO ２ -It is a copolymer with a constituent unit (fa2) containing a lactone-containing cyclic group or a carbonate-containing cyclic group. ２ - Due to the high affinity for developer provided by the constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, it is considered that the precipitation of components such as base resin dissolved in the alkaline developer and the resulting occurrence of bridge defects can be effectively suppressed, especially in the alkaline development process when rinsing with water after development. 【0257】 As described above, the resist composition in this embodiment comprises, as component (F), a constituent unit (f1) represented by the following general formula (f1-1), and a lactone-containing cyclic group, -SO ２ -By including a polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and by not including any compounds having a perfluoroalkyl skeleton or difluoromethyl groups in the polymer compound (F1), it is possible to reduce the environmental burden and achieve both the suppression of WMD and the suppression of bridge defects necessary in the TC-Less process. 【0258】 <Constituent Unit (f1)> The constituent unit (f1) represented by 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. Furthermore, Rf in general formula (f1-1) １ Since the constituent 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 by abstraction of hydrogen fluoride (HF) caused by basic compounds occurs more readily, and sufficient basic decomposition properties are obtained. As a result, segregation of the fluorine additive component (F) on the resist pattern surface is eliminated, and it is presumed that a resist pattern with a good shape can be formed. Furthermore, since the constituent unit (f1) does not contain either a perfluoroalkyl skeleton or a difluoromethyl group, the environmental burden can be reduced. 【0259】 【0260】 [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.] 【0261】 As stated above, the general formula (f1-1) does not contain either a perfluoroalkyl skeleton or a difluoromethyl group. 【0262】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 fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. For R, hydrogen atoms and alkyl groups having 1 to 5 carbon atoms are preferred, and due to their industrial availability, hydrogen atoms or methyl groups are most preferred. 【0263】 nf ２ It is 1 or 2, and is preferably 1. 【0264】 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 Y２１ 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. 【0265】 Rf １ Examples 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 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred. 【0266】 The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred. 【0267】 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. 【0268】 Rf １The 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. 【0269】 Rf １ When 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 １Specifically, 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. 【0270】 Rf １ Examples of substituents that the cyclic hydrocarbon group in the compound may have include groups represented by 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. 【0271】 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. 【0272】 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. 【0273】 Specific examples of constituent units (f1) are given below. In the following formula, R a This represents a hydrogen atom or a methyl group. 【0274】 【0275】 【0276】 【0277】 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 high water-repellent effect and the WMD improvement effect 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. In addition, the occurrence of bridge defects is suppressed and lithography characteristics are improved. 【0278】 <Constituent Unit (fa2)> The polymer compound (F1) is composed of the constituent unit (f1) represented by the general formula (f1-1) above, and also contains a lactone-containing cyclic group, -SO ２ - Containing a constituent unit (fa2) that includes a lactone-containing cyclic group or a carbonate-containing cyclic group. 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 - and carbonate-containing cyclic groups. However, lactone-containing cyclic groups and -SO contained in polymer compounds (F1) are not included. ２ - Constituent units (fa2) containing a cyclic group or a carbonate-containing cyclic group do not include any perfluoroalkyl skeleton or difluoromethyl group. 【0279】 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). 【0280】 【0281】 [In general formula (fa-2), R ０２Vfa 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). 【0282】 【0283】 [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. 【0284】 【0285】 [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. 【0286】 【0287】 [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. 【0288】 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. 【0289】 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'. 【0290】 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''. 【0291】 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''. 【0292】 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. 【0293】 Vfa ０２This 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. 【0294】 n ｆ０２ The value is preferably 0 or 1, and more preferably 0. 【0295】 Rfa ０２ Preferably, the lactone-containing cyclic group is represented by any of the formulas (a2-r-1) to (a2-r-7), and more preferably, the group represented by formula (a2-r-1) or (a2-r-2). 【0296】 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 effect of suppressing bridge defects is improved. Also, by setting it to be below the upper limit, volatility is improved. 【0297】 <Other constituent units> The polymer compound (F1) may have other constituent units other than the above-mentioned constituent unit (f1) and the above-mentioned constituent unit (fa2) (however, excluding the constituent unit (f1), the constituent unit (fa2), those having a perfluoroalkyl skeleton, and those having a difluoromethyl group). 