Resist composition and method for forming resist pattern

Abstract

Provided is a resist composition which generates an acid upon exposure to light, and the solubility of which in a developer solution is changed by the action of the acid. The present invention contains: a resin component (A1), the solubility of which in a developer solution is changed by the action of an acid; an acid generator component (B) which generates an acid upon exposure to light; and a surfactant (G01). The acid generator component (B) and the surfactant (G01) do not contain a difluoromethyl group or a trifluoromethyl group. However, cases where the structure is represented by formula (np1), (np2) or (np3) are excluded. X1 represents -OR1, -N(R2)R1, or -N(R1)2. X2 represents a methyl group or the like. X3 represents a methylene group or the like. R1 and R1 each represent a methylene group or the like.

Description

Resist composition and method for forming a resist pattern

[0001] The present invention relates to a resist composition and a method for forming a resist pattern. This application claims priority based on Japanese Patent Application No. 2024-085142 filed on May 24, 2024, and Japanese Patent Application No. 2025-034684 filed on March 5, 2025, the contents of which are incorporated herein by reference.

[0002] In recent years, advances in lithography technology have led to rapid advances in the miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display devices. A common method for achieving this miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.

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

[0004] In chemically amplified resists, acid generators in which the proximal carbon of the sulfonic acid group is perfluorinated have been put to practical use as acid generators that provide acids with sufficient acid strength for deprotection. Meanwhile, with the recent increase in environmental awareness, low-fluorinated sulfonates with reduced fluorine content have been proposed for the purpose of reducing environmental impact. However, even with low-fluorinated acid generators, the introduction of a fluorine atom into the proximal carbon of the sulfonic acid group is unavoidable in order to ensure acid strength.

[0005]

[0004] It is also known to use perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), or derivatives thereof (PFOAs or PFOSs) as surfactants to improve the coatability of resist compositions to substrates. However, in recent years, there has been an increasing demand for non-PFOA and non-PFOS surfactants, and a switch to non-PFOA and non-PFOS surfactants is desired. For example, Patent Document 1 describes a resist composition containing a fluorine-based surfactant having an alkylene oxide chain.

[0006] Japanese Patent Application Publication No. 2009-31350

[0007] With the further increase in environmental awareness in the future, there is a possibility that the production and use of PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds) will be restricted. However, the resist composition described in Patent Document 1 contains PFAS as an acid generator component. Meanwhile, with further advances in lithography technology, patterns are rapidly becoming finer. Therefore, there is a demand for resist compositions that maintain good sensitivity while exhibiting good lithography properties such as roughness.

[0008] The present invention has been made in light of the above circumstances, and an object of the present invention is to provide a resist composition that contains an acid generator and a surfactant that do not fall under the category of PFAS, and that exhibits excellent lithography properties, and a method of forming a resist pattern using the resist composition.

[0009] In order to solve the above-mentioned problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising: a resin component (A1) whose solubility in a developer changes due to the action of the acid; an acid generator component (B) that generates an acid upon exposure; and a surfactant (G01), wherein the surfactant (G01) is a first resin solution prepared by mixing a solution of the resin (P1) represented by the following formula (P-1) dissolved in propylene glycol monomethyl ether to a concentration of 20% by mass with a solution of the surfactant (G01) dissolved in propylene glycol monomethyl ether acetate to a concentration of 1% by mass, and the first resin solution contains 0.08 parts by mass of the surfactant (G01) per 100 parts by mass of the resin (P1): The resist composition is a surfactant in which a first water contact angle with a first resin film formed using a first resin solution is 8 degrees or more larger than a second water contact angle with a second resin film formed using a second resin solution prepared by dissolving the resin (P1) in propylene glycol monomethyl ether to give a concentration of 20 mass %, and the acid generator component (B) and the surfactant (G01) do not contain a compound having a trifluoromethyl group (excluding cases where the structure is represented by the following general formula (np1)) or a compound having a difluoromethylene group (excluding cases where the structure is represented by the following general formula (np2) or (np3)).

[0010] [In the formula, Mw represents the weight average molecular weight, and Mn represents the number average molecular weight.]

[0011] [In the formula, X １ Ha-OR １ , -N(R ２ ) R １ or -N(R １ ) ２ represents. ２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ３ , -SR ３ , or -NR ３ R ４represents. ３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR １ , -SR １ , -N(R ２ ) R １ or -N(R １ ) ２ Represents R １ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ２ , R ３ , and R ４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

[0012] In a second aspect, the present invention provides a resist composition that generates an acid upon exposure, and whose solubility in a developer changes due to the action of the acid. The resist composition comprises: a resin component (A1) whose solubility in a developer changes due to the action of an acid; an acid generator component (B) that generates an acid upon exposure; and a surfactant (G02), wherein the surfactant (G02) has a structure represented by the following general formula (g0-1), (g0-2), or (g0-3), and the acid generator component (B) and the surfactant (G02) do not contain a compound having a trifluoromethyl group (excluding the case where the trifluoromethyl group is a group represented by the following general formula (np1)) or a compound having a difluoromethylene group (excluding the case where the difluoromethylene group is a group represented by the following general formula (np2) or (np3)).

[0013] [wherein, Rf ０１ represents a fluorinated alkyl group having one carbon atom. ０１ Ha-OR ０１ or -N(R ０２ ) R ０１ Rf ０２ represents a fluorinated alkylene group having 1 carbon atom. ０２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ０３ , -SR ０３ , or -NR ０３ R ０４ represents. ０３represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR ０１ , -SR ０１ , or -N(R ０２ ) R ０１ Represents R ０１ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ０２ , R ０３ , and R ０４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

[0014] [In the formula, X １ Ha-OR １ or -N(R ２ ) R １ represents. ２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ３ , -SR ３ , or -NR ３ R ４ represents. ３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR １ , -SR １ , or -N(R ２ ) R １ Represents R １ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ２ , R ３ , and R ４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

[0015] A third aspect of the present invention is a method of forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition according to the first or second aspect, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.

[0016] According to the present invention, it is possible to provide a resist composition that contains an acid generator and a surfactant that do not fall under the category of PFAS, and that exhibits excellent lithography properties, as well as a method of forming a resist pattern that uses the resist composition.

[0017] In this specification and claims, "aliphatic" is a relative concept to aromatic, and is defined as meaning a group, compound, etc. that does not have aromaticity. "Alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The same applies to alkyl groups in alkoxy groups. "Alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups, unless otherwise specified. "Halogen atom" includes fluorine, chlorine, bromine, and iodine atoms. "Structural unit" means a monomer unit that constitutes a polymer compound (resin, polymer, copolymer). When it is written that "may have a substituent," it means a case where a hydrogen atom (-H) is replaced with a monovalent group, or a case where a methylene group (-CH ２ The term "exposure" encompasses both cases where the radical (-) is substituted with a divalent group.

[0018] An "acid-decomposable group" is a group having acid decomposability in which at least a part of the bond in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of acid-decomposable groups whose polarity increases by the action of an acid include groups that decompose by the action of an acid to generate a polar group. Examples of polar groups include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO ３ More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, groups in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).

[0019] The term "acid-dissociable group" refers to either (i) a group having acid dissociability in which the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) a group in which a portion of the bond is cleaved by the action of an acid, followed by a decarboxylation reaction, in which the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid-dissociable group. Thus, when the acid-dissociable group is dissociated by the action of an acid, a polar group with higher polarity than the acid-dissociable group is generated, thereby increasing the polarity. As a result, the polarity of the entire component (A1) increases. The increase in polarity relatively changes the solubility in the developer, increasing the solubility when the developer is an alkaline developer and decreasing the solubility when the developer is an organic developer.

[0020] A "base component" is an organic compound that has film-forming ability. Organic compounds used as base components are broadly classified into non-polymers and polymers. As non-polymers, those with a molecular weight of 500 or more and less than 4000 are usually used (hereinafter referred to as "low molecular weight compounds"). Hereinafter, when referring to "resin," "high molecular weight compound," or "polymer," it refers to a polymer with a molecular weight of 1000 or more. The molecular weight of the polymer is the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[0021] The term "derived structural unit" refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R αｘ ) is an atom or group other than a hydrogen atom. αｘ ) is substituted with a substituent containing an ester bond, or αｘThis also includes α-hydroxyacrylic esters in which the α-position carbon atom of an acrylic ester is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group. Unless otherwise specified, the α-position carbon atom of an acrylic ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, acrylic esters in which the hydrogen atom bonded to the α-position carbon atom has been replaced with a substituent may be referred to as α-substituted acrylic esters.

[0022] The term "derivative" is used to refer to a compound in which the hydrogen atom at the α-position of the target compound has been substituted with another substituent such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include a compound in which the hydrogen atom of the hydroxyl group of a target compound in which the hydrogen atom at the α-position may be substituted with a substituent has been substituted with an organic group; a compound in which the hydrogen atom at the α-position of the target compound may be substituted with a substituent to which a substituent other than a hydroxyl group is bonded; and the like. Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. Examples of substituents that can be used to replace the hydrogen atom at the α-position of hydroxystyrene include R αｘ The same can be mentioned.

[0023] In this specification and claims, some structures represented by chemical formulas may have asymmetric carbon atoms, and may exist as enantiomers or diastereoisomers. In such cases, a single chemical formula represents all of the isomers. These isomers may be used alone or as a mixture.

[0024] (Resist Composition) The resist composition of this embodiment generates an acid upon exposure, and its solubility in a developer changes due to the action of the acid. This resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer changes due to the action of the acid, an acid generator component (B) (hereinafter also referred to as "component (B)") that generates an acid upon exposure, and a surfactant (G01) or (G02) (hereinafter collectively referred to as "component (G0)").

[0025]

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

[0026] The resist composition of this embodiment may be a positive resist composition or a negative resist composition. Furthermore, the resist composition of this embodiment may be for use in an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or for use in a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.

[0027] <Component (A)> In the resist composition of this embodiment, the component (A) contains a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in a developer changes under the action of an acid. By using the component (A1), the polarity of the base component changes before and after exposure, making it possible to obtain good development contrast not only in an alkaline development process but also in a solvent development process. As the component (A), other polymeric compounds and / or low molecular weight compounds may be used in combination with the component (A1).

[0028] In the resist composition of this embodiment, as the component (A), one type of compound may be used, or two or more types may be used in combination.

[0029] Regarding the Component (A1): The component (A1) is a resin component whose solubility in a developer changes under the action of an acid. The component (A1) preferably contains a structural unit (a1) containing an acid-decomposable group whose polarity increases under the action of an acid. The component (A1) may contain other structural units in addition to the structural unit (a1), as necessary.

[0030] <<Structural Unit (a1)>> The structural unit (a1) is a structural unit that contains an acid-decomposable group whose polarity increases when acted upon by an acid.

[0031] Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups for base resins of chemically amplified resist compositions. Specific examples of acid-dissociable groups that have been proposed as acid-dissociable groups for base resins of chemically amplified resist compositions include the "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," "tertiary alkyloxycarbonyl acid-dissociable groups," and "secondary alkyl ester-type acid-dissociable groups" described below.

[0032] Acetal-Type Acid-Dissociable Group: Among the polar groups, examples of the acid-dissociable group that protects a carboxy group or a hydroxyl group include acid-dissociable groups represented by the following general formula (a1-r-1) (hereinafter, sometimes referred to as "acetal-type acid-dissociable group"):

[0033] [In the formula, Ra' １ , Ra' ２ is a hydrogen atom or an alkyl group. ３ is a hydrocarbon group, and Ra' ３ is Ra' １ , Ra' ２ may be bonded to any one of the following to form a ring.]

[0034] In formula (a1-r-1), Ra' １ and Ra' ２ Among Ra', at least one is preferably a hydrogen atom, and more preferably both are hydrogen atoms. １ or Ra' ２When is an alkyl group, examples of the alkyl group include the same alkyl groups as those exemplified as the substituent that may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylic acid ester above, and alkyl groups having 1 to 5 carbon atoms are preferred. Specific examples include linear or branched alkyl groups. More specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0035] In formula (a1-r-1), Ra' ３ Examples of the hydrocarbon group include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0036] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

[0037] Ra' ３When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic group, and may be a polycyclic group or a monocyclic group. As an aliphatic hydrocarbon group that is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferred. As the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As an aliphatic hydrocarbon group that is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferred, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ ]decane, tetracyclododecane, and the like.

[0038] Ra' ３ When the cyclic hydrocarbon group described above is an aromatic group, the aromatic group is a 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. It may be monocyclic or polycyclic, and may have a substituent that replaces a hydrogen atom of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. The aromatic hydrocarbon ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 5 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent that replaces a hydrogen atom of the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0039] Ra' ３Specific examples of the aromatic group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or the aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or the aromatic heterocycle has been substituted with an alkylene group (e.g., an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0040] Ra' ３ The cyclic hydrocarbon group in may have a substituent. Examples of the substituent include -R Ｐ１ , -R Ｐ２ -O-R Ｐ１ , -R Ｐ２ -CO-R Ｐ１ , -R Ｐ２ -CO-OR Ｐ１ , -R Ｐ２ -O-CO-R Ｐ１ , -R Ｐ２ -OH, -R Ｐ２ -CN or -R Ｐ２ -COOH (hereinafter, these substituents are collectively referred to as "Ra ｘ５ ") etc. Here, R Ｐ１ is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic group having 4 to 30 carbon atoms. Ｐ２ is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic group having 4 to 30 carbon atoms. Ｐ１ and R Ｐ２Some or all of the hydrogen atoms in the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of one type of the above-mentioned substituents, or may have one or more of each of two or more types of the above-mentioned substituents. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0]octanyl group, and the like. ２，６ ]decanyl group, tricyclo[3.3.1.1 ３，７ ] decanyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ ] Examples of the monovalent aromatic group having 4 to 30 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, or phenanthrene.

[0041] Ra' ３ But Ra' １ , Ra' ２ When the cyclic group is bonded to any one of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

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

[0043] [In the formula, Ra' ４ ~Ra' ６ are each a hydrocarbon group, and Ra' ５ , Ra' ６ may be bonded to each other to form a ring.

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

[0045] Ra' ５ and Ra' ６ When Ra' is bonded to each other to form a ring, preferred examples thereof include a group represented by the following general formula (a1-r2-1), a group represented by the following general formula (a1-r2-2), and a group represented by the following general formula (a1-r2-3). ４ ~Ra' ６ When the groups are not bonded to each other and are independent hydrocarbon groups, preferred examples include groups represented by the following general formula (a1-r2-4).

[0046] [In formula (a1-r2-1), Ra' １０ represents a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group. １１ is Ra' １０ represents a group which forms an aliphatic cyclic group together with the carbon atom to which it is bonded. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group which forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra１０１ ~Ra １０３ are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in the linear saturated hydrocarbon group and the cyclic aliphatic saturated hydrocarbon group may be substituted. １０１ ~Ra １０３ Two or more of the above may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra １０４ In formula (a1-r2-4), Ra′ is an aromatic group which may have a substituent. １２ and Ra' １３ are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of this chain saturated hydrocarbon group may be substituted. １４ is a hydrocarbon group which may have a substituent. * indicates a bond (the same applies hereinafter).

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

[0048] Ra' １０ The linear alkyl group in Ra' has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. １０ In the formula (I), the branched alkyl group is the above-mentioned Ra' ３ The same can be mentioned.

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

[0050] In formula (a1-r2-1), Ra' １１ (Ra' １０ The aliphatic cyclic group formed together with the carbon atom to which Ra' is bonded in formula (a1-r-1) is ３ Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl and cyclohexyl groups are more preferred.

[0051] In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya includes Ra' in the formula (a1-r-1). ３ Examples of the cyclic hydrocarbon group include a group in which one or more hydrogen atoms have been further removed from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in the formula (I). The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of the substituent include the above-mentioned Ra' ３ In formula (a1-r2-2), the substituents that the cyclic hydrocarbon group in formula (a1-r2-2) may have are the same as those in formula (a1-r2-2). １０１ ~Ra １０３ In the formula, examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. １０１ ~Ra １０３In the above formula, examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group; ２，６ ]decanyl group, tricyclo[3.3.1.1 ３，７ ] decanyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ ] and polycyclic aliphatic saturated hydrocarbon groups such as a dodecanyl group and an adamantyl group. １０１ ~Ra １０３ Among these, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among these, a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.

[0052] The above Ra １０１ ~Ra １０３ Examples of the substituents that the chain saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the formula (I) include the above-mentioned Ra ｘ５ The same groups as those shown below can be mentioned.

[0053] Ra １０１ ~Ra １０３ Examples of the group containing a carbon-carbon double bond formed by two or more of the above being bonded to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.

[0054] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). ３ In formula (a1-r2-3), the groups exemplified as the aliphatic hydrocarbon group are preferably monocyclic or polycyclic groups. １０４Examples of the aromatic group in the formula (I) include aromatic groups having 4 to 30 carbon atoms, preferably aromatic groups having 4 to 15 carbon atoms, such as groups in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring or an aromatic heterocyclic ring. １０４ is more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, phenanthrene, or thiophene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or thiophene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or thiophene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.

[0055] Ra in formula (a1-r2-3) １０４ Examples of the substituent that may be possessed by the group include a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group), an alkyloxycarbonyl group, and the like.

[0056] In formula (a1-r2-4), Ra' １２ and Ra' １３ are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. １２ and Ra' １３ In the formula (I), the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms includes the above-mentioned Ra １０１ ~Ra １０３ The monovalent saturated chain hydrocarbon group having 1 to 10 carbon atoms in the formula (1) may be substituted in part or in whole. １２ and Ra' １３ Among these, Ra' is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. １２ and Ra' １３ In the case where the chain saturated hydrocarbon group represented by the formula: ｘ５ The same groups as those shown below can be mentioned.

[0057] In formula (a1-r2-4), Ra' １４ is a hydrocarbon group which may have a substituent. １４ The hydrocarbon group in the formula (I) includes a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0058] Ra' １４ The linear alkyl group in the formula (I) preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0059] Ra' １４ The branched alkyl group in the formula (I) preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

[0060] Ra' １４ When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic group, and may be a polycyclic group or a monocyclic group. As an aliphatic hydrocarbon group that is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferred. As the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specific examples thereof include cyclopentane and cyclohexane. As an aliphatic hydrocarbon group that is a polycyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferred, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferred, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ２，６ ]decane, tetracyclododecane, and the like.

[0061] Ra' １４ As the aromatic group in １０４ Among them, the aromatic groups Ra' are the same as those in １４is an aromatic group having 4 to 15 carbon atoms, preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene. １４ Examples of the substituent that may be possessed by Ra include １０４ Examples of the substituents include the same as those that may be possessed by the group.

[0062] Ra' in formula (a1-r2-4) １４ When Ra' in formula (a1-r2-4) is a naphthyl group, the position at which it is bonded to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group. １４ When is an anthryl group, the position at which it is bonded to the tertiary carbon atom in the formula (a1-r2-4) may be any one of the 1st, 2nd, and 9th positions of the anthryl group.

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

[0064]

[0065]

[0066]

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

[0068]

[0069]

[0070]

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

[0072]

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

[0074]

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

[0076] [In the formula, Ra' ７ ~Ra' ９ are each an alkyl group.

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

[0078] Secondary Alkyl Ester-Type Acid-Dissociable Group: Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-4).

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

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

[0081] Ra' １０ and Ra' １１ａ or Ra' １１ｂ may be bonded to each other to form a ring. The ring may be polycyclic or monocyclic, and may be an alicyclic or aromatic ring. The alicyclic and aromatic rings may contain heteroatoms.

[0082] Ra' １０ and Ra' １１ａ or Ra' １１ｂ and are bonded to each other to form a ring, among the above, a monocycloalkene, a ring in which a portion of the carbon atoms of a monocycloalkene is substituted with a heteroatom (such as an oxygen atom or a sulfur atom), or a monocycloalkadiene is preferred, a cycloalkene having 3 to 6 carbon atoms is preferred, and cyclopentene or cyclohexene is preferred.

[0083] Ra' １０ and Ra' １１ａ or Ra' １１ｂ The ring formed by bonding these may be a fused ring. Specific examples of such a fused ring include indan.

[0084] Ra' １０ and Ra' １１ａ or Ra' １１ｂ The ring formed by bonding together may have a substituent. Examples of the substituent include the above-mentioned Ra ｘ５ etc.

[0085] Ra' １１ａor Ra' １１ｂ and Ra' １２ and may be bonded to each other to form a ring, and the ring may include Ra' １０ and Ra' １１ａ or Ra' １１ｂ and the ring formed by bonding with each other are exemplified.

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

[0087]

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

[0089] Of the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. Preferred specific examples of such structural unit (a1) include structural units represented by the following general formula (a1-1) or (a1-2):

[0090] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. １ is a divalent hydrocarbon group which may have an ether bond. ａ１ is an integer from 0 to 2. １ is an acid-dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4). １ is n ａ２ is a monovalent hydrocarbon group, n ａ２ is an integer from 1 to 3, and Ra ２is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

[0091] In the formula (a1-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. A fluorine atom is particularly preferred as the halogen atom. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoints of industrial availability and reducing the burden on the environment, a hydrogen atom or a methyl group is most preferred.

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

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

[0094] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0095] Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0096] Va １The aromatic group as a divalent hydrocarbon group in the formula (I) is a group having at least one aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 4 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring contained in the aromatic group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (an arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (an aryl group) has been substituted with an alkylene group (for example, a group in which one further hydrogen atom has been removed from the aryl group of an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0097] In the formula (a1-1), Ra １ is an acid-dissociable group represented by the above formula (a1-r-1), (a1-r-2) or (a1-r-4).

[0098] In the formula (a1-2), Wa １ (n ａ２The (+1)-valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure. ａ２ The +1) valency is preferably 2 to 4, more preferably 2 or 3.

[0099] In the formula (a1-2), Ra ２ is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

[0100] Specific examples of the structural unit (a1) are shown below. In each of the following formulas, R α represents a hydrogen atom or a methyl group.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] The structural unit (a1) contained in the component (A1) may be of one type, or may be of two or more types. As the structural unit (a1), a structural unit represented by the above formula (a1-1) is more preferred, as this tends to further improve characteristics (sensitivity, shape, etc.) in lithography using electron beams or EUV. Among these, as the structural unit (a1), one containing a structural unit represented by the following general formula (a1-1-1) is particularly preferred.

[0111] [In the formula, Ra １ " is an acid-dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4). * represents a bond.]

[0112] In the formula (a1-1-1), R, Va １ and n ａ１ represents R, Va in the formula (a1-1). １ and n ａ１ is the same as:

[0113] The acid-dissociable group represented by general formula (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4) is as described above. Among these, it is preferable to select an acid-dissociable group that is a cyclic group, as this is suitable for use with EB or EUV and can enhance reactivity.

[0114] The proportion of the structural unit (a1) in the component (A1), based on the total (100 mol%) of all structural units constituting the component (A1), is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 70 mol%. By ensuring that the proportion of the structural unit (a1) is at least the lower limit of the above-mentioned preferred range, lithography properties such as sensitivity, resolution, and roughness improvement are improved. On the other hand, by ensuring that the proportion is at most the upper limit of the above-mentioned preferred range, a balance with other structural units can be achieved, resulting in various favorable lithography properties.

[0115] <Other Structural Units> The component (A1) may contain other structural units, as necessary, in addition to the structural unit (a1) described above. Examples of other structural units include the structural unit (a10) represented by the following general formula (a10-1): a lactone-containing cyclic group, —SO ２ Examples of such structural units include (a2) structural units containing an --containing cyclic group or a carbonate-containing cyclic group; (a3) ​​structural units containing a polar group-containing aliphatic hydrocarbon group; (a4) structural units containing an acid-non-dissociable aliphatic cyclic group; and (st) structural units derived from styrene or a styrene derivative.

[0116] Structural Unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0117] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ｘ１ is a single bond or a divalent linking group. ｘ１ is an aromatic group. ａｘ１ is an integer of 1 or greater.

[0118] In the formula (a10-1), R is the same as R in the general formula (a1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoints of industrial availability and reducing the burden on the environment, a hydrogen atom or a methyl group is particularly preferred.

[0119] In the formula (a10-1), Ya ｘ１ is a single bond or a divalent linking group. ｘ１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0120] Divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group which may have a substituent may be an aliphatic hydrocarbon group or an aromatic group.

[0121] Aliphatic hydrocarbon group: An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups that contain a ring in their structure.

[0122] ...Straight-chain or branched-chain aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ The branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched chain aliphatic hydrocarbon group, a branched chain alkylene group is preferred, and specifically, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0123] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0124] ...Aliphatic hydrocarbon groups containing a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon groups include those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and the like.

[0125] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and even more preferably a methoxy group or an ethoxy group. The halogen atom as the substituent is preferably a fluorine atom. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. The cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure substituted with a substituent containing a heteroatom. The substituent containing a hetero atom includes —O—, —C(═O)—O—, —S—, and —S(═O) ２ -, -S(=O) ２ —O— is preferred.

[0126] Aromatic Group: The aromatic group is a 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. It may be monocyclic or polycyclic, and may have a substituent substituting a hydrogen atom of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. The aromatic hydrocarbon ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 5 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent substituting a hydrogen atom of the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. Heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0127] The number of carbon atoms in the aromatic group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 15, and particularly preferably 4 to 12. Specific examples of the aromatic group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or the aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or the aromatic heterocycle (aryl groups or heteroaryl groups), in which one hydrogen atom has been substituted with an alkylene group (e.g., groups in which one further hydrogen atom has been removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0128] The aromatic group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0129] Divalent linking group containing a hetero atom: Examples of the divalent linking group containing a hetero atom include -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, and -S(=O). ２ -, -S(=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ -, -Y ２１ -OC(=O)-Y ２２ - or -Y ２１ -S(=O) ２ -O-Y ２２ -, wherein Y ２１ and Y ２２are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer of 1 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. In the general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ -, -Y ２１ -OC(=O)-Y ２２ - or -Y ２１ -S(=O) ２ -O-Y ２２ -Middle, Y ２１ and Y ２２ are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as those described above. ２１ As Y, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred. ２２ is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. ２１ -C(=O)-O] ｍ” -Y ２２ In the group represented by -, m" is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. That is, the group represented by the formula -[Y ２１ -C(=O)-O] ｍ”-Y ２２ The group represented by - includes the group represented by the formula -Y ２１ -C(=O)-O-Y ２２ Among them, groups represented by the formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) ｂ’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0130] Ya ｘ１ is preferably a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, and more preferably a single bond or an ester bond [-C(=O)-O-, -O-C(=O)-].

[0131] In the formula (a10-1), Wa ｘ１ is an aromatic group. ｘ１ The aromatic group in the formula (n) is an aromatic ring which may have a substituent. ａｘ１ Examples of the aromatic ring include a group in which 4n+1) hydrogen atoms have been removed. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Wa ｘ１ The aromatic group in the formula (I) preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, even more preferably 4 to 15 carbon atoms, and particularly preferably 4 to 12 carbon atoms. ｘ１The aromatic group in (n) is selected from aromatic compounds containing an aromatic ring which may have two or more substituents (for example, biphenyl, fluorene, etc.). ａｘ１ Also included are groups in which one or more hydrogen atoms have been removed. ｘ１ Examples of the aryl group include benzene, naphthalene, anthracene, and biphenyl (n ａｘ１ A group in which (n +1) hydrogen atoms have been removed is preferred, and a group in which (n +1) hydrogen atoms have been removed from benzene or naphthalene is preferred. ａｘ１ A group in which (n +1) hydrogen atoms have been removed from benzene is more preferred, ａｘ１ A group in which 1) hydrogen atoms have been removed is more preferred.

[0132] Wa ｘ１ The aromatic group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include Ya ｘ１ Examples of the substituent include the same as those exemplified as the substituent of the cyclic aliphatic hydrocarbon group in Wa. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. ｘ１ The aromatic group in the formula (I) preferably has no substituent.

[0133] In the formula (a10-1), n ａｘ１ is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0134] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below. α represents a hydrogen atom or a methyl group.

[0135]

[0136]

[0137]

[0138] The structural unit (a10) contained in the component (A1) may be one type, or two or more types. The component (A1) may or may not contain the structural unit (a10), but preferably contains the structural unit (a10). When the component (A1) contains the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a10) is at or above the lower limit, sensitivity is likely to be further improved. On the other hand, by ensuring that the proportion is at or below the upper limit, it is easier to achieve a balance with other structural units.

[0139] Structural unit (a2): The component (A1) may include a structural unit (a2) (excluding those corresponding to the structural unit (a1)) that includes a lactone-containing cyclic group. When the component (A1) is used to form a resist film, the lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate. Furthermore, the presence of the structural unit (a2) provides effects such as appropriate adjustment of the acid diffusion length, improved adhesion of the resist film to the substrate, and appropriate adjustment of solubility during development, resulting in improved lithography properties.

[0140] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) that contains -O-C(=O)- within its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is also another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. There are no particular restrictions on the lactone-containing cyclic group in the structural unit (a2), and any group can be used. Specific examples include groups represented by the following general formulae (a2-r-1) to (a2-r-7).

[0141] [In the formula, Ra' ２１are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A″ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (—O—) or a sulfur atom (—S—), an oxygen atom, or a sulfur atom; n′ is an integer of 0 to 2, and m′ is 0 or 1. * represents a bond (the same applies hereinafter).

[0142] In the general formulas (a2-r-1) to (a2-r-7), Ra' ２１ The alkyl group in Ra' is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred. Ra' ２１ The alkoxy group in the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, ２１ Examples of the alkyl groups include those mentioned as examples of the alkyl group in the above formula and an oxygen atom (—O—). ２１ The halogen atom in Ra' is preferably a fluorine atom. ２１ As the halogenated alkyl group in the formula Ra′, ２１ Examples of the halogenated alkyl group include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0143] Ra' ２１In -COOR" and -OC(=O)R" in the formula (I), R" is either a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group for R" may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R" is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group. When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably has 4 to 12 carbon atoms, and most preferably has 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; ２，６ ] decane, tetracyclododecane, and other polycycloalkanes in which one or more hydrogen atoms have been removed. Examples of the lactone-containing cyclic group in R" include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7). Ra' ２１ The hydroxyalkyl group in the formula (R a ) preferably has 1 to 6 carbon atoms. ２１ and a group in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0144] Ra' ２１ Among the above, each of the groups is preferably independently a hydrogen atom or a cyano group.