【0298】The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If 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. 【0299】 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. 【0300】 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). 【0301】 <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). 【0302】It is preferable that components (D) and (S) do not contain compounds corresponding to PFAS. It is preferable that components (D) and (S) do not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. Furthermore, it is even more preferable that they do not contain fluorine atoms. 【0303】 ≪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. 【0304】 It is preferable that component (D) does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group. It is preferable that 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, it is preferable that component (D) does not contain any compounds corresponding to PFAS. Furthermore, it is preferable that component (D) does not contain any fluorine atoms. 【0305】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 decomposes upon exposure and loses 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. 【0306】 【0307】 [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. 【0308】 {(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 １Preferred 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, fluorine atoms, fluorinated alkyl 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). 【0309】 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. 【0310】 When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. 【0311】The following are preferred specific examples of the anion portion of component (d1-1). 【0312】 【0313】 - 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 the cations represented by any of the formulas (ca-1-1) to (ca-1-67) being even more preferred. The (d1-1) component may be used alone or in combination of two or more types. 【0314】 {(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). １Examples 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. 【0315】 The following are preferred specific examples of the anion portion of component (d1-2). 【0316】 【0317】 - 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. 【0318】 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. 【0319】 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. 【0320】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 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), and aromatic amines are more preferred. 【0321】 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. 【0322】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. 【0323】 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. 【0324】 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. 【0325】 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. 【0326】≪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 "(S) component"). The (S) component can be any component that can dissolve each component used to form a homogeneous solution, and any component can be appropriately selected from those conventionally known as solvents for chemically amplified resist compositions. In the resist composition of this embodiment, the (S) component 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. 【0327】 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. 【0328】 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. 【0329】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. 【0330】 The resist composition preferably does not contain any compounds having a perfluoroalkyl skeleton or any compounds having a difluoromethyl group, and preferably does not contain any compounds corresponding to PFAS. The components contained in the resist composition preferably do not contain any compounds having a trifluoromethyl group, any compounds having a difluoromethyl group, and any compounds having a difluoromethylene group. Furthermore, it is more preferable that the resist composition does not contain any fluorine atoms. 【0331】 The resist composition of this embodiment described above comprises a base component (A) whose solubility in a developer solution changes due to the action of an acid, an acid generating agent component (B) that generates acid upon exposure, and a constituent unit (f1) represented by the above general formula (f1-1) and a lactone-containing cyclic group, -SO ２ - Contains a polymer compound (F1) having a constituent unit (f2) containing a cyclic group or a carbonate-containing cyclic group, and a fluorine-containing additive component (F). Component (F) contains Rf in the constituent unit (f1). １ Because it represents a specific group and is bulky, sufficient base decomposition properties are obtained. In addition, because it contains an aryl group having one or more fluorine atoms, it is a highly hydrophobic structural unit, which enhances the hydrophobicity of the resist film. Furthermore, component (F) is a lactone-containing cyclic group, -SO ２ - Because it contains a constituent unit (fa2) that includes a cyclic group containing a carbonate-containing cyclic group, it has excellent affinity for the developer. For this reason, it is presumed that the resist composition of this embodiment, when used with the above-mentioned component (F), can achieve both better lithography and defect characteristics in the TC-Less process due to the hydrophobicity of the resist film and hydrophilization by base decomposition during development. 【0332】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. 【0333】 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. 【0334】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.). 