[0145] In the general formulae (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms for A" is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between carbon atoms of the alkylene group, such as -O-CH ２ -, -CH ２ -O-CH ２ -, -S-CH ２ -, -CH ２ -S-CH ２ A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

[0146] Specific examples of the groups represented by the general formulae (a2-r-1) to (a2-r-7) are listed below.

[0147]

[0148]

[0149] Of the structural units (a2), structural units derived from acrylate esters in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent are preferred. Such structural units (a2) are preferably structural units represented by the following general formula (a2-1):

[0150] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ２１ is a single bond or a divalent linking group. ２１ represents -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. ２１ When is -O-, Ya ２１ does not become -CO-. ２１ is a lactone-containing cyclic group.

[0151] In the formula (a2-1), R is the same as defined above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoints of industrial availability and reducing the burden on the environment, a hydrogen atom or a methyl group is particularly preferred.

[0152] In the formula (a2-1), Ya ２１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. ２１ As the divalent linking group in the general formula (a10-1), ｘ１ Examples of the divalent linking group include the same as the divalent linking group in the above formula.

[0153] Ya ２１ is preferably a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof.

[0154] In the formula (a2-1), Ya ２１ is a single bond, and La ２１ is preferably —COO— or —OCO—.

[0155] In the formula (a2-1), Ra ２１ is a lactone-containing cyclic group. ２１ Suitable examples of the lactone-containing cyclic group in the formula (a2-r-1) include the groups represented by the general formulae (a2-r-1) to (a2-r-7) described above.

[0156] The structural unit (a2) contained in the component (A1) may be of one type, or may contain two or more types. The component (A1) may or may not contain the structural unit (a2). When the component (A1) contains the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, relative to the total (100 mol %) of all structural units constituting the component (A1). When the proportion of the structural unit (a2) is at least the preferred lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the aforementioned effects. When the proportion is at or below the upper limit, a balance with the other structural units can be achieved, resulting in various favorable lithography properties.

[0157] Regarding the structural unit (a3): In addition to the structural unit (a1), the component (A1) may further include a structural unit (a3) ​​(excluding those corresponding to the structural unit (a1) or the structural unit (a2)) that includes a polar group-containing aliphatic hydrocarbon group. When the component (A1) includes the structural unit (a3), the hydrophilicity of the component (A) is enhanced, contributing to improved resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0158] Examples of polar groups include hydroxyl groups, cyano groups, carboxy groups, and hydroxyalkyl groups in which some of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms, with hydroxyl groups being particularly preferred. Examples of aliphatic hydrocarbon groups include linear or branched hydrocarbon groups (preferably alkylene groups) having 1 to 10 carbon atoms, and cyclic aliphatic hydrocarbon groups (cyclic groups). The cyclic group may be either a monocyclic group or a polycyclic group, and can be appropriately selected from the many groups proposed for use in resins for ArF excimer laser resist compositions, for example.

[0159] When the cyclic group is a monocyclic group, it more preferably has 3 to 10 carbon atoms. Among these, structural units derived from acrylate esters containing an aliphatic monocyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which some of the alkyl group's hydrogen atoms are substituted with fluorine atoms are more preferred. Examples of such monocyclic groups include groups in which two or more hydrogen atoms have been removed from a monocycloalkane. Specific examples include groups in which two or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane, or cyclooctane. Of these monocyclic groups, groups in which two or more hydrogen atoms have been removed from cyclopentane and groups in which two or more hydrogen atoms have been removed from cyclohexane are industrially preferred.

[0160] When the cyclic group is a polycyclic group, the polycyclic group more preferably has 7 to 30 carbon atoms. Among them, structural units derived from acrylate esters containing an aliphatic polycyclic group containing a hydroxyl group, a cyano group, a carboxy group, or a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms are more preferred. Examples of such polycyclic groups include groups in which two or more hydrogen atoms have been removed from bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc. Specific examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ]decane, tetracyclododecane, and other polycycloalkanes by removing two or more hydrogen atoms. Among these polycyclic groups, groups by removing two or more hydrogen atoms from adamantane, groups by removing two or more hydrogen atoms from norbornane, and groups by removing two or more hydrogen atoms from tetracyclododecane are industrially preferred.

[0161] The structural unit (a3) ​​is not particularly limited, and any structural unit can be used as long as it contains a polar group-containing aliphatic hydrocarbon group. The structural unit (a3) ​​is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and which contains a polar group-containing aliphatic hydrocarbon group. When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a3) ​​is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid. Furthermore, when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, preferred structural units for the structural unit (a3) ​​include structural units represented by the following formulas (a3-1), (a3-2), and (a3-3); when the hydrocarbon group is a monocyclic group, preferred structural units include structural units represented by formula (a3-4).

[0162] [In the formula, R is the same as defined above, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, l is an integer of 0 to 5, and s is an integer of 1 to 3.]

[0163] In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, the hydroxyl group is preferably bonded to the 3rd position of the adamantyl group. j is preferably 1, and the hydroxyl group is particularly preferably bonded to the 3rd position of the adamantyl group.

[0164] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the norbornyl group.

[0165] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. In these, a 2-norbornyl group or a 3-norbornyl group is preferably bonded to the terminal of the carboxyl group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5- or 6-position of the norbornyl group.

[0166] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluorinated alkyl alcohol is preferably bonded to the 3- or 5-position of the cyclohexyl group.

[0167] The structural unit (a3) ​​contained in the component (A1) may be one type, or two or more types. When the component (A1) contains the structural unit (a3), the proportion of the structural unit (a3) ​​is preferably 1 to 30 mol %, more preferably 2 to 25 mol %, and even more preferably 5 to 20 mol %, based on the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a3) ​​is at least the preferred lower limit, the effects achieved by including the structural unit (a3) ​​can be fully obtained due to the effects described above. By ensuring that the proportion is at most the preferred upper limit, a balance with the other structural units can be achieved, resulting in various favorable lithography properties.

[0168] Regarding the structural unit (a4): In addition to the structural unit (a1), the component (A1) may further include a structural unit (a4) containing an acid-non-dissociable aliphatic cyclic group. When the component (A1) includes the structural unit (a4), the dry etching resistance of the formed resist pattern is improved. Furthermore, the hydrophobicity of the component (A) is enhanced. Improved hydrophobicity contributes to improvements in resolution, resist pattern shape, and the like, particularly in solvent development processes. The "acid-non-dissociable cyclic group" within the structural unit (a4) is a cyclic group that, when acid is generated in the resist composition upon exposure (for example, when acid is generated from a structural unit that generates acid upon exposure or from the component (B)), remains intact within the structural unit without dissociating even when acted upon by the acid.

[0169] Preferred examples of the structural unit (a4) include structural units derived from acrylate esters containing an acid-non-dissociable aliphatic cyclic group. The cyclic group can be any of the numerous groups conventionally known for use in resin components of resist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers), and the like. In terms of industrial availability, the cyclic group is preferably at least one selected from the group consisting of a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent. Specific examples of the structural unit (a4) include structural units represented by the following general formulas (a4-1) to (a4-7):

[0170] [In the formula, R α is the same as above.]

[0171] The structural unit (a4) contained in the component (A1) may be of one type, or may be of two or more types. When the component (A1) contains the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 40 mol %, and more preferably 5 to 20 mol %, relative to the total (100 mol %) of all structural units constituting the component (A1). By ensuring that the proportion of the structural unit (a4) is at least as high as the preferred lower limit, the effects of including the structural unit (a4) can be fully obtained, while by ensuring that the proportion is at most as high as the preferred upper limit, it is easier to achieve a balance with the other structural units.

[0172] Regarding the structural unit (st): The structural unit (st) is a structural unit derived from styrene or a styrene derivative. "Structural unit derived from styrene" refers to a structural unit formed by cleavage of the ethylenic double bond of styrene. "Structural unit derived from a styrene derivative" refers to a structural unit formed by cleavage of the ethylenic double bond of a styrene derivative.

[0173] The term "styrene derivative" refers to a compound in which at least some of the hydrogen atoms of styrene have been substituted with a substituent. Examples of styrene derivatives include those in which the hydrogen atom at the α-position of styrene has been substituted with a substituent, those in which one or more hydrogen atoms on the benzene ring of styrene have been substituted with a substituent, and those in which the hydrogen atom at the α-position of styrene and one or more hydrogen atoms on the benzene ring have been substituted with a substituent.

[0174] Examples of the substituent substituting the hydrogen atom at the α-position of styrene include an alkyl group having 1 to 5 carbon atoms and a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. A fluorine atom is particularly preferred as the halogen atom. The substituent substituting the hydrogen atom at the α-position of styrene is preferably an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group from the viewpoint of industrial availability.

[0175] Examples of substituents substituting hydrogen atoms on the benzene ring of styrene include alkyl groups, alkoxy groups, halogen atoms, and halogenated alkyl groups. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and even more preferably a methoxy group or an ethoxy group. The halogen atom as the substituent is preferably a fluorine atom. Examples of halogenated alkyl groups as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. The substituent substituting hydrogen atoms on the benzene ring of styrene is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0176] The structural unit (st) is preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, more preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with a methyl group, and even more preferably a structural unit derived from styrene.

[0177] The structural unit (st) contained in the component (A1) may be of one type, or may consist of two or more types. When the component (A1) contains the structural unit (st), the amount of the structural unit (st) is preferably 1 to 30 mol %, and more preferably 3 to 20 mol %, relative to the total (100 mol %) of all structural units constituting the component (A1).

[0178] The resist composition may contain one type of component (A1), or two or more types of components may be used in combination.

[0179] Examples of the component (A1) include polymeric compounds that include repeating structures of the structural unit (a1), the structural unit (a10), and the structural unit (st).

[0180] The component (A1) can be produced by dissolving the monomers that derive each structural unit in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the solution and polymerizing. Alternatively, the component (A1) can be produced by dissolving a monomer that derives the structural unit (a1) and a monomer that derives any structural unit (e.g., structural unit (a10), etc.) in a polymerization solvent, adding a radical polymerization initiator such as those described above to polymerize, and then carrying out a deprotection reaction. During the polymerization, for example, HS-CH ２ -CH ２ -CH ２ -C(CF ３ ) ２ By using a chain transfer agent such as —OH in combination, it is possible to obtain a chain with —C(CF ３ ) ２ A copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms is thus introduced, and is effective in reducing development defects and LER (line edge roughness: non-uniform irregularities on the line sidewalls).

[0181] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene standards measured by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 30,000. When the Mw of component (A1) is equal to or less than the preferred upper limit of this range, the component has sufficient solubility in a resist solvent for use as a resist, while when the Mw is equal to or greater than the preferred lower limit of this range, the component exhibits good dry etching resistance and resist pattern cross-sectional shape. The dispersity (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Here, Mn represents the number-average molecular weight.

[0182] Regarding the component (A2): The resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as "component (A2)") that does not fall under the category of the component (A1) and whose solubility in a developer changes under the action of acid. There are no particular limitations on the component (A2), and it may be arbitrarily selected from the many base components conventionally known for use in chemically amplified resist compositions. The component (A2) may be a polymeric compound or a low molecular weight compound, and may be used either alone or in combination of two or more types.

[0183] The proportion of the component (A1) in the component (A), relative to the total mass of the component (A), is preferably 25 mass% or more, more preferably 50 mass% or more, and even more preferably 75 mass% or more, and may even be 100 mass%. When this proportion is 25 mass% or more, a resist pattern that is excellent in various lithography properties, such as high sensitivity, resolution, and improved roughness, is more likely to be formed.

[0184] The amount of the component (A) in the resist composition of this embodiment may be adjusted depending on factors such as the thickness of the resist film to be formed.

[0185] Component (A) is preferably a polymer compound that does not fall under the category of PFAS. That is, component (A1) is preferably a compound that does not fall under the category of PFAS. When component (A) contains component (A2), component (A2) is preferably a compound that does not fall under the category of PFAS. "PFAS" refers to a compound having a trifluoromethyl group (-CF ３ ) and compounds containing a difluoromethylene group (—CF ２ -). However, even if a compound contains a trifluoromethyl group, if all of the trifluoromethyl groups contained in the compound have a structure represented by the following general formula (np1), it does not fall under the category of PFAS. Furthermore, even if a compound contains a difluoromethylene group, if all of the difluoromethylene groups contained in the compound have a structure represented by the following general formula (np2) or (np3), it does not fall under the category of PFAS.

[0186] [In the formula, X １ Ha-OR １ , -N(R ２ ) R１ or -N(R １ ) ２ represents. ２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ３ , -SR ３ , or -NR ３ R ４ represents. ３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR １ , -SR １ , -N(R ２ ) R １ or -N(R １ ) ２ Represents R １ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ２ , R ３ , and R ４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

[0187] In the formulas (np1), (np2), and (np3), X １ -OR in １ , -N(R ２ ) R １ or -N(R １ ) ２ In the formula, CF ３ In the formula (np2), X is bonded to O or N. ２ -OR in ３ , -SR ３ , or -NR ３ R ４ In the formula, CF ２ The bond to X is O, S, or N. ３ -OR in １ , -SR １ , -N(R ２ ) R １ or -N(R １ ) ２ In the formula, CF ２ The bond to X is O, S, or N. ２The monovalent aromatic hydrocarbon group which may have a substituent in the formula (np3) is a group in which one hydrogen atom has been removed from an aromatic ring which has a substituent or an aromatic ring which has no substituent. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring may be a monocycle or a polycycle. In the formula (np3), X ３ The optionally substituted divalent aromatic hydrocarbon group in the formula (I) is a group obtained by removing two hydrogen atoms from a substituted or unsubstituted aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring may be a monocycle or a polycycle.

[0188] The component (A) preferably contains a polymer compound that does not contain a trifluoromethyl group (provided that this does not result in a structure represented by general formula (np1) above) or a difluoromethylene group (provided that this does not result in a structure represented by general formula (np2) or (np3) above).

[0189] <Acid Generator Component (B)> In addition to the component (A), the resist composition of this embodiment further contains an acid generator component (component (B)) that generates acid upon exposure.

[0190] Component (B) does not contain any compounds that fall under the category of PFAS. Component (B) contains only compounds that do not fall under the category of PFAS. That is, component (B) does not contain any compound having a trifluoromethyl group (excluding the group represented by general formula (np1) above) or any compound having a difluoromethylene group (excluding the group represented by general formula (np2) or (np3) above).

[0191] The component (B) preferably contains a compound (B0) (hereinafter also referred to as “component (B0)”) represented by the following general formula (b0):

[0192] [In the formula, Ar represents an aromatic ring. ０ represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ０ is -C(=O)-O-, -O-C(=O)- or -O-S(=O) ２ represents a divalent linking group containing -. ０ represents a cyclic group.０ represents an organic group. n01 is an integer of 1 or more as long as the valence allows. n02 is an integer of 0 or more as long as the valence allows. ０ -Yb ０ is -O-C(=O)-Yb ０ If Yb ０ is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. ０ may be the same or different. When n02 is 2 or more, a plurality of Rb ０ may be the same or different, m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation.

[0193] {Anion Moiety} In the formula (b0), the aromatic ring in Ar is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include, but are not limited to, pyridine rings, thiophene rings, and furan rings.

[0194] The aromatic ring in Ar is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0195] In the formula (b0), Rf ０ The fluorinated alkyl group having 1 to 5 carbon atoms is a group in which some of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are replaced with fluorine atoms or —CH ２Rf is a group substituted with F. The fluorinated alkyl group may be linear or branched, but is preferably linear. ０ The linear fluorinated alkyl group in Rf preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. ０ The branched fluorinated alkyl group in the formula (I) preferably has 3 or 4 carbon atoms, and more preferably 3 carbon atoms.

[0196] Rf ０ is more preferably a fluorine atom from the viewpoint of acid strength.

[0197] In the formula (b0), Rb ０ The organic group in the formula (I) is a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group.

[0198] Rb ０ The aliphatic hydrocarbon group in Rb preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. ０ The aliphatic hydrocarbon group in Rb may be saturated or unsaturated, but is preferably saturated. ０ The aliphatic hydrocarbon group in is preferably a linear or branched alkyl group.

[0199] Rb ０ The linear alkyl group in Rb preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. ０ The branched alkyl group in Rb preferably has 3 or 4 carbon atoms, more preferably 3 carbon atoms. ０ The organic group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and further preferably an ethyl group or a methyl group.

[0200] Rb ０ The organic group in the formula (I) preferably does not contain an acid-dissociable group.

[0201] In the formula (b0), n01 is an integer of 1 or more as far as the valence allows. n01 is preferably 1 to 4, more preferably 2 to 4, even more preferably 3 or 4, and particularly preferably 4.

[0202] In the formula (b0), n02 is, as far as the valence allows, an integer of 0 or greater. n02 is preferably 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0203] In the formula (b0), L ０ The divalent linking group in the formula (I) includes -C(=O)-O-, -O-C(=O)-, and -O-S(=O) ２ -, and a combination of one or more of these with an alkylene group. ０ The divalent linking group in the formula (I) is -C(=O)-O-, -O-C(=O)-, or -O-S(=O) ２ -, then L ０ -Yb ０ is -C(=O)-O-Yb ０ , -OC(=O)-Yb ０ , or —O—S(═O) ２ -Yb ０ It is. ０ -C(=O)-O-, -O-C(=O)-, and -O-S(=O) ２ - is a combination of one or more of the above with an alkylene group, the alkylene group may be linear or branched.

[0204] L ０ Examples of the divalent linking group in the formula (L0-1) include linking groups represented by the following general formula (L0-1).

[0205] [In the formula, Lb ０１ and Lb ０２ each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms; L ０１ is -C(=O)-O-, -O-C(=O)-, or -O-S(=O) ２ -; n03 represents an integer of 1 to 3. However, when n03 is 2 or 3, Lb ０１ When n03 is 2 or 3, a plurality of Lb ０may be the same or different. When n03 is 2 or more, multiple L ０１ may be the same or different. * represents a bond bonded to Ar in the formula (b0), and ** represents a bond bonded to Yb in the formula (b0). ０１ is a bond that bonds to

[0206] In the formula (L0-1), Lb ０１ and Lb ０２ The alkylene group having from 1 to 5 carbon atoms in Lb may be linear or branched, but is preferably linear. ０１ and Lb ０２ The linear alkylene group in Lb preferably has 1 to 3 carbon atoms, and more preferably has 1 or 2 carbon atoms. ０１ and Lb ０２ The branched alkylene group in the formula (I) preferably has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms.

[0207] In the formula (L0-1), n03 is preferably 1 or 2, and more preferably 1.

[0208] L ０ Examples of the divalent linking group in the formula (L01-1) include linking groups represented by the following general formulae (L01-1) to (L03-1).

[0209] [In the formula, Lb ０１１ ~Lb ０３１ Lb each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. ０１２ ~Lb ０３２ each independently represents a single bond or a divalent linking group. nb01 to nb03 each independently represents an integer of 1 to 3. However, when nb01 to nb03 are 2 or 3, Lb ０１１ ~Lb ０３１ When nb01 is 2 or 3, multiple Lb ０１１ may be the same or different. When nb02 is 2 or 3, multiple Lb ０２１ may be the same or different. When nb03 is 2 or 3, a plurality of Lb ０３１may be the same or different. * represents a bond bonded to Ar in the general formula (b0), ** represents Yb in the general formula (b0), ０ represents a bond bonded to the

[0210] In the formulae (L01-1) to (L01-3), Lb ０１１ ~Lb ０３１ As the alkylene group having 1 to 5 carbon atoms, Lb ０１ In the formulae (L01-1) to (L01-3), Lb ０１２ ~Lb ０３２ The divalent linking group in the formula (I) is -C(=O)-O-, -O-C(=O)-, or -O-S(=O) ２ Examples of the alkylene group having 1 to 5 carbon atoms include alkylene groups having 1 to 5 carbon atoms, which may have a - group. Examples of the alkylene group having 1 to 5 carbon atoms include Lb ０１ In the formulae (L01-1) to (L01-3), nb01 to nb03 are preferably 1 or 2, and more preferably 1.

[0211] L in the formula (b0) ０ Examples of the group include groups represented by any one of the following general formulas (L0-1-1) to (L0-1-5).

[0212] [In the formula, Vb ０１ and Vb ０２ each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. ０３ represents an alkylene group having 1 to 5 carbon atoms. * represents a bond bonded to Ar in the formula (b0), and ** represents a bond bonded to Yb in the formula (b0). ０１ is a bond that bonds to

[0213] In the above formulas (L0-1-1) to (L0-1-5), Vb ０１ and Vb ０２ The alkylene group having 1 to 5 carbon atoms in Vb may be linear or branched, but is preferably linear. ０１ and Vb ０２ The linear alkylene group in Vb preferably has 1 to 3 carbon atoms, and more preferably has 1 or 2 carbon atoms.０１ and Vb ０２ The branched alkylene group in the formula (I) preferably has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms.

[0214] L ０ The divalent linking group in the formula (I) preferably does not contain an acid-dissociable group.

[0215] <Yb ０ About≫ L ０ -Yb ０ is -O-C(=O)-Yb ０ If not: L ０ -Yb ０ is -O-C(=O)-Yb ０ otherwise, Yb ０ is a cyclic group. ０ The cyclic group in (I) is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably saturated.

[0216] Yb ０ The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The 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 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. ０ Specific examples of the aromatic ring of the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. ０Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.), etc. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0217] Yb ０ Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed within a linear or branched aliphatic hydrocarbon group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and preferred polycycloalkanes have 7 to 30 carbon atoms. Among them, the polycycloalkanes include adamantane, norbornane, isobornane, bornane, tricyclo[5.2.1.0 ２，６ ] Polycycloalkanes having a polycyclic skeleton of a bridged ring system such as decane and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton are preferred.

[0218] Yb ０The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group, a norbornyl group, or a bornyl group, and particularly preferably an adamantyl group.

[0219] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２ -], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ -] and the like. The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0220] Also, Yb ０ The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specifically, lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above, —SO 2 represented by the general formulae (b5-r-1) to (b5-r-4) below, ２ -containing cyclic groups, heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16), etc. ０ represents a bond bonded to

[0221] [In the formula, Rb' ５１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group; R″ is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or —SO ２-containing cyclic group; B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; n' is an integer of 0 to 2; * represents a bond.

[0222]

[0223] In the general formulae (b5-r-1) and (b5-r-2), B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. B" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0224] In the general formulae (b5-r-1) to (b5-r-4), Rb' ５１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group, and among these, are each independently preferably a hydrogen atom or a cyano group.

[0225] Specific examples of the groups represented by general formulae (b5-r-1) to (b5-r-4) are listed below, where "Ac" represents an acetyl group.

[0226]

[0227]

[0228]

[0229] Yb ０The cyclic group in may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. The halogen atom as a substituent is preferably a fluorine atom, a bromine atom, or an iodine atom. Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the halogen atoms. The carbonyl group as a substituent is a methylene group (-CH) constituting a cyclic hydrocarbon group. ２ -) is a group that substitutes

[0230] Yb ０ The cyclic hydrocarbon group in may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a bridged ring polycyclic skeleton to which one or more aromatic rings are fused. Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. ０ Specific examples of the fused cyclic group in formula (b0) include groups represented by the following formulae (r-br-1) to (r-br-2). ０ Rx represents a bond bonded to ０ represents a substituent.

[0231]

[0232] Yb ０Examples of the substituent that the fused cyclic group in formula (r-hr-1) may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic group, and an alicyclic hydrocarbon group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the fused cyclic group are the same as those exemplified as the substituent of the cyclic group. Examples of the aromatic group as the substituent of the fused cyclic group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), and a heterocyclic group represented by each of the above formulas (r-hr-1) to (r-hr-6). Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include a group in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane or cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ a group in which one hydrogen atom has been removed from a polycycloalkane such as decane or tetracyclododecane; a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7); a —SO 2 group represented by each of the general formulae (b5-r-1) to (b5-r-4), ２ -containing cyclic group: heterocyclic groups represented by the above formulae (r-hr-7) to (r-hr-16), respectively.

[0233] The substituent of the fused cyclic group may be an alkyl group partially substituted with a heteroatom-containing group. In the alkyl group as a substituent of the fused cyclic group, for example, some of the hydrogen atoms may be substituted with a heteroatom-containing group. Alternatively, in the alkyl group as a substituent of the fused cyclic group, some of the carbon atoms (e.g., methylene groups) constituting the hydrocarbon chain may be substituted with a heteroatom-containing group. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0234] Examples of the heteroatom-containing group that substitutes a hydrogen atom of an alkyl group include a hydroxyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a carboxy group.

[0235] Examples of heteroatom-containing groups that substitute for carbon atoms constituting the hydrocarbon chain of an alkyl group include -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, and -S(=O) ２ -, -S(=O) ２ Examples of the heteroatom-containing group include -O-, -C(=O)-O-, -O-C(=O)-, and -S(=O) ２ —O— is preferred, and —C(═O)—O— is more preferred.

[0236] The substituent of the fused ring group is —C(═O)—O—Rx ０１ Examples of the group include a group represented by the following formula: ０１ represents an alkyl group, which may be linear, branched, or cyclic. Examples of linear alkyl groups include those having 1 to 5 carbon atoms, with methyl, ethyl, n-propyl, or n-butyl being preferred. Examples of branched alkyl groups include those having 3 to 5 carbon atoms, with isopropyl, tert-butyl, sec-butyl, or isobutyl being preferred. Examples of cyclic alkyl groups include those in which one hydrogen atom has been removed from a cycloalkane having 1 to 8 carbon atoms, with cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl being preferred, and cyclopentyl or cyclohexyl being more preferred.

[0237] Yb ０ Examples of the cyclic groups include an adamantyl group which may have a substituent; a cyclic group having a steroid skeleton which may have a substituent; a lactone-containing cyclic group represented by each of the formulae (a2-r-1) to (a2-r-7); and a —SO cyclic group represented by each of the formulae (b5-r-1) to (b5-r-4). ２-containing cyclic groups; fused cyclic groups containing a fused ring formed by condensing an aliphatic hydrocarbon ring with an aromatic ring; and aromatic hydrocarbon groups which may have a substituent. As the fused cyclic groups, groups represented by the formula (r-br-1) or (r-br-2) are preferred. Examples of the substituents on the adamantyl group include a hydroxy group and a carbonyl group.

[0238] L ０ -Yb ０ is -O-C(=O)-Yb ０ If not L ０ Examples of the linking group include a divalent linking group containing -C(=O)-O-; -S(=O) ２ a divalent linking group containing —O—; a group represented by the formula (L01-3) (wherein nb03 is 1 and Lb ０３１ and Lb ０３２ The divalent linking group containing -C(=O)-O- includes a group represented by the formula (L01-1), and preferably a group represented by the formula (L0-1-1), (L0-1-2) or (L0-1-5). ２ Examples of the divalent linking group containing —O— include groups represented by formula (L02-1) above, and groups represented by formula (L0-1-4) or (L0-1-5) are preferred.

[0239] L ０ -Yb ０ is -O-C(=O)-Yb ０ In this case, Yb ０ is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent. In the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group.

[0240] Yb ０ The alicyclic group which may have a substituent in "L ０ -Yb ０ is -O-C(=O)-Yb ０Examples of the alicyclic group include a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane; a cyclic group having a steroid skeleton; a lactone-containing cyclic group represented by each of the above formulae (a2-r-1) to (a2-r-7); and —SO ２ -containing cyclic group: heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16), etc. ０ The substituents of the alicyclic group include "L ０ -Yb ０ is -O-C(=O)-Yb ０ Examples of cases where the above is not the case include "if

[0241] Yb ０ The fused ring group of an aliphatic ring and an aromatic ring in ０ -Yb ０ is -O-C(=O)-Yb ０ Examples of the fused cyclic group include the groups represented by the formula (r-br-1) or (r-br-2). ０ The substituents of the fused cyclic group include "L ０ -Yb ０ is -O-C(=O)-Yb ０ Examples of cases where the above is not the case include "if

[0242] Yb ０ The aromatic hydrocarbon group having a substituent in "L ０ -Yb ０ is -O-C(=O)-Yb ０ However, in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. The aromatic ring may have an alkyl group, an alkoxy group, or both an alkyl group and an alkoxy group. The aromatic ring preferably has an alkoxy group.

[0243] The aromatic ring may have a substituent other than an alkyl group or an alkoxy group. Examples of the substituent include a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. Among these, the aromatic ring preferably has a halogen atom as a substituent, and more preferably has an iodine atom as a substituent.

[0244] Yb ０ The aromatic ring contained in the aromatic hydrocarbon group in the formula (I) is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

[0245] L ０ -Yb ０ is -O-C(=O)-Yb ０ In this case, the formula (b0) can be expressed by the following formula (b02-1):

[0246] [In the formula, Ar, Rf ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , n01, and n02, respectively. ００ is an alicyclic group which may have a substituent, a fused cyclic group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation.

[0247] Yb ０ The cyclic group in the formula (b02-1) preferably does not contain an acid-dissociable group. ００ It is also preferable that the hydroxyl group does not contain an acid-dissociable group.

[0248] The component (B0) is preferably a compound represented by the following general formula (b0-1).

[0249] [wherein, Rf ０１ represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ０１ is -C(=O)-O-, -O-C(=O)- or -O-S(=O) ２ represents a divalent linking group containing -.０１ represents a cyclic group. ０１ represents an organic group, n011 is an integer of 1 or more, n021 is an integer of 0 or more, and n011 + n021 ≦ 4. ０１ -Yb ０１ is -O-C(=O)-Yb ０１ If Yb ０１ is an alicyclic group which may have a substituent, a fused cyclic group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. ０１ may be the same or different. When n021 is 2 or more, a plurality of Rb ０１ may be the same or different, m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation.

[0250] In the formula (b0-1), Rf ０１ , Rb ０１ , L ０１ , and Yb ０１ is Rf in the formula (b0). ０ , Rb ０１ , L ０ , and Yb ０ n011 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, even more preferably 3 or 4, and particularly preferably 4. n021 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0. Rb ０１ , L ０１ , and Yb ０１ It is preferable that the alkyl group does not contain an acid-dissociable group.

[0251] The component (B0) is more preferably a compound represented by the following general formula (b0-1-1).

[0252] [In the formula, L ０１ and Yb ０１ represents L in the formula (b0-1). ０１ and Yb ０１ m is an integer of 1 or more, and Mｍ＋ represents an m-valent organic cation.