【0335】 The resist composition of this embodiment is preferably such that the measured value of the receding angle (receding angle 1) in the dynamic contact angle of a resist film with a thickness of 80 nm, prepared by applying the resist composition onto a 12-inch silicon wafer using a spinner, pre-baking it on a hot plate at 100°C for 60 seconds, and drying it, is 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 is preferable because it indicates sufficient hydrophobicity of the resist film and superior lithography characteristics. It is also preferable because it allows for faster scanning speeds in immersion exposure. 【0336】 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, and even more preferably 7° or more. If the Δcontact angle is 7° or more, the effect of suppressing bridge defects is improved. Also, the Δcontact angle is preferably 20° or less, more preferably 17° or less, and even more preferably 15° or less. If the Δcontact angle is 20° or less, the affinity to the developer is increased, and the stability over time is excellent. 【0337】 (Formula 1): Δcontact angle = receding angle 1 - receding angle 2 【0338】The Δ contact angle is the difference between the receding angle 1 and the receding angle 2, and serves as an indicator of defect characteristics. 【0339】 (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. 【0340】 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. 【0341】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. 【0342】 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. 【0343】 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. 【0344】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. 【0345】 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. 【0346】 Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile. 【0347】 Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicone-based surfactants can be used. 【0348】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). 【0349】 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). 【0350】 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). 【0351】 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. 【0352】[Polymer Compound] The polymer compound according to the third embodiment of the present invention comprises a constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - It contains a constituent unit (fa2) that includes a cyclic group containing a carbonate-containing cyclic group, and does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0353】 【0354】 [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.] 【0355】 The polymer compound (F1) according to the third embodiment of the present invention is the same as described above for the polymer compound (F1) in the resist composition according to the embodiments of the present invention, and the preferred polymer compound is also the same. 【0356】 Such polymer compound (F1) is useful as a fluorine additive component (F) for resist compositions. By using such polymer compound (F1) in a chemically amplified resist composition, it is possible to form a resist pattern that reduces environmental impact and has excellent lithographic properties during resist pattern formation. 【0357】 [Fluorine additive component] The fluorine additive component according to the fourth embodiment of the present invention comprises a constituent unit (f1) represented by the general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - Contains a polymer compound having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and does not contain any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. 【0358】 【0359】 [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.] 【0360】 The polymer compound (F1) in the fluorine additive component (F) according to the fourth embodiment of the present invention is the same as described above for the polymer compound (F1) according to the embodiments of the present invention, and the preferred polymer compound is also the same. 【0361】 Such fluorine additive component (F) is the same as described above for the fluorine additive component (F) for the resist composition according to the embodiments of the present invention, and preferred components are also the same. By using such fluorine additive component (F) in a chemically amplified resist composition, it is possible to form a resist pattern that reduces environmental impact and achieves both the suppression of WMD necessary in the TC-Less process and the suppression of bridge defects. 【0362】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 【0363】 <Examples of compound synthesis> [Synthesis Example 1: Synthesis of compound (f)-1] Compound (f)-1 was synthesized using the following synthesis method. 【0364】 【0365】 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%). 【0366】 NMR measurements were performed on the obtained compound (f)-1, and its structure was identified based on the following analytical results. 【0367】 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). 【0368】 [Synthesis Example 2: Synthesis of Compound (f)-2] Compound (f)-2 was synthesized using the following synthesis method. 【0369】 【0370】 Compound (f)-4 was obtained in the same manner as in Synthesis Example 1, except that compound (X1) was replaced with compound (X2) in equimolar amounts. 【0371】 The obtained compound (f)-2 was subjected to NMR measurement, and its structure was identified based on the following analytical results. 【0372】 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). 【0373】 [Synthesis Example 3: Synthesis of Compound (f)-3] 【0374】 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. 【0375】 The obtained compound (f)-3 was subjected to NMR measurement, and its structure was identified based on the following analytical results. 【0376】 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). 【0377】 [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. 【0378】 For the obtained polymer compound (F)-1, the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by GPC measurement, was 25,000, 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. 