[0253] In the formula (b0-1-1), L ０１ , and Yb ０１ It is preferable that the alkyl group does not contain an acid-dissociable group.

[0254] Specific examples of the component (B0) are shown below, but are not limited to these. In the following formula, m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation.

[0255]

[0256]

[0257]

[0258] {Cation moiety} In the formula (b0), M ｍ＋ represents an m-valent onium cation. The onium cation is preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more.

[0259] Preferred cationic moieties ((M ｍ＋ ) １／ｍ ) includes organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0260] [In the formula, R ２０１ ~R ２０７ R each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. ２０１ ~R ２０３ , R ２０６ ~R ２０７ may be bonded to each other to form a ring together with the sulfur atom in the formula. ２０８ ~R ２０９ R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１０ represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an —SO ２ -containing cyclic group. ２０１represents —C(═O)— or —C(═O)—O—.]

[0261] In the above general formulas (ca-1) to (ca-3), R ２０１ ~R ２０７ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２０１ ~R ２０７ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２０１ ~R ２０７ , and R ２１０ Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulae (ca-r-1) to (ca-r-7):

[0262] [In the formula, R' ２０１ are each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0263] Cyclic group which may have a substituent: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic 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.

[0264] R' ２０１The aromatic group in the formula (I) is a 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. It may be monocyclic or polycyclic, and may have a substituent substituting a hydrogen atom on the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which a portion of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. The aromatic hydrocarbon ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 5 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent substituting a hydrogen atom on the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0265] R' ２０１ Specific examples of the aromatic group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0266] R' ２０１Examples of the cyclic aliphatic hydrocarbon group in the formula (I) include aliphatic hydrocarbon groups containing a ring within their structure. Examples of aliphatic hydrocarbon groups containing a ring within their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed within a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be either a polycyclic group or a monocyclic group. Preferred monocyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a monocycloalkane. Preferred monocycloalkanes have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Preferred polycyclic alicyclic hydrocarbon groups are groups in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0] ２，６ ] Polycycloalkanes having a polycyclic skeleton of a bridged ring system, such as decane and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid skeleton, are more preferred.

[0267] Among them, R' ２０１ The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0268] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, a methylene group [—CH ２-], ethylene group [-(CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, —CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ alkylethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ alkyltrimethylene groups such as -; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0269] Also, R' ２０１ The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specifically, lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7), —SO 2 represented by the general formulae (b5-r-1) to (b5-r-4), ２ -containing cyclic groups, and other heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16), respectively.

[0270] R' ２０１ Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. The halogen atom as a substituent is preferably a fluorine atom. Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group, in which some or all of the hydrogen atoms have been substituted with the halogen atoms. The carbonyl group as a substituent is a methylene group (-CH ２ -) is a group that substitutes

[0271] A chain alkyl group which may have a substituent: R' ２０１The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0272] A chain alkenyl group which may have a substituent: R' ２０１ The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Examples of linear alkenyl groups include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of branched alkenyl groups include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, a linear alkenyl group is preferred, a vinyl group or a propenyl group is more preferred, and a vinyl group is particularly preferred.

[0273] R' ２０１ Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above-mentioned R' ２０１ Examples of the cyclic groups include the cyclic groups shown in the formula:

[0274] R' ２０１In addition to the above-mentioned optionally substituted cyclic groups, optionally substituted chain alkyl groups, and optionally substituted chain alkenyl groups, examples of the optionally substituted cyclic groups or optionally substituted chain alkyl groups include those similar to the acid-dissociable group represented by formula (a1-r-2) above.

[0275] Among them, R' ２０１ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7); ２ -containing cyclic groups are preferred.

[0276] In the above general formulas (ca-1) to (ca-3), R ２０１ ~R ２０３ , R ２０６ ~R ２０７ When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not substituted with heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or with carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -COO-, -CONH- or -N(R Ｎ )-(the R Ｎ is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0277] R ２０８ ~R ２０９each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0278] R ２１０ represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an —SO ２ -containing cyclic group. ２１０ The aryl group in R is an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. ２１０ The alkyl group in R is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in R preferably has 2 to 10 carbon atoms. ２１０ -SO which may have a substituent ２ Examples of the -containing cyclic group include "-SO ２ -containing polycyclic group" is preferred, and a group represented by the above general formula (b5-r-1) is more preferred.

[0279] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-96).

[0280]

[0281]

[0282] [In the formula, g2 and g3 represent the number of repeating units, g2 is an integer of 0 to 20, and g3 is an integer of 1 to 20.]

[0283]

[0284]

[0285] [In the formula, R” ２０１ is a hydrogen atom or a substituent, and the substituent is the same as R ２０１ ~R ２０７ , and R２１０ The substituents are the same as those exemplified as the substituents that may be possessed by

[0286]

[0287]

[0288]

[0289] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0290] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0291]

[0292] Among the above, the cation part ((M ｍ＋ ) １／ｍ ) is preferably a cation represented by general formula (ca-1).

[0293] Specific examples of the component (B0) are shown below, but are not limited to these.

[0294]

[0295]

[0296]

[0297]

[0298] In the resist composition of this embodiment, the component (B0) may be used alone, or two or more types may be used in combination. In the resist composition of this embodiment, the amount of component (B0) relative to 100 parts by mass of component (A) is preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass. When the amount of component (B0) is at least as large as the lower limit of the above-mentioned preferred range, lithography properties such as sensitivity and reduced LWR (line width roughness) are further improved during resist pattern formation. On the other hand, when the amount is at most the upper limit of the preferred range, a homogeneous solution is more likely to be obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.

[0299] The proportion of the component (B0) in the entire component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more, and may be 100% by mass.

[0300] The component (B) may contain an acid generator component (B1) (hereinafter also referred to as "component (B1)") other than the above-mentioned component (B0). However, the component (B1) is a compound that does not fall under the category of PFAS. In other words, the component (B1) does not include any compound having a trifluoromethyl group (excluding the group represented by the general formula (np1)) or any compound having a difluoromethylene group (excluding the group represented by the general formula (np2) or (np3)).

[0301] Examples of the component (B1) include a wide variety of acid generators, such as onium salt-based acid generators such as iodonium salts and sulfonium salts; oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

[0302] In the resist composition of this embodiment, the component (B1) may be used alone, or two or more types may be used in combination. When the resist composition of this embodiment contains the component (B1), the proportion of the component (B1) relative to the entire component (B) is preferably less than 50 mass%, more preferably 40 mass% or less, even more preferably 30 mass% or less, and particularly preferably less than 20 mass%. From the perspective of environmental impact, it is preferable that the resist composition of this embodiment does not contain the component (B1).

[0303] <<Method for Producing Compound (B0)>> Compound (B0) can be produced by combining known methods.

[0304] L in the formula (b0) ０ The compound in which is a divalent linking group containing —C(═O)—O— (hereinafter also referred to as “compound (B0-a)”) can be obtained by the following reaction (Ia) and reaction (IIa).

[0305] Reaction (Ia): In reaction (Ia), a compound represented by the following general formula (Xa) reacts with a compound represented by the following general formula (Ya) to obtain a compound represented by the following general formula (Bpre0-a).

[0306] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ａ and Ly ａ are each independently a single bond or a divalent linking group.

[0307] Lx ａ and Ly ａ The divalent linking group in formula (L0-1) is preferably an alkylene group having 1 to 5 carbon atoms. ０１ The same can be mentioned.

[0308] Reaction (IIa): In reaction (IIa), a compound represented by general formula (Bpre0-a) is subjected to a salt exchange reaction with a compound represented by the following general formula (Z) to obtain a compound (B0-a).

[0309] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ａ and Ly ａ are each independently a single bond or a divalent linking group.

[0310] L in the formula (b0) ０ The compound in which is a divalent linking group containing —O—S(═O)— (hereinafter also referred to as “compound (B0-b)”) can be obtained by the following reaction (Ib) and reaction (IIb).

[0311] Reaction (Ib): In reaction (Ib), a compound represented by the following general formula (Xb) reacts with a compound represented by the following general formula (Yb) to obtain a compound represented by the following general formula (Bpre0-b).

[0312] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ｂ and Ly ｂ are each independently a single bond or a divalent linking group.

[0313] Lx ｂ and Ly ｂ The divalent linking group in formula (L0-1) is preferably an alkylene group having 1 to 5 carbon atoms. ０１ The same can be mentioned.

[0314] Reaction (IIb): In reaction (IIb), a compound represented by general formula (Bpre0-b) is subjected to a salt exchange reaction with a compound represented by the following general formula (Z) to obtain a compound (B0-b).

[0315] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ｂ and Ly ｂ are each independently a single bond or a divalent linking group.

[0316] L in the formula (b0) ０ The compound in which is a divalent linking group containing —O—C(═O)— (hereinafter also referred to as “compound (B0-c)”) can be obtained by the following reaction (Ic) and reaction (IIc).

[0317] Reaction (Ic): In reaction (Ic), a compound represented by the following general formula (Xc) reacts with a compound represented by the following general formula (Yc) to obtain a compound represented by the following general formula (Bpre0-c).

[0318] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ｃ and Ly ｃ are each independently a single bond or a divalent linking group.

[0319] Lx ｃ and Ly ｃ The divalent linking group in formula (L0-1) is preferably an alkylene group having 1 to 5 carbon atoms. ０１ The same can be mentioned.

[0320] Reaction (IIc): In reaction (IIc), a compound (B0-c) is obtained by carrying out a salt exchange reaction between a compound represented by general formula (Bpre0-c) and a compound represented by the following general formula (Z):

[0321] [In the reaction formula, Ar, Rf ０ , Rb ０ , Yb ０ , n01, and n02 represent Ar, Rf in the formula (b0). ０ , Rb ０ , Yb ０ , n01, and n02, respectively. ｃ and Ly ｃ are each independently a single bond or a divalent linking group.

[0322] The temperature conditions for reaction (Ia) are not particularly limited and are, for example, about −10 to 120° C., preferably 0 to 100° C., and more preferably 10 to 70° C. The reaction time for reaction (Ia) is not particularly limited and is, for example, about 1 to 72 hours, and preferably 1 to 24 hours.

[0323] Examples of the reaction solvent used in the above reaction (Ia) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0324] The condensation reaction in reaction (Ia) may be carried out in the presence of a condensing agent, such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, or carbonyldiimidazole (CDI).

[0325] Reaction (Ia) may be carried out using a basic catalyst, and specific examples of the basic catalyst include tertiary amines such as trimethylamine, triethylamine, and tributylamine, aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine, diazabicyclononene (DBN), and diazabicycloundecene (DBU).

[0326] The temperature conditions for reactions (Ib) and (Ic) are not particularly limited and are, for example, about −10 to 50° C., preferably 0 to 20° C., and more preferably 0 to 10° C. The reaction times for reactions (Ib) and (Ic) are not particularly limited and are, for example, about 1 to 72 hours, and preferably 1 to 24 hours.

[0327] Examples of reaction solvents used in the above reactions (Ib) and (Ic) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0328] Reactions (Ib) and (Ic) may be carried out using a basic catalyst, specifically, tertiary amines such as trimethylamine, triethylamine, and tributylamine, aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine, diazabicyclononene (DBN), diazabicycloundecene (DBU), and the like.

[0329] The temperature conditions for reactions (IIa) to (IIc) are not particularly limited and are, for example, about 0 to 50° C. The reaction times for reactions (IIa) to (IIc) are not particularly limited and are, for example, about 1 minute to 24 hours.

[0330] The reaction solvent for reactions (IIa) to (IIc) is preferably, for example, a mixed solvent of an organic solvent and water. Examples of the organic solvent include ketone solvents such as cyclohexanone, methyl ethyl ketone, and diethyl ketone; ether solvents such as diethyl ether, t-butyl methyl ether, and diisopropyl ether; halogenated solvents such as tetrahydrofuran, 1,3-dioxolane, dichloromethane (methylene chloride), and 1,2-dichloroethane; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate; propionitrile; and mixed solvents thereof.

[0331] After the completion of the reactions (IIa) to (IIc), the compound (B0) in the reaction mixture may be isolated and purified. For the isolation and purification, a conventionally known method can be used, for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc., which can be used alone or in combination of two or more of these. The structure of the compound obtained as described above is １ H-nuclear magnetic resonance (NMR) spectroscopy, １３ C-NMR spectroscopy, １９ This can be confirmed by common organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.

[0332] <Surfactant Component (G)> The resist composition of this embodiment contains, in addition to the above-described components (A) and (B), a surfactant component (G) (component (G)). The component (G) contains component (G0). The component (G0) contains at least one surfactant selected from the group consisting of components (G01) and (G02) described below.

[0333] Component (G) does not contain any compound that falls under PFAS. That is, component (G) does not contain any compound having a trifluoromethyl group (excluding the group represented by general formula (np1)) or any compound having a difluoromethylene group (excluding the group represented by general formula (np2) or (np3)). Furthermore, components (G01) and (G02) are compounds that do not fall under PFAS. That is, components (G01) and (G02) do not contain any compound having a trifluoromethyl group (excluding the group represented by general formula (np1)) or any compound having a difluoromethylene group (excluding the group represented by general formula (np2) or (np3)).

[0334] <<(G01) Component>> The (G01) component is a surfactant that is prepared by mixing a solution of the (G01) component, in which a resin (P1) represented by the following formula (P-1) is dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 20% by mass, with a solution of the (G01) component, in which the (G01) component is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 1% by mass. A first water contact angle with respect to a first resin film formed using the first resin solution containing 0.08 parts by mass of the (G01) component per 100 parts by mass of the resin (P1) is 8 degrees or more larger than a second water contact angle with respect to a second resin film formed using a second resin solution prepared by dissolving the resin (P1) in propylene glycol monomethyl ether to a concentration of 20% by mass.

[0335]

[0336] Whether a surfactant can be used as the component (G01) can be evaluated, for example, as follows, as described in the Examples below.

[0337] Resin (P1) is dissolved in PGME to a final concentration of 20% by mass to prepare a PGME solution of resin (P1). A surfactant is dissolved in PGMEA to a final concentration of 1% by mass to prepare a PGMEA solution of the surfactant. The PGMEA solution of the surfactant is added to the PGME solution of resin (P1) to prepare a resin (P1) / surfactant solution. In this case, the resin (P1) / surfactant solution is prepared so that the surfactant is present in an amount of 0.08 parts by mass per 100 parts by mass of resin (P1). A first resin film is formed on a silicon wafer using the resin (P1) / surfactant solution. The resin (P1) / surfactant solution is applied to a silicon wafer, baked on a hot plate or the like at 100°C for 60 seconds, and dried to form a first resin film. On the other hand, a second resin film is formed on a silicon wafer using a PGME solution of resin (P1) without the addition of a PGMEA solution of surfactant. The PGME solution of resin (P1) is applied to a silicon wafer, baked on a hot plate or the like at 100°C for 60 seconds, and then dried to form a second resin film. Water is dropped onto the first resin film, and the contact angle of water (contact angle of the first water) is measured using a contact angle meter or the like. Water is dropped onto the second resin film, and the contact angle of water (contact angle of the second water) is measured using a contact angle meter or the like. If the contact angle of the first water is 8 degrees or more larger than the contact angle of the second water, the surfactant can be used as the (G01) component. The contact angle measurement can be performed at room temperature (15 to 30°C, for example, 25°C).

[0338] Examples of the component (G01) include silicone surfactants. Silicon surfactants are surfactants that include a structure represented by the following general formula (g01-1):

[0339] [In the formula, Rg ０１１ and Rg ０１２ each independently represents an alkyl group having 1 to 6 carbon atoms.

[0340] In the formula (g01-1), Rg ０１１ and Rg ０１２The alkyl group in Rg may be linear or branched, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. ０１１ and Rg ０１２ As the alkyl group, a methyl group is preferred.

[0341] Examples of surfactants containing a structure represented by general formula (g01-1) include surfactants containing a structure represented by general formula (g01-2) below.

[0342] [In the formula, Rg ０２１１ are each independently an alkyl group having 1 to 6 carbon atoms or —OSi(Rg ０２１４ ) ３ A group represented by (Rg ０２１４ Rg each independently represents an alkyl group having 1 to 3 carbon atoms. ０２１２ and Rg ０２１３ each independently represents an alkyl group having 1 to 6 carbon atoms, and w represents the number of repetitions, and the number average value of w is in the range of 1 to 100.

[0343] In the formula (g01-2), Rg ０２１１ , Rg ０２１２ , and Rg ０２１３ The alkyl group in may be linear or branched, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.

[0344] Rg ０２１１ is -OSi(Rg ０２１４ ) ３ When Rg is a group represented by ０２１４ The alkyl group in Rg may be linear or branched, but is preferably linear. ０２１４ is preferably a methyl group. ０２１４ may be the same or different, but are preferably the same.

[0345] In the general formula (g01-2), Rg ０２１１ is preferably a methyl group or a trimethylsiloxy group, and Rg ０２１２ and Rg０２１３ is preferably a methyl group.

[0346] In the general formula (g01-2), w represents the number of repeating units, and may be, for example, an integer of 1 or greater. The number average of w is in the range of 1 to 50, preferably in the range of 1 to 45, more preferably in the range of 2 to 45, and even more preferably in the range of 3 to 45. The number average of w can be calculated by measuring the number average molecular weight of the silicone surfactant represented by the general formula (g01-2) using the method described in the Examples. The "number average of w" refers to the average number of repeating units in parentheses per molecule of the silicone surfactant containing the structure represented by the general formula (g01-2).

[0347] In the general formula (g01-2), a plurality of Rg ０２１１ Similarly, multiple Rg ０２１２ may be the same or different from each other.

[0348] Examples of silicone surfactants include compounds represented by the following general formula (g01-1-1):

[0349] [In the formula, Rg １１ represents a methyl group or a group represented by the following general formula (Rg01-1): １２ each independently represents an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (Rg01-1), where a is an integer of 0 or more, and b is an integer of 1 or more. １１ is a methyl group, a is 0.

[0350] [In the formula, p represents an integer of 1 or more, s and t represent integers of 0 or more, and q represents an integer of 1 or more, provided that s + t ≧ 1. １３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a (meth)acrylic group.

[0351] In the formula (g01-1-1), p can be an integer of 1 to 6. In the formula (g01-1-1), s can be an integer of 0 to 50. In the formula (g01-1-1), t can be an integer of 0 to 50. In the formula (g01-1-1), q can be an integer of 1 to 10. The addition pattern of the ethylene oxide groups and propylene oxide groups in [ ] may be block or random.

[0352] Examples of silicone surfactants include those described in WO 2023 / 140036 and WO 2024 / 101164. Examples of such silicone surfactants include silicone chain-containing polymers whose polymerization components are a polymerizable monomer (1) containing a structure represented by the general formula (g01-1) and a polymerizable monomer (2) having one or more groups selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain. The proportion of the polymerizable monomer (1) in the polymerization components is preferably 20% by weight or less. Examples of the polymerizable monomer (1) include a polymerizable monomer (1-2) containing a structure represented by the general formula (g01-2).

[0353] When the polymerizable monomer (1) is a compound represented by the following general formula (g01-2-1a), the weight-average molecular weight of the silicone chain-containing polymer is preferably 1,000 to 500,000, more preferably 2,000 to 100,000, even more preferably 3,000 to 40,000, and particularly preferably 4,000 to 25,000. When the polymerizable monomer (1) is a compound represented by the following general formula (g01-2-1), the weight-average molecular weight of the silicone chain-containing polymer is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 15,000 or more.

[0354] Examples of the polymerizable monomer (1) or (1-2) include compounds represented by the following general formula (g01-2-1a).

[0355] [In the formula, Rg０２１１ , Rg ０２１２ , Rg ０２１３ and w is Rg in general formula (g01-2). ０２１１ , Rg ０２１２ , Rg ０２１３ , and w, respectively. ０２１５ represents a hydrogen atom or a methyl group. ０２１ represents a single bond or a divalent linking group.

[0356] In the formula (g01-2-1a), Lg ０２１ Examples of the divalent linking group in include an alkylene group having 1 to 50 carbon atoms which may have a substituent, and an alkyleneoxy group having 1 to 50 carbon atoms which may have a substituent.

[0357] Lg ０２１ The alkylene group having 1 to 50 carbon atoms in Lg may be linear or branched. ０２１ The alkylene group having 1 to 50 carbon atoms in Lg preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 or 1 to 5 carbon atoms. ０２１ Specific examples of the alkylene group having 1 to 50 carbon atoms in the formula (I) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0358] Lg ０２１ The alkylene group having 1 to 50 carbon atoms in the formula (I) is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.

[0359] Lg ０２１ The alkyleneoxy group having 1 to 50 carbon atoms in ２ - is substituted with -O-. ０２１The alkylene group contained in the alkyleneoxy group having 1 to 50 carbon atoms in the formula (I) may be linear or branched. ０２１ The alkyleneoxy group having 1 to 50 carbon atoms in the formula (Lg) preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 or 1 to 5 carbon atoms. ０２１ The alkyleneoxy group having 1 to 50 carbon atoms in the formula (I) is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.

[0360] Lg ０２１ The alkylene group having 1 to 50 carbon atoms or the alkyleneoxy group having 1 to 50 carbon atoms in the formula (I) may have a substituent. The substituent is one or more —CH ２ It may be a divalent group substituting -, or a monovalent group substituting one or more hydrogen atoms on an alkylene chain. ２ Examples of the divalent group substituting the - include a carbonyl group (-C(=O)-), a phenylene group, an ester bond, an amide bond, and a urethane bond. Examples of the monovalent group substituting the hydrogen atom include a hydroxyl group.

[0361] Examples of the compound represented by the above general formula (g01-2-1a) include compounds represented by the following general formula (g01-2-1).

[0362] [In the formula, Rg ０１１ ~Rg ０１５ Rg each independently represents an alkyl group having 1 to 6 carbon atoms. z represents the number of repetitions, the number average value of which is 20 or more. ０１６ represents a hydrogen atom or a methyl group. ０１ represents a single bond or a divalent linking group.

[0363] In the formula (g01-2-1), Rg ０１１ ~Rg ０１５The alkyl group in Rg may be linear or branched, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. ０１１ ~Rg ０１５ As the alkyl group, a methyl group is preferred.

[0364] Lg ０１ The divalent linking group in Lg is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms. The alkylene group and alkyleneoxy group preferably have 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. ０１ As the alkylene group having 1 to 50 carbon atoms and the alkyleneoxy group having 1 to 50 carbon atoms, Lg ０２１ Examples include those similar to those in

[0365] The alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (2) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group, etc. The aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (2) may include a phenyl group, a naphthyl group, an anthracen-1-yl group, a phenanthrene-1-yl group, etc.

[0366] The group containing a polyoxyalkylene chain contained in the polymerizable monomer (2) may be a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.

[0367] Examples of the polymerizable monomer (2) include groups represented by the following general formula (g01-3-1) or (g01-3-2).

[0368] [In the formula, Rg ０１７ represents a hydrogen atom or a methyl group. ０１８ represents an alkyl group having 1 to 18 carbon atoms.０１９ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, n represents an integer of 1 to 4, and m represents an integer of 1 to 200.

[0369] In the formula (g01-3-2), C in parentheses ｎ H2 ｎ n in O may be the same or different for each repeating unit. When n is two or more types, two or more types of (C ｎ H2 ｎ The addition pattern of n) of O may be random or block. n is preferably 2 or 3.

[0370] In the synthesis of the silicone chain-containing polymer, the mass ratio of the polymerizable monomer (1) to the polymerizable monomer (2) is preferably polymerizable monomer (1):polymerizable monomer (2)=5:95 to 95:5, more preferably 20:80 to 80:20, even more preferably 30:70 to 80:20, and particularly preferably 40:60 to 80:20.

[0371] The silicone surfactant may be synthesized by a known method or may be a commercially available product. The silicone surfactant may contain a silane condensate having either a urethane bond or a urea bond, or both.

[0372] The component (G01) may be used alone or in combination of two or more types.

[0373] <Component (G02)> The component (G02) is a surfactant containing a structure represented by the following general formula (g0-1), (g0-2), or (g0-3). However, the component (G02) is a compound that does not fall under the category of PFAS. In other words, the component (G02) does not contain any compound having a trifluoromethyl group (excluding the group represented by the general formula (np1)) or any compound having a difluoromethylene group (excluding the group represented by the general formula (np2) or (np3)).

[0374] [wherein, Rf ０１ represents a fluorinated alkyl group having one carbon atom. ０１ , each independently, is -OR０１ or -N(R ０２ ) R ０１ Rf ０２ each independently represents a fluorinated alkylene group having 1 carbon atom. ０２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ０３ , -SR ０３ , or -NR ０３ R ０４ represents. ０３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR ０１ , -SR ０１ , or -N(R ０２ ) R ０１ Represents R ０１ R each independently represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ０２ , R ０３ , and R ０４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

[0375] In the formulae (g0-1), (g0-2) and (g0-3), X ０１ -OR in ０１ or -N(R ０２ ) R ０１ In the formula, Rf ０１ or Rf ０２ The bond to R is O or N. ０１ Examples of the divalent aromatic hydrocarbon group which may have a substituent in the above formula include groups in which two carbon atoms have been removed from an aromatic ring. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. R ０１ The divalent aromatic hydrocarbon group in R may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and a hydroxyl group.０２ The monovalent aromatic hydrocarbon group in the formula (I) which may have a substituent includes a group in which one hydrogen atom has been removed from an aromatic ring which may have a substituent. ０１ The substituents are the same as those in the above R ０１ Examples include those similar to those in

[0376] In the formula (g0-2), X ０２ -OR in ０３ , -SR ０３ , or -NR ０３ R ０４ In the formula, Rf ０２ In the formula (g0-2), X is bonded to O, S or N. ０２ The monovalent aromatic hydrocarbon group in the formula (I) which may have a substituent includes a group in which one hydrogen atom has been removed from an aromatic ring which may have a substituent. ０１ The substituents are the same as those in the above R ０１ Examples include those similar to those in R ０３ and R ０４ The monovalent aromatic hydrocarbon group which may have a substituent in X ０２ The monovalent aromatic hydrocarbon group may be the same as the optionally substituted monovalent aromatic hydrocarbon group in the above formula (1).

[0377] In the formula (g0-3), X ０３ -OR in ０１ , -SR ０１ , or -N(R ０２ ) R ０１ In the formula, Rf ０２ In the formula (g0-3), X is bonded to O, S or N. ０３ The optionally substituted divalent aromatic hydrocarbon group in R ０１ The same can be mentioned.

[0378] In the formula (g0-1), Rf ０１ In the formula, the monovalent fluorinated alkyl group is —CH ２ F, -CHF ２ , -CF ３ Examples include:

[0379] In the formulas (g0-2) and (g0-3), Rf ０２ Examples of the monovalent fluorinated alkylene group in the formula (I) include -CHF- and -CF ２ - are listed.

[0380] Examples of the component (G02) include compounds containing a structure represented by the following general formula (g02-1) or (g02-2).

[0381] [In the formula, Rg ０２２ and Rg ０２３ Rg each independently represents a single bond or a divalent hydrocarbon group. ０２４ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n represents 0 or 1. k represents 0 or 1. Rf ０２１ represents a group represented by the general formula (g0-1) or (g0-2). ０２２ represents a group represented by general formula (g0-3). ０２５ represents a monovalent hydrocarbon group which may have an oxygen atom.

[0382] In the formula (g02-1), Rg ０２２ and Rg ０２３ The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkylene group. The alkylene group may be linear or branched, but is preferably linear. Examples of the alkylene group include those having 1 to 5 carbon atoms, preferably those having 1 to 3 carbon atoms, and preferably an ethylene group or a methylene group. Examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from an aromatic ring, and preferably a phenylene group.

[0383] In the formula (g02-2), Rg ０２５ The hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the aromatic hydrocarbon group include a group in which one hydrogen atom has been removed from an aromatic ring, and a group in which one hydrogen atom of the group in which one hydrogen atom has been removed from an aromatic ring is substituted with an alkylene group.

[0384] Examples of the component (G02) include compounds represented by the following general formula (g02-3).

[0385] [In the formula, A represents an alkylene group or a polyoxyalkylene group, and a, b, x, and y each independently represent an integer of 1 or greater.]

[0386] In formula (g02-3), the alkylene group for A may be linear or branched. The alkylene group for A preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0387] In the formula (g02-3), the polyoxyalkylene group for A is preferably a linear polyoxyalkylene group. The polyoxyalkylene group for A is preferably a polyoxyethylene group or a polyoxypropylene group. In the polyoxyalkylene group for A, the number of oxyalkylene units is preferably 1 to 30, more preferably 2 to 25, and even more preferably 2 to 20. Specific examples of A include -CH ２ C(CH ３ ) ２ CH ２ -, -(C ３ H ６ O) １７ - are listed.

[0388] In formula (g02-3), a+b is preferably 10 to 50, more preferably 10 to 30, and even more preferably 15 to 25. A specific example is a+b=20. In formula (g02-3), x+y is preferably 10 to 50, more preferably 10 to 30, and even more preferably 15 to 25. A specific example is x+y=20.

[0389] The (G02) component is preferably a surfactant such that the first water contact angle with respect to a first resin film formed using the first resin solution containing 0.08 parts by mass of the (G02) component per 100 parts by mass of the resin (P1) is greater by 8 degrees or more than the second water contact angle with respect to a second resin film formed using a second resin solution prepared by dissolving the resin (P1) in propylene glycol monomethyl ether (PGME) to a concentration of 20% by mass. In other words, the (G02) component is preferably a surfactant that also corresponds to the (G01) component.

[0390] When a surfactant corresponding to the component (G01) contains a structure represented by any one of the formulae (g0-1) to (g0-3), the surfactant corresponds to both the component (G01) and the component (G02).

[0391] The component (G02) may be synthesized by combining known methods such as those described in Japanese Patent No. 4017988, or a commercially available product may be used.

[0392] The component (G02) may be used alone or in combination of two or more types.

[0393] In the resist composition of this embodiment, the component (G0) may be used alone or in combination with two or more different surfactants. The component (G0) may be the component (G01) or the component (G02), or the components (G01) and (G02) may be used in combination, or a surfactant corresponding to both the components (G01) and (G02) may be used.

[0394] Within the resist composition of this embodiment, the amount of the component (G0) relative to 100 parts by mass of the component (A) is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.01 to 1 part by mass.