【0379】 ​[Synthesis of Polymer Compound (F)-2 to Polymer Compound (F)-5, Polymer Compound (F2)-1 to Polymer Compound (F2)-4] Polymer Compound (F)-2 to Polymer Compound (F)-5 and Polymer Compound (F2)-1 to Polymer Compound (F2)-4 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. 【0380】 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. 【0381】 【0382】 【0383】 【0384】 <Preparation of Resist Compositions> (Examples 1-10, Comparative Examples 1-4) The resist compositions for each example were prepared by mixing and dissolving the components shown in Table 1. 【0385】 【0386】 In Table 1, each abbreviation has the following meaning. The unit of composition is parts by mass. 【0387】 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. 【0388】 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. 【0389】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. 【0390】 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. 【0391】 【0392】 B-1 to B-2: Acid generators consisting of the following compounds (B)-1 to (B)-2, respectively. 【0393】 【0394】 D-1 to D-3: Acid diffusion control agents consisting of compounds represented by the following chemical formulas (D)-1 to (D)-3. 【0395】 【0396】 F-1 to F-5, F2-1 to F2-4: Fluorine additive components consisting of compounds represented by (F)-1 to (F)-5 and (F2)-1 to (F2)-4 above. 【0397】 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. 【0398】 <Formation of Resist Film> The resist compositions of Examples 1 to 10 and Comparative Examples 1 to 4 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. 【0399】 <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. 【0400】 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 【0401】 <Evaluation of Bridge 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 10 and Comparative Examples 1 to 4 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. 【0402】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 each example, 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. The number of bridge defects per silicon wafer was measured and evaluated according to the following evaluation criteria. 【0403】 (Evaluation Criteria) ◎: Number of bridge defects is 0 to 20 ○: Number of bridge defects is 21 to 50 ×: Number of bridge defects is more than 50 【0404】 <WMD Evaluation> For the LS patterns described above, the number of WMDs per silicon wafer was measured using the same KLA2905 and evaluated according to the following evaluation criteria. The WMDs were limited to those with a particle size of 1 μm or larger. 【0405】 (Evaluation Criteria) ◎: 0 bridge defects ○: 1 to 10 bridge defects ×: More than 10 bridge defects 【0406】 <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 a difluoromethyl group. NG (Poor): The (F) component contains either a compound having a perfluoroalkyl skeleton or a compound having a difluoromethyl group. 【0407】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 resists, 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 reduces environmental impact and achieves both the suppression of WMD necessary in the TC-Less process and the suppression of bridge defects. 【0408】 According to the present invention, it is possible to provide a resist composition and a resist pattern formation method that can form a resist pattern that reduces environmental impact and achieves both the suppression of WMD and the suppression of bridge defects necessary in the TC-Less process. 【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. 2024-213887 filed on 6 December 2024, the contents of which are incorporated herein by reference.

Claims

1. 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 constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ A resist composition comprising a polymer compound (F1) having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.] 2. The structural unit (fa2) containing a lactone-containing cyclic group, a -SO ２ -containing cyclic group or a carbonate-containing cyclic group is the resist composition according to claim 1, which contains a structural unit (fa-2) represented by the following general formula (fa-2). [In the 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 is a lactone-containing cyclic group represented by any one of the following formulas (a2-r-1) to (a2-r-7), a -SO ２ -containing cyclic group represented by any one of the following formulas (a5-r-1) to (a5-r-4), or a carbonate-containing cyclic group represented by any one of the following formulas (ax3-r-1) to (ax3-r-3).] [In the formulas (a2-r-1) to (a2-r-7), Ra' ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ２ -containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1. * indicates a bond.] [In the formulas (a5-r-1) to (a5-r-4), Ra' ５１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -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.

3. 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 by exposure from the acid generating agent component (B).

4. 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.

5. A constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - A polymer compound having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.] 6. A constituent unit (f1) represented by the following general formula (f1-1), a lactone-containing cyclic group, and -SO ２ - A fluorine additive component containing a polymer compound having a constituent unit (fa2) containing a cyclic group or a carbonate-containing cyclic group, and not containing any compounds having a perfluoroalkyl skeleton or compounds having a difluoromethyl group. [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. nf ２ It is either 1 or 2. Lf １ 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 １ [ is an integer greater than or equal to 1.]

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