[0395] <Other Components> The resist composition of this embodiment may further contain other components in addition to the above-described components (A), (B), and (G). Examples of other components include the following components (D), (E), and (S).

[0396] It is preferable that the components (D), (E), and (S) do not contain a compound that corresponds to PFAS. It is preferable that the components (D), (E), and (S) do not contain any compound having a trifluoromethyl group (excluding the group represented by the general formula (np1)) or a compound having a difluoromethylene group (excluding the group represented by the general formula (np2) or (np3)).

[0397] <<Base Component (D)>> In addition to the components (A) and (B), the resist composition of this embodiment may contain a base component (component (D)) that traps acid generated upon exposure (i.e., controls the diffusion of acid). The component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure. Examples of the component (D) include a photodegradable base (D1) (hereinafter referred to as “component (D1)”) that decomposes upon exposure and loses its ability to control acid diffusion, and a nitrogen-containing organic compound (D2) (hereinafter referred to as “component (D2)”) that does not fall under the category of component (D1). Among these, the photodegradable base (component (D1)) is preferred because it is likely to enhance all of the properties of high sensitivity, reduced roughness, and suppressed coating defects.

[0398] Regarding the component (D1): The component (D1) is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"). The components (d1-1) to (d1-3) decompose and lose their acid diffusion controllability (basicity) in the exposed areas of the resist film, and therefore do not act as quenchers, but act as quenchers in the unexposed areas of the resist film.

[0399] [In the formula, Rd １ ~Rd ４ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. ２ In the formula, no fluorine atom is bonded to the carbon atom adjacent to the S atom. １ is a single bond or a divalent linking group; m is an integer of 1 or more; M ｍ＋ are each independently an m-valent organic cation.

[0400] {Component (d1-1)} Anion portion In formula (d1-1), Rd １ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each of the R' ２０１ Among these, Rd １is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-7), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following formulas (y-al-1) to (y-al-5). Note that Rd １ In the following general formulas (y-al-1) to (y-al-8), when the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group has, as a substituent, a linking group represented by each of the following general formulas (y-al-1) to (y-al-8), Rd in formula (d1-1) １ The carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in the formula (y-al-1) to (y-al-8) is bonded to V' １０１ is.

[0401] [In the formula, V' １０１ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' １０２ is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0402] 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.

[0403] V' １０１ and V' １０２ The alkylene group in V' may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. １０１ and V' １０２ Specific examples of the alkylene group in ２-]; -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) ２ -, -C(CH ３ ) (CH 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 -]; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, etc.; a trimethylene group (n-propylene group) [—CH ２ CH ２ CH ２ -]; -CH(CH ３ ) CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ an alkyltrimethylene group such as -; a tetramethylene group [-CH ２ CH ２ CH ２ CH ２ -]; -CH(CH ３ ) CH ２ CH ２ CH ２ -, -CH ２ CH (CH ３ ) CH ２ CH ２ -, etc.; an alkyltetramethylene group such as a pentamethylene group [—CH ２ CH ２ CH ２ CH ２ CH ２-]. Also, V' １０１ or V' １０２ In the formula (a1-r-1), some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by Ra' in the formula (a1-r-1). ３ A divalent group obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group) of the above formula (I) is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0404] Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure). Suitable examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, tricyclo[5.2.1.0], ２，６

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

[0405] When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0406] Specific examples of preferred anion moieties for the component (d1-1) are shown below. Of the anion moieties listed below, those that do not contain trifluoromethyl groups or difluoromethylene groups are more preferred from the perspective of reducing the burden on the environment.

[0407]

[0408] ...cation moiety In formula (d1-1), M ｍ＋ is an m-valent organic cation. ｍ＋ Suitable examples of the organic cation include the same as the cations represented by the general formulas (ca-1) to (ca-3), with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the general formulas (ca-1-1) to (ca-1-96) being even more preferred. One type of component (d1-1) may be used alone, or two or more types may be used in combination.

[0409] {Component (d1-2)} Anion portion In formula (d1-2), Rd ２ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ However, Rd ２ In the formula, the carbon atom adjacent to the S atom is not bonded to a fluorine atom (is not substituted with fluorine). This makes the anion of component (d1-2) an appropriately weak acid anion, improving the quenching ability of component (D). ２ The alkyl group is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.

[0410] The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10. The aliphatic cyclic group includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0], ２，６] a group (which may have a substituent) in which one or more hydrogen atoms have been removed from decane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor is more preferred.

[0411] Rd ２ The hydrocarbon group may have a substituent, and the substituent may be Rd １ Examples of the substituents include the same as those that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above.

[0412] Specific examples of preferred anion moieties of component (d1-2) are shown below.

[0413]

[0414] In formula (d1-2), M ｍ＋ is an m-valent organic cation, and M in the formula (d1-1) ｍ＋ The component (d1-2) may be used alone or in combination of two or more.

[0415] {Component (d1-3)} Anion portion In formula (d1-3), Rd ３ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ Among these, a fluorinated alkyl group is preferred, and the Rd １ The same fluorinated alkyl groups as those mentioned above are more preferred.

[0416] In formula (d1-3), Rd ４ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and ２０１ Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent, is preferable. ４The alkyl group in Rd is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. ４ A part of the hydrogen atoms of the alkyl group may be substituted with a hydroxyl group, a cyano group, etc. ４ The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.

[0417] Rd ４ The alkenyl group in R' ２０１ Examples include the same alkenyl groups as those in the above, and vinyl, propenyl (allyl), 1-methylpropenyl, and 2-methylpropenyl groups are preferred. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

[0418] Rd ４ The cyclic group in the formula (I) is the same as the R' ２０１ Examples thereof include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0], and the like. ２，６ ] An alicyclic group in which one or more hydrogen atoms have been removed from a cycloalkane such as decane or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group is preferred. ４ When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in excellent lithography properties. ４ When is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition exhibits excellent light absorption efficiency, and exhibits favorable sensitivity and lithography properties.

[0419] In formula (d1-3), Yd １ represents a single bond or a divalent linking group. １The divalent linking group in is not particularly limited, but examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. ２１ Examples of the divalent linking group include the same divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom as those mentioned in the description of the divalent linking group in １ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.

[0420] Specific examples of preferred anion moieties of component (d1-3) are shown below.

[0421]

[0422]

[0423] In formula (d1-3), M ｍ＋ is an m-valent organic cation, and M in the formula (d1-1) ｍ＋ The component (d1-3) may be used alone or in combination of two or more.

[0424] The component (D1) may use either a single kind of any one of the above components (d1-1) to (d1-3), or a combination of two or more kinds. From the standpoint of reducing the burden on the environment, the component (D1) is preferably either a single kind of the component (d1-1) or the component (d1-2), or a combination of two or more kinds thereof. When the resist composition contains the component (D1), the amount of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0425] The component (D1) preferably contains the component (d1-1). The content of the component (d1-1) in the entire component (D1) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. The component (D1) may consist solely of the compound component (d1-1).

[0426] Production method of component (D1): The production methods of the components (d1-1) and (d1-2) are not particularly limited, and they can be produced by known methods. The production method of component (d1-3) is also not particularly limited, and it can be produced, for example, by the method described in US 2012-0149916.

[0427] Regarding the (D2) component: The (D) component may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not fall under the category of the above-mentioned (D1) component. The (D2) component is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of the (D1) component, and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. Examples of the aliphatic amine include ammonia NH ３Examples of the amine include amines in which at least one hydrogen atom is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), and cyclic amines. Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

[0428] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. Specific examples of aliphatic polycyclic amines include those having 6 to 10 carbon atoms, such as 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0429] 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, and the like, with triethanolamine triacetate being preferred.

[0430] Furthermore, the component (D2) may be an aromatic amine, such as 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole, or a derivative thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, or 2,6-di-tert-butylpyridine.

[0431] The component (D2) may be used singly, or in combination of two or more types. When the resist composition contains the component (D2), the amount of the component (D2) within the resist composition is typically within a range from 0.01 to 5 parts by mass per 100 parts by mass of the component (A1). By ensuring that the amount is within this range, the resist pattern shape and stability over time during storage can be improved.

[0432] <<At least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxo acids and their derivatives>> The resist composition of this embodiment may contain at least one compound (E) (hereinafter referred to as "component (E)") selected from the group consisting of organic carboxylic acids, and phosphorus oxo acids and their derivatives as an optional component for the purposes of preventing sensitivity degradation and improving resist pattern shape and post-exposure stability. Specific examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, with salicylic acid being preferred. Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.

[0433] In the resist composition of this embodiment, the component (E) may be used singly, or two or more different components may be used in combination. When the resist composition contains the component (E), the amount of the component (E) per 100 parts by mass of the component (A) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. By ensuring that the amount is within this range, lithography properties are further improved.

[0434] <Organic Solvent Component (S)> The resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as "component (S)"). In the resist composition of this embodiment, the component (S) may be used alone, or as a mixed solvent of two or more different solvents. Of these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0435] Also preferred as the (S) component is a mixed solvent of PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into consideration the compatibility of PGMEA with the polar solvent, etc. Also preferred as the (S) component is a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of the (S) component is not particularly limited and is appropriately set according to the coating film thickness at a concentration that allows application to a substrate, etc. The (S) component is generally used so that the solids concentration of the resist composition is within the range of 0.1 to 20 mass%, preferably 0.2 to 15 mass%.

[0436] In the resist composition of this embodiment, after dissolving the resist material in component (S), impurities may be removed using a polyimide porous film, a polyamideimide porous film, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film. Examples of the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.

[0437] The resist composition preferably does not contain a compound that corresponds to PFAS. In other words, the components contained in the resist composition preferably do not contain a compound having a trifluoromethyl group (excluding the group represented by general formula (np1) above) or a compound having a difluoromethylene group (excluding the group represented by general formula (np2) or (np3) above).

[0438] The resist composition of the present embodiment described above contains compounds (B0) and (G0) as acid generator components, enabling the formation of resist patterns with excellent pattern shapes comparable to those of resist compositions containing PFAS. Compound (B0) has a bulky structure due to the presence of an aromatic ring containing a fluorine atom as a substituent between the cyclic group and the sulfonic acid group. It is believed that such a bulky structure provides sufficient acid strength and improves lithography properties. Furthermore, because the carbon atom adjacent to the sulfonic acid group of compound (B0) is not fluorinated, it is believed that there is a low risk of it being subject to future use and production restrictions. Because components (G) and (B) do not contain compounds that fall under the PFAS category, it is believed that there is a low risk of it being subject to future use and production restrictions.

[0439] (Method of Forming a Resist Pattern) The method of forming a resist pattern pertaining to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition pertaining to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern. One embodiment of the method of forming a resist pattern can be exemplified by a method of forming a resist pattern as follows.

[0440] First, the resist composition of the above-described embodiment is applied to a support using a spinner or the like, and baked (post-applied bake (PAB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C to form a resist film. Next, the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF lithography device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with electron beams without a mask pattern. The resist film is then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C. Next, the resist film is developed. In the case of an alkali development process, the development is performed using an alkaline developer, and in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0441] After the development treatment, a rinse treatment is preferably carried out. In the case of an alkaline development process, the rinse treatment is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse solution containing an organic solvent is preferably used. In the case of a solvent development process, after the development treatment or rinse treatment, a treatment may be carried out to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After the development treatment or rinse treatment, drying is carried out. Furthermore, in some cases, a bake treatment (post-bake) may be carried out after the development treatment.

[0442] The support is not particularly limited, and conventionally known supports can be used, such as substrates for electronic components and those on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials that can be used for the wiring pattern include copper, aluminum, nickel, and gold.

[0443] The wavelength used for exposure is not particularly limited, and may be an ArF excimer laser, a KrF excimer laser, or a F ２Radiation such as excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray can be used.

[0444] The exposure method for the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion exposure (liquid immersion lithography). Liquid immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure apparatus is filled in advance with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in this state. The liquid immersion medium is preferably a solvent having a refractive index greater than that of air and smaller than that of the resist film to be exposed, and examples thereof include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent. Water is preferably used as the liquid immersion medium.

[0445] An example of an alkaline developer used in the development treatment in the alkaline development process is a 0.1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent that can dissolve component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0446] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0447] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0448] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants.

[0449] The development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying the developer onto the surface of the support (spray method), or a method of continuously applying the developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0450] The organic solvent contained in the rinse solution used in the rinsing treatment after development in the solvent development process can be appropriately selected from the organic solvents listed above as organic solvents used in the organic developer, as long as they do not easily dissolve the resist pattern. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination with two or more. They may also be used in combination with other organic solvents or water.

[0451] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method, such as a method of continuously applying the rinse solution onto a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse solution for a certain period of time (dipping method), or a method of spraying the rinse solution onto the surface of the support (spray method).

[0452] According to the resist pattern forming method of the present embodiment as explained above, the resist composition described above is used, and therefore it is possible to form a resist pattern with an excellent pattern shape equivalent to that achieved when a resist composition containing PFAS is used, while reducing the environmental impact.

[0453] The resist composition of the above-described embodiment and the various materials used in the pattern formation method of the above-described embodiment (e.g., resist solvent, developer, rinse, anti-reflective coating composition, top coat composition, etc.) preferably do not contain impurities such as metals, halogen-containing metal salts, acids, alkalis, or components containing sulfur or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free of impurities (below the detection limit of the measuring device).

[0454] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0455] <Surfactants> In the following tests, the following surfactants (G0-1), (G0-2), (G1-1) to (G1-4) were used. Each surfactant can be synthesized by combining known methods such as those described in Japanese Patent No. 4017988 (particularly Examples M1 to M4, P1 to P3, and CP).

[0456] G0-1: a surfactant represented by the following formula (g-1): １ and R ２ is CF ３ O-Ph-, a+b=20, and x+y=20. Ph represents a phenylene group. G0-2: A surfactant represented by the following formula (g-2). In the following formula (g-2), R １ and R ２ is CF ３ O-Ph-, a+b=20, and x+y=20. G1-1: A surfactant represented by the following formula (g-1), where R １ and R ２ is C ２０ H ４１ and CH ３ O (C ３ H ６ O) (C ３ H ６ ) R １ and R ２ is C ２０ H ４１ For the structural unit, a+b=2 and x+y=2. １ and R ２ is CH ３ O (C ３ H ６ O) (C ３ H ６ G1-2: A surfactant represented by the following formula (g-1): In the following formula (g-1), １ and R ２ is C ４ H９ and CH ３ O (C ３ H ６ O) (C ３ H ６ ) R １ and R ２ is C ２０ H ４１ For a constitutional unit, a+b=4 and x+y=4. １ and R ２ is CH ３ O (C ３ H ６ O) (C ３ H ６ G1-3: A surfactant represented by the following formula (g-1): In the following formula (g-1), R １ and R ２ is C ４ H ９ and CH ３ O (C ３ H ６ O) (C ３ H ６ ) R １ and R ２ is C ４ H ９ For a constitutional unit, a+b=4 and x+y=4. １ and R ２ is CH ３ O (C ３ H ６ O) (C ３ H ６ G1-4: A surfactant represented by the following formula (g-1), wherein in the following formula (g-1), R １ and R ２ is C １０ H ２１ , a+b=6, and x+y=6.

[0457]

[0458] [Surfactant Solubility Evaluation Test] Each surfactant was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a final concentration of 1% by mass. The solution was then visually observed, and the solubility was evaluated according to the following evaluation criteria. The results are shown in Table 1 as "Solubility." (Evaluation criteria) A: No cloudiness B: Cloudiness

[0459]

[0460] The surfactants (G0-1) and (G0-2) were confirmed to have good solubility.

[0461] <Formation of Resin Film> A resin (P1) solution was prepared by dissolving a resin (P1) represented by the following formula (P-1) in propylene glycol monomethyl ether (PGME) to a final concentration of 20% by mass. A surfactant solution was also prepared by dissolving the surfactant of each example in propylene glycol monomethyl ether acetate (PGMEA) to a final concentration of 1% by mass. The surfactant PGMEA solution was then added to the resin (P1) solution to prepare a resin (P1) / surfactant solution. The surfactant was added at 0.08 parts by mass or 0.30 parts by mass per 100 parts by mass of resin (P1).

[0462]

[0463] The resin (P1) / surfactant solution was applied onto a silicon wafer, baked on a hot plate at 100° C. for 60 seconds, and dried to form a resin film.

[0464] [Contact angle measurement] Water was dropped onto the resin film formed in <Formation of resin film>, and the contact angle was measured using a contact angle meter. The results are shown in Table 2 as "contact angle." The results in Table 2 are shown as an increase or decrease in the contact angle compared to the contact angle measured for a resin film formed using a resin (P1) solution to which no surfactant was added. A value indicated by "+" indicates an increase compared to the contact angle for the resin (P1) film. A value indicated by "-" indicates a decrease compared to the contact angle for the resin (P1) film.

[0465] [Wafer Visual Inspection Test] The resin film formed in <Formation of Resin Film> was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 2 as "Coating Property". (Evaluation Criteria) A: No coating unevenness B: Coating unevenness

[0466] [Film Thickness Leveling] The film thickness of the resin film formed in <Formation of Resin Film> was measured at 25 points in the lateral direction using a film thickness measuring device Nanospec (manufactured by Nanometrics). The standard deviation calculated from the measurement results is shown in Table 2 as "film thickness leveling." A smaller value indicates better leveling.

[0467]

[0468] In Table 2, the abbreviations have the following meanings: The numbers in brackets [ ] are the blend amounts (parts by mass).

[0469] P1: the above resin (P1) G0-1, G0-2: the above surfactants (G0-1) and (G0-2) G0-3: a silicone surfactant (a silicone chain-containing polymer obtained by polymerization of polypropylene glycol-polybutylene glycol-monomethacrylate (average repeat number of propylene glycol: 1, average repeat number of butylene glycol: 6) with a monomethacrylate compound having a polysiloxane bond represented by the following formula (g03-1). This was synthesized by the method described in Synthesis Example 1 of WO 2023 / 140036). G0-4: a silicone surfactant (a silicone chain-containing polymer obtained by polymerization of polypropylene glycol monomethacrylate with a monomethacrylate compound having a polysiloxane bond represented by the following formula (g04-1). This was synthesized by the method described in Synthesis Example 2 of WO 2024 / 101164).

[0470] [Wherein the formula, the number average of x1 is 65.]

[0471] [Wherein the formula, the number average of x2 is 10.]

[0472] G1-1 to G1-4: The above surfactants (G1-1) to (G1-4) G2-1: Fluorine-based surfactant (trade name: R-40, manufactured by DIC Corporation); a surfactant corresponding to PFAS

[0473] From the results shown in Table 2, it was confirmed that the surfactants (G0-1) to (G0-4) improve the coating properties and film thickness leveling properties of the resin liquid.

[0474] <Synthesis Examples of Compounds> [Synthesis Example 1: Compound (B0-1)] Under a nitrogen atmosphere, 20.0 g of compound (X1), 13.3 g of compound (Y1), 18.5 g of triethylamine, and 100 g of dichloromethane were added to a three-neck flask and stirred at 10°C or below. 12.0 g of diisopropylcarbodiimide was added thereto while maintaining the temperature, and the mixture was stirred at 10°C or below for 0.5 hours. The temperature was then raised to 25°C and the mixture was stirred for 12 hours. Thereafter, the reaction solution was filtered, and the filtrate was washed with 100 g of a 1% aqueous hydrochloric acid solution and then washed four times with 100 g of water. After washing, the mixture was added dropwise to 500 g of hexane with stirring, stirred for 30 minutes, and then filtered. The resulting powder was dried to obtain 20.4 g of compound (Bpre-1).

[0475]

[0476] Precursor (Bpre0-1) (20 g, 58 mmol) and compound Z1 (28 g, 55 mmol) were dissolved in dichloromethane (80 g), and ultrapure water (80 g) was added. The mixture was allowed to react at room temperature for 30 minutes. After the reaction was completed, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (80 g). The organic phase was concentrated to dryness using a rotary evaporator to obtain compound (B0-1) (30 g, yield = 82%).

[0477]

[0478] The resulting compound (B0-1) was subjected to NMR measurement, and its structure was identified from the following analytical results. １H-NMR (DMSO, 400MHz): δ (ppm) = 1.60-1.91 (m, CH + CH2, 3H), 2.13-2.25 (m, CH2, 2H ), 2.62-2.84 (m, CH, 2H), 4.65 (m, CH, 1H), 5.23 (m, CH, 1H), 7.74-7.90 (m, CH, 15H)

[0479] Synthesis Example 2: Compound (B0-2) In a nitrogen atmosphere, 15.2 g of compound (X2), 14.4 g of triethylamine (TEA), and dichloromethane (CH ２ Cl ２ 60.8 g of compound (Y2) and dichloromethane (CH ２ Cl ２ A 13.5 g solution of 1% hydrochloric acid was added while maintaining the temperature below 10°C, and the mixture was stirred at 10°C or below for 16 hours. The reaction mixture was then washed with 60.8 g of a 1% aqueous hydrochloric acid solution and then washed four times with 60.8 g of water. After washing, the mixture was added dropwise to 304 g of hexane while stirring, and after stirring for 30 minutes, the mixture was filtered. The resulting powder was dried, yielding 20.1 g of compound (Bpre0-2).

[0480]

[0481] Precursor (Bpre0-2) (22 g, 42 mmol) and compound Z2 (15 g, 44 mmol) were dissolved in dichloromethane (60 g), and ultrapure water (60 g) was added. The mixture was allowed to react at room temperature for 30 minutes. After the reaction was completed, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (60 g). The organic phase was concentrated to dryness using a rotary evaporator to obtain compound (B0-2) (23 g, yield = 79%).

[0482]

[0483] The resulting compound (B0-2) was subjected to NMR measurement, and its structure was identified from the following analytical results. １H-NMR (DMSO, 400MHz): δ (ppm) = 2.11-2.37 (m, CH2, 2H), 2.81 (m, CH, 1H), 3.8 1 (m, CH, 1H), 4.44 (m, CH, 1H), 1.19-7.31 (m, CH, 8H), 7.77-7.98 (m, Ph, 11H)

[0484] <Preparation of Resist Composition> (Examples 7 to 9, Reference Examples 2 to 4) Resist compositions for each example were prepared by mixing and dissolving the components shown in Table 3. The resist composition for each example was adjusted so that the solids concentration was 21% by mass.

[0485]

[0486] In Table 3, the abbreviations have the following meanings: The numbers in brackets [ ] are the blend amounts (parts by mass).

[0487] (A1)-1: A polymer compound represented by the following formula (A1-1): The weight average molecular weight (Mw) calculated in terms of standard polystyrene as determined by GPC measurement is 10,000, and the molecular weight dispersity (Mw / Mn) is 2.3. １３ The copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 64 / 24 / 12.

[0488]

[0489] (B0)-1, (B0)-2: Acid generators comprising the above compounds (B0-1) and (B0-2). (B1)-1: Acid generator comprising the following compound (B1-1).

[0490]

[0491] (D1)-1: Triisopropanolamine. (E)-1: Phenylphosphonic acid.

[0492] (G0)-1: The above surfactant (G0-1) (G0)-3: The above silicone surfactant (G0-3) (G2)-1: Fluorine-based surfactant (trade name: R-40, manufactured by DIC Corporation); a surfactant corresponding to PFAS (G2)-2: Fluorine-based surfactant (trade name: PF656, manufactured by OMNOVA); a surfactant corresponding to PFAS

[0493] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether=20 / 80 (mass ratio).

[0494] <Formation of Resist Pattern> Step (i): Each resist composition of the example was applied using a spinner onto a 6-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then prebaked (PAB) on a hot plate at 100°C for 60 seconds, followed by drying to form a resist film with a thickness of 1.7 μm. Step (ii): Next, using a KrF exposure system NSR-S205C [manufactured by Nikon Corporation; NA (numerical aperture) = 0.6, Sigma = 0.5], the resist film was selectively irradiated with a KrF excimer laser (248 nm) through a photomask (binary mask). This was followed by PEB treatment at 100°C for 60 seconds. Step (iii): Next, alkaline development was performed for 60 seconds using a 2.38% by mass aqueous solution of TMAH (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., followed by rinsing with pure water for 30 seconds and then shaking and drying. As a result, in each example, a 1:1 line and space (LS) pattern with a line width of 400 nm and a pitch of 800 nm was formed.

[0495] [Evaluation of LS Pattern Shape] The shape of the LS pattern formed by the <Formation of Resist Pattern> above was observed using a cross-sectional SEM (scanning electron microscope, accelerating voltage 800V, product name: SU-8000, manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The results are shown in Table 4 as "pattern shape". (Evaluation Criteria) A: The LS pattern is rectangular. B: The LS pattern is not rectangular.

[0496] With respect to the components of the resist composition of each example, the component corresponding to PFAS is shown in Table 4 as "PFAS".

[0497]

[0498] As shown in Table 4, it was confirmed that in Examples 7 to 9, similar to Reference Examples 2 to 4, LS patterns with high rectangularity were obtained.

[0499] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims.

Claims

A resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, a resin component (A1) whose solubility in a developer changes under the action of an acid; an acid generator component (B) that generates an acid upon exposure to light; A surfactant (G01), The surfactant (G01) is a first resin solution prepared by mixing a solution of the resin (P1) represented by the following formula (P-1) dissolved in propylene glycol monomethyl ether to a concentration of 20% by mass with a solution of the surfactant (G01) dissolved in propylene glycol monomethyl ether acetate to a concentration of 1% by mass, wherein a first water contact angle with respect to a first resin film formed using the first resin solution containing 0.08 parts by mass of the surfactant (G01) relative to 100 parts by mass of the resin (P1) is larger by 8 degrees or more than a second water contact angle with respect to a second resin film formed using a second resin solution prepared by dissolving the resin (P1) in propylene glycol monomethyl ether to a concentration of 20% by mass: the acid generator component (B) and the surfactant (G01) do not contain a compound having a trifluoromethyl group (excluding the case where the structure is represented by the following general formula (np1)) and a compound having a difluoromethylene group (excluding the case where the structure is represented by the following general formula (np2) or (np3)), Resist composition. [In the formula, Mw represents the weight average molecular weight, and Mn represents the number average molecular weight.] [In the formula, X １ Ha-OR １ , -N(R ２ ) R １ or -N(R １ ) ２ represents. ２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ３ , -SR ３ , or -NR ３ R ４ represents. ３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR １ , -SR １ , -N(R ２ ) R １ or -N(R １ ) ２ Represents R １ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ２ , R ３ , and R ４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent.

2. The resist composition according to claim 1, wherein the surfactant (G01) is a silicon-based surfactant. 　 A resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, a resin component (A1) whose solubility in a developer changes under the action of an acid; an acid generator component (B) that generates an acid upon exposure to light; A surfactant (G02), The surfactant (G02) is a surfactant containing a structure represented by the following general formula (g0-1), (g0-2), or (g0-3): The acid generator component (B) and the surfactant (G02) do not contain a compound having a trifluoromethyl group (excluding the case where the trifluoromethyl group is a group represented by the following general formula (np1)) or a compound having a difluoromethylene group (excluding the case where the difluoromethylene group is a group represented by the following general formula (np2) or (np3)), Resist composition. [wherein, Rf ０１ represents a fluorinated alkyl group having one carbon atom. ０１ Ha-OR ０１ or -N(R ０２ ) R ０１ Rf ０２ represents a fluorinated alkylene group having 1 carbon atom. ０２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ０３ , -SR ０３ , or -NR ０３ R ０４ represents. ０３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR ０１ , -SR ０１ , or -N(R ０２ ) R ０１ Represents R ０１ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ０２ , R ０３ , and R ０４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent. [In the formula, X １ Ha-OR １ , -N(R ２ ) R １ or -N(R １ ) ２ represents. ２ represents a methyl group, a monovalent aromatic hydrocarbon group which may have a substituent, -OR ３ , -SR ３ , or -NR ３ R ４ represents. ３ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, a carbonyl group, -OR １ , -SR １ , -N(R ２ ) R １ or -N(R １ ) ２ Represents R １ represents a methylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a carbonyl group. ２ , R ３ , and R ４ each independently represents a hydrogen atom, a methyl group, or a monovalent aromatic hydrocarbon group which may have a substituent. The surfactant (G02) is a first resin solution prepared by mixing a solution of the resin (P1) represented by the following formula (P-1) dissolved in propylene glycol monomethyl ether to a concentration of 20% by mass with a solution of the surfactant (G02) dissolved in propylene glycol monomethyl ether acetate to a concentration of 1% by mass, wherein the first resin film formed using the first resin solution containing 0.08 parts by mass of the surfactant (G02) relative to 100 parts by mass of the resin (P1) has a first water contact angle that is 8 degrees or more larger than the second water contact angle with a second resin film formed using a second resin solution prepared by dissolving the resin (P1) in propylene glycol monomethyl ether to a concentration of 20% by mass: The resist composition according to claim 3 . The acid generator component (B) contains a compound (B0) represented by the following general formula (b0): The resist composition according to claim 1 or 3. [In the formula, Ar represents an aromatic ring. ０ represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ０ is -C(=O)-O-, -O-C(=O)- or -O-S(=O) ２ represents a divalent linking group containing -. ０ represents a cyclic group. ０ represents an organic group. n01 is an integer of 1 or more as long as the valence allows. n02 is an integer of 0 or more as long as the valence allows. ０ -Yb ０ is -O-C(=O)-Yb ０ If Yb ０ is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. ０ may be the same or different. When n02 is 2 or more, a plurality of Rb ０ may be the same or different, m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation.

6. The resist composition according to claim 5, wherein the compound (B0) is a compound represented by the following general formula (b0-1): [wherein, Rf ０１ represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ０１ is -C(=O)-O-, -O-C(=O)- or -O-S(=O) ２ represents a divalent linking group containing -. ０１ represents a cyclic group. ０１ represents an organic group, n011 is an integer of 1 or more, n021 is an integer of 0 or more, and n011 + n022 ≦ 4. ０１ -Yb ０１ is -O-C(=O)-Yb ０１ If Yb ０１ is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. ０１ may be the same or different. When n021 is 2 or more, a plurality of Rb ０１ may be the same or different, m is an integer of 1 or more, and M ｍ＋ represents an m-valent cation. A method for forming a resist pattern, comprising: a step of forming a resist film on a support using the resist composition according to any one of claims 1 to 4; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

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